WO2009118665A2 - Thermoplastic starch for use in melt-extruded substrates - Google Patents

Thermoplastic starch for use in melt-extruded substrates Download PDF

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Publication number
WO2009118665A2
WO2009118665A2 PCT/IB2009/050478 IB2009050478W WO2009118665A2 WO 2009118665 A2 WO2009118665 A2 WO 2009118665A2 IB 2009050478 W IB2009050478 W IB 2009050478W WO 2009118665 A2 WO2009118665 A2 WO 2009118665A2
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WO
WIPO (PCT)
Prior art keywords
starch
melt
substrate
acid
foregoing
Prior art date
Application number
PCT/IB2009/050478
Other languages
French (fr)
Other versions
WO2009118665A3 (en
Inventor
Bo Shi
James H. Wang
Original Assignee
Kimberly-Clark Worldwide, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kimberly-Clark Worldwide, Inc. filed Critical Kimberly-Clark Worldwide, Inc.
Publication of WO2009118665A2 publication Critical patent/WO2009118665A2/en
Publication of WO2009118665A3 publication Critical patent/WO2009118665A3/en

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Definitions

  • thermoplastic starches either alone or in combination with other polymers, are often used in the manufacture of articles for which water or biological degradation are considered important.
  • the thermoplastic starch is typically formed by plasticizing a native starch with a functional plasticizer or mixture of plasticizers, such as polyfunctional alcohols (e.g., ethylene glycol, propylene glycol, or glycerol).
  • a functional plasticizer or mixture of plasticizers such as polyfunctional alcohols (e.g., ethylene glycol, propylene glycol, or glycerol).
  • polyfunctional alcohols e.g., ethylene glycol, propylene glycol, or glycerol
  • melt-extruded substrates e.g., nonwoven webs, films, etc.
  • thermoplastic starches typically require polymers of appropriate molecular weights and suitable melt viscosity for processing. It is often difficult, however, to achieve both mechanical strength and water/biological degradation from such polymers. As such, a need currently exists for a thermoplastic starch that exhibits good mechanical properties and is capable of water and/or biological degradation.
  • a melt- extruded substrate that comprises a thermoplastic starch formed from about 30 wt. % to about 95 wt.% of at least one starch, from about 1 wt.% to about 35 wt.% of at least one plasticizer, and from about 1 wt.% to about 35 wt.% of at least one weak organic acid.
  • the thermoplastic starch has a weight average molecular weight of from about 1 ,000,000 to about 5,000,000, polydispersity index of from about 0.5 to about 20, and apparent meit viscosity of from about 50 to about 800 Pascal-seconds, determined at a temperature of 150 0 C and a shear rate of 100 sec "1 .
  • a method for forming a substrate comprises melt blending a composition comprising from about 30 wt.% to about 95 wt.% of at least one starch, from about 1 wt.% to about 35 wt.% of at least one plasticizer, and from about 1 wt.% to about 35 wt.% of at least one weak organic acid to form a thermoplastic starch.
  • the thermoplastic starch has a weight average molecular weight of from about 1 ,000,000 to about 5,000,000, polydispersity index of from about 0.5 to about 20, and apparent melt viscosity of from about 50 to about 800 Pascal-seconds, determined at a temperature of 150 0 C and a shear rate of 100 sec "1 .
  • the thermoplastic starch is extruded onto a surface to form a substrate. Other features and aspects of the present invention are discussed in greater detail below.
  • Fig. 1 is a schematic illustration of one embodiment of a method for forming a melt-extruded substrate in accordance with the present invention
  • Fig. 2 is a graphical representation of the apparent melt viscosity (Pa-s) of the thermoplastic starches of Examples 1-4 versus shear rate (s "1 );
  • Fig. 3 is a graphical representation of the apparent melt viscosity (Pa-s) of the thermoplastic starches of Examples 5-6 versus shear rate (s "1 );
  • Fig. 4 is a graphical representation of the apparent melt viscosity (Pa-s) of the thermoplastic starches of Examples 7-8 versus shear rate (s "1 ); and Fig. 5 is a top view of an absorbent article that may be formed in accordance with one embodiment of the present invention. Repeat use of references characters in the present specification and drawings is intended to represent same or analogous features or elements of the invention.
  • nonwoven web generally refers to a web having a structure of individual fibers or threads which are interlaid, but not in an identifiable manner as in a knitted fabric.
  • suitable nonwoven fabrics or webs include, but are not limited to, meltblown webs, spunbond webs, bonded carded webs, airlaid webs, coform webs, hydraulically entangled webs, and so forth.
  • meltblown web generally refers to a nonwoven web that is formed by a process in which a molten thermoplastic material is extruded through a plurality of fine, usually circular, die capillaries as molten fibers into converging high velocity gas (e.g., air) streams that attenuate the fibers of molten thermoplastic material to reduce their diameter, which may be to microfiber diameter. Thereafter, the meltblown fibers are carried by the high velocity gas stream and are deposited on a collecting surface to form a web of randomly dispersed meltblown fibers.
  • high velocity gas e.g., air
  • meltblown fibers may be microfibers that are substantially continuous or discontinuous, generally smaller than 10 micrometers in diameter, and generally tacky when deposited onto a collecting surface.
  • spunbond web generally refers to a web containing small diameter substantially continuous fibers.
  • the fibers are formed by extruding a molten thermoplastic material from a plurality of fine, usually circular, capillaries of a spinnerette with the diameter of the extruded fibers then being rapidly reduced as by, for example, eductive drawing and/or other well-known spunbonding mechanisms.
  • the production of spunbond webs is described and illustrated, for example, in U.S. Patent Nos. 4,340,563 to Appel, et al.. 3,692,618 to Dorschner, et al..
  • Spunbond fibers are generally not tacky when they are deposited onto a collecting surface. Spunbond fibers may sometimes have diameters less than about 40 micrometers, and are often between about 5 to about 20 micrometers.
  • the present invention is directed to a melt-extruded substrate (e.g., film, nonwoven web, etc.) that contains a thermoplastic starch formed from a starch and plasticizer.
  • a thermoplastic starch formed from a starch and plasticizer.
  • the starch and plasticizer are melt blended together in the presence of a weak organic acid (e.g., lactic acid, formic acid, acetic acid, etc.).
  • the starch may be hydrolyzed in a highly efficient manner to form compositions having a comparably lower weight average molecular weight, polydispersity index, and viscosity, which are particularly suitable for use in the formation of melt-extruded substrates.
  • certain parameters of the melt blending process e.g., extrusion temperature, content of the components, etc.
  • the present inventors have discovered that the starch may be hydrolyzed in a highly efficient manner to form compositions having a comparably lower weight average molecular weight, polydispersity index, and viscosity, which are particularly suitable for use in the formation of melt-extruded substrates.
  • various embodiments of the present invention will now be described in more detail.
  • Starch is a natural polymer composed of amylose and amylopectin.
  • Amylose is essentially a linear polymer having a molecular weight in the range of 100,000-500,000, whereas amylopectin is a highly branched polymer having a molecular weight of up to several million.
  • typical sources includes seeds of cereal grains, such as corn, waxy corn, wheat, sorghum, rice, and waxy rice; tubers, such as potatoes; roots, such as tapioca (i.e., cassava and manioc), sweet potato, and arrowroot; and the pith of the sago paim.
  • native (unmodified) and/or modified starches may be employed in the present invention.
  • Modified starches may be employed that have been chemically modified by typical processes known in the art (e.g., esterification, etherification, oxidation, enzymatic hydrolysis, etc.).
  • Starch ethers and/or esters may be particularly desirable, such as hydroxyalkyl starches, carboxymethyl starches, etc.
  • the hydroxyalkyl group of hydroxylalkyl starches may contain, for instance, 2 to 10 carbon atoms, in some embodiments from 2 to 6 carbon atoms, and in some embodiments, from 2 to 4 carbon atoms.
  • Representative hydroxyalkyl starches such as hydroxyethyl starch, hydroxypropyl starch, hydroxybutyl starch, and derivatives thereof.
  • Starch esters may be prepared using a wide variety of anhydrides (e.g., acetic, propionic, butyric, and so forth), organic acids, acid chlorides, or other esterification reagents.
  • the degree of esterification may vary as desired, such as from 1 to 3 ester groups per glucosidic unit of the starch.
  • the starch may contain different percentages of amylose and amylopectin, different size starch granules and different polymeric weights for amylose and amylopectin.
  • High amylose starches contain greater than about 50% by weight amylose and low amylose starches contain less than about 50% by weight amylose.
  • low amylose starches having an amylose content of from about 10% to about 40% by weight, and in some embodiments, from about 15% to about 35% by weight are particularly suitable for use in the present invention. Examples of such low amylose starches include corn starch and potato starch, both of which have an amylose content of approximately 20% by weight.
  • Such low amylose starches typically have a number average molecular weight (“M n ”) ranging from about 50,000 to about 1 ,000,000 grams per mole, in some embodiments from about 75,000 to about 800,000 grams per mole, and in some embodiments, from about 100,000 to about 600,000 grams per mole, as well as a weight average molecular weight (“M w ”) ranging from about 5,000,000 to about 25,000,000 grams per mole, in some embodiments from about 5,500,000 to about 15,000,000 grams per mole, and in some embodiments, from about 6,000,000 to about 12,000,000 grams per mole.
  • M w number average molecular weight
  • the "polydispersity index" is also relatively high.
  • the poiydispersity index may range from about 20 to about 100.
  • the weight and number average molecular weights may be determined by methods known to those skilled in the art.
  • a plasticizer is also employed in the thermoplastic starch to help render the starch melt-processible. Starches, for instance, normally exist in the form of granules that have a coating or outer membrane that encapsulates the more water-soluble amylose and amylopectin chains within the interior of the granule. When heated, plasticizers may soften and penetrate the outer membrane and cause the inner starch chains to absorb water and swell.
  • Suitable plasticizers may include, for instance, polyhydric alcohol plasticizers, such as sugars (e.g., glucose, sucrose, fructose, raffinose, maltodextrose, galactose, xylose, maltose, lactose, mannose, and erythrose), sugar alcohols (e.g., erythritol, xylitol, malitol, mannitol, and sorbitol), polyols (e.g., ethylene glycol, glycerol, propylene glycol, dipropylene glycol, butylene glycol, and hexane triol), etc.
  • polyhydric alcohol plasticizers such as sugars (e.g., glucose, sucrose, fructose, raffinose, maltodextrose, galactose, xylose, maltose, lactose, mannose, and erythrose), sugar alcohols (e.g
  • Suitable are hydrogen bond forming organic compounds which do not have hydroxy! group including urea and urea derivatives; anhydrides of sugar alcohols such as sorbitan; animal proteins such as gelatin; vegetable proteins such as sunflower protein, soybean proteins, cotton seed proteins; and mixtures thereof.
  • Other suitable plasticizers may include phthalate esters, dimethyl and diethylsuccinate and related esters, glycerol triacetate, glycerol mono and diacetates, glycerol mono, di, and tripropionates, butanoates, stearates, lactic acid esters, citric acid esters, adipic acid esters, stearic acid esters, oleic acid esters, and other acid esters.
  • Aliphatic acids may also be used, such as copolymers of ethylene and acrylic acid, polyethylene grafted with maleic acid, polybutadiene-co-acryiic acid, poiybutadiene-co-maieic acid, poiypropylene-co- acrylic acid, polypropylene-co-maleic acid, and other hydrocarbon based acids.
  • a low molecular weight plasticizer is preferred, such as less than about 20,000 g/mol, preferably less than about 5,000 g/mol and more preferably less than about 1 ,000 g/mol.
  • the starch is hydrolyzed into lower molecular weight carbohydrates in the presence of a weak organic acid, which acts as a chain scission catalyst by splitting primarily the ⁇ -1 ,4 glycosidic bonds in the starch macromolecule.
  • organic acids that may be used in the present invention include organophosphoric acids; organosulfuric acids; organoboric acids; carboxylic acids, such as acrylic acid, methacrylic acid, malonic acid, succinic acid, salicylic acid, sulfosalicylic acid, adipic acid, maleic acid, malic acid, oleic acid, gallic acid, tartaric acid, citric acid, formic acid, acetic acid, glycolic acid, oxalic acid, tartaric acid (e.g., dextotartaric acid, mesotartaric acid, etc.), propionic acid, phthalic acid, isophthalic acid, glutaric acid, gluconic acid, lactic acid, aspartic acid
  • Anhydrides e.g., maleic anhydride
  • salts of organic acids may also be employed.
  • Particularly suitable organic acids for use in the present invention are those having an acid dissociation constant (pK a ) ranging from 0 to about 8, in some embodiments from about 1 to about 5, and in some embodiments, from about 2 to about 4, determined at 25 0 C, such as lactic acid (pK a of 3.85), formic acid (pK a of 3.75), and acetic acid (pK a of 4.76).
  • the relative amount of starch, weak organic acid, and plasticizer employed in the thermoplastic starch may vary depending on a variety of factors, such as the desired molecular weight, the type of starch, the affinity of the plasticizer for the starch, etc.
  • the native starch constitutes from about 30 wt.% to about 95 wt.%, in some embodiments from about 40 wt.% to about 90 wt.%, and in some embodiments, from about 50 wt.% to about 85 wt.% of the thermoplastic starch.
  • the weak organic acid may constitute from about 1 wt.% to about 35 wt.%, in some embodiments from about 2 wt.% to about 30 wt.%, and in some embodiments, from about 5 wt.% to about 25 wt.% of the thermoplastic starch.
  • the piasticizer typically constitutes from about i wt.% to about 35 wt.%, in some embodiments from about 2 wt.% to about 30 wt.%, and in some embodiments, from about 5 wt.% to about 25 wt.% of the thermoplastic composition.
  • the weight of starch referenced herein includes any bound water that naturally occurs in the starch before mixing it with other components to form the thermoplastic starch.
  • Starches typically have a bound water content of about 5% to 16% by weight of the starch.
  • other additives may also be employed in the thermoplastic starch to facilitate its use in various types of substrates.
  • Dispersion aids for instance, may be employed to help create a uniform dispersion of the starch/plasticizer mixture and retard or prevent separation of the thermoplastic starch into constituent phases. Likewise, the dispersion aids may also improve the water dispersibility of the substrate.
  • the dispersion aid(s) typically constitute from about 0.01 wt.% to about 10 wt.%, in some embodiments from about 0.1 wt.% to about 5 wt.%, and in some embodiments, from about 0.5 wt.% to about 4 wt.% of the thermoplastic starch.
  • HLB hydrophilic/lipophilic balance
  • the HLB index is well known in the art and is a scale that measures the balance between the hydrophilic and lipophilic solution tendencies of a compound.
  • the HLB scale ranges from 1 to approximately 50, with the lower numbers representing highly lipophilic tendencies and the higher numbers representing highly hydrophilic tendencies.
  • the HLB value of the surfactants is from about 1 to about 20, in some embodiments from about 1 to about 15 and in some embodiments, from about 2 to about 10.
  • two or more surfactants may be employed that have HLB values either below or above the desired value, but together have an average HLB value within the desired range.
  • One particularly suitable class of surfactants for use in the present invention are nonionic surfactants, which typically have a hydrophobic base (e.g., long chain alkyl group or an alkylated aryl group) and a hydrophilic chain (e.g., chain containing ethoxy and/or propoxy moieties).
  • nonionic surfactants include, but are not limited to, ethoxylated alkylphenols, ethoxylated and propoxylated fatty alcohols, polyethylene glycol ethers of methyl glucose, polyethylene glycol ethers of sorbitol, ethylene oxide- propylene oxide block copolymers, ethoxylated esters of fatty (Cs -Ci 8 ) acids, condensation products of ethylene oxide with long chain amines or amides, condensation products of ethylene oxide with alcohols, fatty acid esters, monoglyceride or diglycerides of long chain alcohols, and mixtures thereof.
  • the nonionic surfactant may be a fatty acid ester, such as a sucrose fatty acid ester, glycerol fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, pentaerythritol fatty acid ester, sorbitol fatty acid ester, and so forth.
  • the fatty acid used to form such esters may be saturated or unsaturated, substituted or unsubstituted, and may contain from 6 to 22 carbon atoms, in some embodiments from 8 to 18 carbon atoms, and in some embodiments, from 12 to 14 carbon atoms.
  • mono- and di-glycerides of fatty acids may be employed in the present invention. II. Melt Blending
  • thermoplastic starch of the present invention is formed by melt blending the components together in an extruder.
  • the mechanical shear and heat provided by the extruder facilitates the hydrolysis of the starch and allows the components to be blended together in a highly efficient manner.
  • Batch and/or continuous melt blending techniques may be employed in the present invention. For example, a mixer/kneader, Banbury mixer, Farrel continuous mixer, single-screw extruder, twin-screw extruder, roll mill, etc., may be utilized.
  • One particularly suitable melt- blending device is a co-rotating, twin-screw extruder (e.g., USALAB twin-screw extruder available from Thermo Electron Corporation of Stone, England or an extruder available from Werner-Pfreiderer from Ramsey, New Jersey).
  • extruders may include feeding and venting ports and provide high intensity distributive and dispersive mixing.
  • a starch may be initially fed to a feeding port of the twin-screw extruder. Thereafter, a plasticizer and weak organic acid may be injected into the starch.
  • the components may be simultaneously fed to the feed throat of the extruder or separately at a different point along its length.
  • melt blending typically occurs at a temperature of from about 4O 0 C to about 16O 0 C, in some embodiments, from about 5O 0 C to about 150 0 C, and in some embodiments, from about 60 0 C to about 140 0 C.
  • the apparent shear rate during melt blending may range from about 100 seconds "1 to about 10,000 seconds "1 , in some embodiments from about 500 seconds "1 to about 5000 seconds "1 , and in some embodiments, from about 800 seconds "1 to about 1200 seconds "1 .
  • the apparent shear rate is equal to 4Q/ ⁇ R 3 , where Q is the volumetric flow rate ("m 3 /s") of the polymer melt and R is the radius ("m") of the capillary (e.g., extruder die) through which the melted polymer flows.
  • Q is the volumetric flow rate ("m 3 /s") of the polymer melt
  • R is the radius ("m") of the capillary (e.g., extruder die) through which the melted polymer flows.
  • the thermoplastic starch may have a weight average molecular weight ranging from about 1 ,000,000 to about 5,000,000 grams per mole, in some embodiments from about 1 ,500,000 to about 4,000,000 grams per mole, and in some embodiments, from about 2,000,000 to about 3,500,000 grams per mole.
  • the thermoplastic starch may have a number average molecular weight ranging from about 50,000 to about 1 ,000,000 grams per mole, in some embodiments from about 75,000 to about 800,000 grams per mole, and in some embodiments, from about 100,000 to about 600,000 grams per mole.
  • the polydispersity index may be from about 0.5 to about 20, in some embodiments from about 1 to about 15, and in some embodiments, from about 2 to about 10.
  • the thermoplastic starch may also have an apparent melt viscosity of from about 50 to about 800 Pascal seconds (Pa-s), in some embodiments from about 100 to about 700 Pa-s, and in some embodiments, from about 200 to about 600 Pa-s, as determined at a temperature of 150 0 C and a shear rate of 100 sec "1 .
  • the melt flow index of the thermoplastic starch may range from about 0.1 to about 30 grams per 10 minutes, in some embodiments from about 0.5 to about 10 grams per 10 minutes, and in some embodiments, from about 1 to about 5 grams per 10 minutes.
  • the melt flow index is the weight of a polymer (in grams) that may be forced through an extrusion rheometer orifice (0.0825-inch diameter) when subjected to a load of 2160 grams in 10 minutes at a certain temperature (e.g., 170 0 C), measured in accordance with ASTM Test Method D1238-E.
  • a certain temperature e.g. 170 0 C
  • the meit flow index of the thermoplastic starch will ultimately depend upon the selected forming process. For example, when extruded as a cast film, higher melt flow index polymers are typically desired, such as about 4 grams per 10 minutes or more, in some embodiments, from about 5 to about 12 grams per 10 minutes, and in some embodiments, from about 7 to about 9 grams per 10 minutes.
  • melt flow index polymers are typically desired, such as less than about 12 grams per 10 minutes or less, in some embodiments from about 1 to about 7 grams per 10 minutes, and in some embodiments, from about 2 to about 5 grams per 10 minutes.
  • thermoplastic starch of the present invention may be incorporated into any known melt-extruded substrate, such as films, nonwoven webs (e.g., spunbond webs, meltblown webs, and so forth), etc.
  • the substrate may contain a single layer or multiple layers and may also contain additional materials such that it is considered a composite.
  • the thermoplastic starch may constitute at least about 50 wt.%, in some embodiments from about 60 wt.% to about 99 wt.%, and in some embodiments, from about 75 to about 95 wt.% of the polymer content of the substrate.
  • other polymer(s) may be employed to impart certain properties to the substrate (e.g., strength, solubility, etc.).
  • the thermoplastic starch may constitute from about 10 wt.% to about 80 wt.%, in some embodiments from about 20 wt.% to about 70 wt.%, and in some embodiments, from about 30 to about 60 wt.% of the polymer content of the substrate, while such additional polymer(s) typically constitute from about 10 wt.% to about 80 wt.%, in some embodiments from about 20 wt.% to about 70 wt.%, and in some embodiments, from about 30 to about 60 wt.% of the polymer content of the substrate.
  • the substrate may include one or more bioldegradable polyesters.
  • biodegradable generally refers to a material that degrades from the action of naturally occurring microorganisms, such as bacteria, fungi, and algae; environmental heat; moisture; or other environmental factors, such as determined according to ASTM Test Method 5338.92.
  • the biodegradable polyesters employed in the present invention typically have a relatively low glass transition temperature (“T 9 ”) to reduce stiffness of the substrate and improve the processability of the polymers.
  • T 9 glass transition temperature
  • the T 9 may be about 25°C or less, in some embodiments about 0 0 C or less, and in some embodiments, about -1 O 0 C or less.
  • the melting point of the biodegradable polyesters is also relatively low to improve the rate of biodegradation.
  • the melting point is typically from about 50 0 C to about 18O 0 C, in some embodiments from about 80 0 C to about 16O 0 C, and in some embodiments, from about 100 0 C to about 14O 0 C.
  • the melting temperature and glass transition temperature may be determined using differential scanning calorimetry ("DSC") in accordance with ASTM D-3417 as is well known in the art. Such tests may be employed using a DSC Q100 Differential Scanning Calorimeter (outfitted with a liquid nitrogen cooling accessory) and with a THERMAL ADVANTAGE (release 4.6.6) analysis software program, which are available from T.A.
  • the biodegradable polyesters may also have a number average molecular weight ("M n ”) ranging from about 40,000 to about 120,000 grams per mole, in some embodiments from about 50,000 to about 100,000 grams per mole, and in some embodiments, from about 60,000 to about 85,000 grams per mole.
  • M n number average molecular weight
  • the polyesters may also have a weight average molecular weight (“M w ”) ranging from about 70,000 to about 300,000 grams per mole, in some embodiments from about 80,000 to about 200,000 grams per mole, and in some embodiments, from about 100,000 to about 150,000 grams per mole.
  • the ratio of the weight average molecular weight to the number average molecular weight (“M w /M n "), i.e., the "polydispersity index" is also relatively low.
  • the polydispersity index typically ranges from about 1.0 to about 4.0, in some embodiments from about 1.2 to about 3.0, and in some embodiments, from about 1.4 to about 2.0.
  • suitable biodegradable polyesters include aliphatic polyesters, such as polycaprolactone, polyesteramides, modified polyethylene terephthalate, polylactic acid (PLA) and its copolymers, terpolymers based on polylactic acid, polyglycolic acid, polyalkylene carbonates (such as polyethylene carbonate), polyhydroxyalkanoates (PHA), poly-3-hydroxybutyrate (PHB), poly-Shi yd roxy valerate (PHV), poiy-3-hydroxybutyrate-co-4-hydroybutyrate, poly-3- hydroxybutyrate-co-3-hydroxyvalerate copolymers (PHBV), poly-3- hydroxybutyrate-co-3-hydroxyhexanoate, ⁇ oly-3-hydroxybutyrate-co-3- hydroxyoctanoate, poly-S-hydroxybutyrate-co-S-hydroxydecanoate, poly-3- hydroxybutyrate-co-3-hydroxyoctadecanoate, and succinate-based
  • the biodegradable polyester is an aliphatic-aromatic copolyester (e.g., block, random, graft, etc.).
  • the aliphatic-aromatic copolyester may be synthesized using any known technique, such as through the condensation polymerization of a polyol in conjunction with aliphatic and aromatic dicarboxylic acids or anhydrides thereof.
  • the polyols may be substituted or unsubstituted, linear or branched, polyols selected from polyols containing 2 to about 12 carbon atoms and polyalkylene ether glycols containing 2 to 8 carbon atoms.
  • polyols examples include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, 2,2-dimethyl-1 ,3-propanediol, 1 ,2- butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,2-pentanediol, 1 ,5-pentanediol, 1 ,6- hexanediol, polyethylene glycol, diethylene glycol, 2,2,4-trimethyl-1 ,6-hexanediol, thiodiethanol, 1 ,3-cyclohexanedimethanol, 1 ,4-cyclohexanedimethanol, 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol, cyclopentane
  • Preferred polyols include 1 ,4-butanediol; 1 ,3-propanediol; ethylene glycol; 1 ,6-hexanediol; diethylene glycol; and 1 ,4-cyclohexanedimethanol.
  • Representative aliphatic dicarboxylic acids that may be used include substituted or unsubstituted, linear or branched, non-aromatic dicarboxylic acids selected from aliphatic dicarboxylic acids containing 1 to about 10 carbon atoms, and derivatives thereof.
  • Non-limiting examples of aliphatic dicarboxylic acids include malonic, malic, succinic, oxalic, glutaric, adipic, pimelic, azelaic, sebacic, fumaric, 2,2-dimethyl glutaric, suberic, 1 ,3-cyclopentanedicarboxylic, 1 ,4- cyclohexanedicarboxylic, 1 ,3-cyclohexanedicarboxylic, diglycolic, itaconic, maleic, and 2,5-norbomanedicarboxylic.
  • aromatic dicarboxylic acids that may be used include substituted and unsubstituted, linear or branched, aromatic dicarboxylic acids selected from aromatic dicarboxylic acids containing 8 or more carbon atoms, and derivatives thereof.
  • aromatic dicarboxylic acids include terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, 2,6-napthalene dicarboxyiic acid, dimethyi-2,6- naphthalate, 2,7-naphthalenedicarboxylic acid, dimethyl-2,7-naphthalate, 3,4'- diphenyl ether dicarboxylic acid, dimethyl-3,4'diphenyl ether dicarboxylate, 4,4'- diphenyl ether dicarboxylic acid, dimethyl-4,4'-diphenyl ether dicarboxylate, 3,4'- diphenyl sulfide dicarboxylic acid, dimethyl-3,4'-
  • the polymerization may be catalyzed by a catalyst, such as a titanium- based catalyst (e.g., tetraisopropyltitanate, tetraisopropoxy titanium, dibutoxydiacetoacetoxy titanium, or tetrabutyltitanate).
  • a catalyst such as a titanium- based catalyst (e.g., tetraisopropyltitanate, tetraisopropoxy titanium, dibutoxydiacetoacetoxy titanium, or tetrabutyltitanate).
  • a diisocyanate chain extender may be reacted with the copolyester to increase its molecular weight.
  • Representative diisocyanates may include toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthylene-1 ,5- diisocyanate, xylylene diisocyanate, methylene diphenyl isocyanate ("MDI”), hexamethylene diisocyanate (“HMDI”), isophorone diisocyanate and methylenebis(2-isocyanatocyclohexane).
  • MDI methylene diphenyl isocyanate
  • HMDI hexamethylene diisocyanate
  • isophorone diisocyanate and methylenebis(2-isocyanatocyclohexane
  • Trifunctional isocyanate compounds may also be employed that contain isocyanurate and/or biurea groups with a functionality of not less than three, or to replace the diisocyanate compounds partially by tri-or polyisocyanates.
  • the preferred diisocyanate is hexamethylene diisocyanate.
  • the amount of the chain extender employed is typically from about 0.3 to about 3.5 wt.%, in some embodiments, from about 0.5 to about 2.5 wt.% based on the total weight percent of the polymer.
  • the copolyesters may either be a linear polymer or a long-chain branched polymer.
  • Long-chain branched polymers are generally prepared by using a low molecular weight branching agent, such as a polyol, polycarboxylic acid, hydroxy acid, and so forth.
  • a low molecular weight branching agent such as a polyol, polycarboxylic acid, hydroxy acid, and so forth.
  • Representative low molecular weight polyols that may be employed as branching agents include glycerol, trimethylolpropane, trimethyioiethane, polyethertriols, 1 ,2,4-butanetrioi, pentaerythritol, 1 ,2,6- hexanetriol, sorbitol, 1 ,1 ,4,4,-tetrakis (hydroxymethyl) cyclohexane, tris(2- hydroxyethyl) isocyanurate, and dipentaerythritol.
  • Representative higher molecular weight polyols (molecular weight of 400 to 3000) that may be used as branching agents include triols derived by condensing alkylene oxides having 2 to 3 carbons, such as ethylene oxide and propylene oxide with polyol initiators.
  • polycarboxylic acids that may be used as branching agents include hemimellitic acid, trimellitic (1 ,2,4-benzenetricarboxylic) acid and anhydride, trimesic (1 ,3,5-benzenetricarboxylic) acid, pyromellitic acid and anhydride, benzenetetracarboxylic acid, benzophenone tetracarboxylic acid, 1 ,1 ,2,2-ethane- tetracarboxylic acid, 1 ,1 ,2-ethanetricarboxylic acid, 1 ,3,5-pentanetricarboxylic acid, and 1 ,2,3,4-cyclopentanetetracarboxylic acid.
  • hydroxy acids that may be used as branching agents include malic acid, citric acid, tartaric acid, 3- hydroxyglutaric acid, mucic acid, trihydroxyglutaric acid, 4-carboxyphthalic anhydride, hydroxyisophthalic acid, and 4-(beta-hydroxyethyl)phthalic acid.
  • Such hydroxy acids contain a combination of 3 or more hydroxyl and carboxyl groups.
  • Especially preferred branching agents include trimellitic acid, trimesic acid, pentaerythritol, trimethylol propane and 1 ,2,4-butanetriol.
  • the aromatic dicarboxylic acid monomer constituent may be present in the copolyester in an amount of from about 10 mole% to about 40 mole%, in some embodiments from about 15 mole% to about 35 mole%, and in some embodiments, from about 15 mole% to about 30 mole%.
  • the aliphatic dicarboxylic acid monomer constituent may likewise be present in the copolyester in an amount of from about 15 mole% to about 45 mole%, in some embodiments from about 20 mole% to about 40 mole%, and in some embodiments, from about 25 mole% to about 35 mole%.
  • the polyol monomer constituent may also be present in the aliphatic-aromatic copolyester in an amount of from about 30 mole% to about 65 mole%, in some embodiments from about 40 mole% to about 50 mole%, and in some embodiments, from about 45 mole% to about 55 mole%.
  • the aliphatic-aromatic copolyester may comprise the following structure: O— (CH 2 ) m — O— wherein, m is an integer from 2 to 10, in some embodiments from 2 to 4, and in one embodiment, 4; n is an integer from 0 to 18, in some embodiments from 2 to 4, and in one embodiment, 4; p is an integer from 2 to 10, in some embodiments from 2 to 4, and in one embodiment, 4; x is an integer greater than 1 ; and y is an integer greater than 1.
  • a copolyester is polybutylene adipate terephthalate, which is commercially available under the designation ECOFLEX® F BX 7011 from BASF Corp.
  • a suitable copolyester containing an aromatic terephtalic acid monomer constituent is available under the designation ENPOLTM 8060M from IRE Chemicals (South Korea).
  • ENPOLTM 8060M an aromatic terephtalic acid monomer constituent
  • Other suitable aliphatic-aromatic copolyesters may be described in U.S. Patent Nos. 5,292,783; 5,446,079; 5,559,171 ; 5,580,911 ; 5,599,858; 5,817,721 ; 5,900,322; and 6,258,924, which are incorporated herein in their entirety by reference thereto for all purposes.
  • the substrate may also include one or more water-soluble polymers.
  • Such polymers may be formed from monomers such as vinyl pyrrolidone, hydroxyethyl acrylate or methacrylate (e.g., 2-hydroxyethyl methacrylate), hydroxypropyl acrylate or methacrylate, acrylic or methacrylic acid, acrylic or methacrylic esters or vinyl pyridine, acrylamide, vinyl acetate, vinyl alcohol (hydrolyzed from vinyl acetate), ethylene oxide, derivatives thereof, and so forth.
  • Other examples of suitable monomers are described in U.S. Patent No.
  • the resulting polymers may be homopolymers or interpolymers (e.g., copolymer, terpolymer, etc.), and may be nonionic, anionic, cationic, or amphoteric.
  • the polymer may be of one type (i.e., homogeneous), or mixtures of different polymers may be used (i.e., heterogeneous).
  • the water-soluble polymer contains a repeating unit having a functional hydroxyl group, such as polyvinyl alcohol (“PVOH”), copolymers of polyvinyl alcohol (e.g., ethylene vinyl alcohol copolymers, methyl methacrylate vinyl alcohol copolymers, etc.), etc.
  • PVH polyvinyl alcohol
  • Vinyl alcohol polymers for instance, have at least two or more vinyl alcohol units in the molecule and may be a homopolymer of vinyl alcohol, or a copolymer containing other monomer units.
  • Vinyl alcohol homopolymers may be obtained by hydrolysis of a vinyl ester polymer, such as vinyl formate, vinyl acetate, vinyl propionate, etc.
  • Vinyl alcohol copolymers may be obtained by hydrolysis of a copolymer of a vinyl ester with an olefin having 2 to 30 carbon atoms, such as ethylene, propylene, 1- butene, etc.; an unsaturated carboxylic acid having 3 to 30 carbon atoms, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, etc., or an ester, salt, anhydride or amide thereof; an unsaturated nitrile having 3 to 30 carbon atoms, such as acrylonitrile, methacrylonitrile, etc.; a vinyl ether having 3 to 30 carbon atoms, such as methyl vinyl ether, ethyl vinyl ether, etc.; and so forth.
  • the degree of hydrolysis may be selected to optimize solubility, etc., of the polymer.
  • the degree of hydrolysis may be from about 60 mole% to about 95 mole%, in some embodiments from about 80 mole% to about 90 mole%, and in some embodiments, from about 85 mole% to about 89 mole%.
  • suitable partially hydrolyzed polyvinyl alcohol polymers are available under the designation CELVOLTM 203, 205, 502, 504, 508, 513, 518, 523, 530, or 540 from Celanese Corp.
  • Other suitable partially hydrolyzed polyvinyl alcohol polymers are available under the designation ELVANOLTM 50-14, 50-26, 50-42, 51-03, 51-04, 51-05, 51-08, and 52-22 from DuPont.
  • additives may also be incorporated into the substrate of the present invention, such as dispersion aids, melt stabilizers, processing stabilizers, heat stabilizers, light stabilizers, antioxidants, heat aging stabilizers, whitening agents, antiblocking agents, bonding agents, lubricants, fillers, etc.
  • Dispersion aids such as described above, may be employed to help create a uniform dispersion of a thermoplastic starch and other polymers and retard or prevent separation into constituent phases.
  • the dispersion aids may also improve the water dispersibility of the substrate.
  • the dispersion aid(s) typically constitute from about 0.01 wt.% to about 15 wt.%, in some embodiments from about 0.1 wt.% to about 10 wt.%, and in some embodiments, from about 0.5 wt.% to about 5 wt.% of the substrate.
  • Fillers may aiso be employed in the substrate of the present invention.
  • Fillers are particulates or other forms of material that may be added to the substrate polymer extrusion blend and that will not chemically interfere with the extruded substrate, but which may be uniformly dispersed throughout the substrate.
  • Fillers may serve a variety of purposes, including enhancing opacity and/or breathability (i.e., vapor-permeable and substantially liquid-impermeable).
  • filled films may be made breathable by stretching, which causes the polymer to break away from the filler and create microporous passageways. Breathable microporous films are described, for example, in U.S. Patent Nos.
  • hindered phenols are commonly used as an antioxidant in the production of substrates.
  • Some suitable hindered phenols include those available from Ciba Specialty Chemicals under the trade name "Irganox®", such as Irganox® 1076, 1010, or E 201.
  • bonding agents may also be added to the substrate to facilitate bonding of the substrate to additional materials (e.g., nonwoven webs). Examples of such bonding agents include hydrogenated hydrocarbon resins. Other suitable bonding agents are described in U.S. Patent Nos. 4,789,699 to Kieffer et al. and 5,695,868 to
  • a film may be formed by blowing, casting, flat die extruding, etc., a compounded material as is known in the art.
  • the film may be formed by a blown process in which a gas (e.g., air) is used to expand a bubble of the extruded polymer blend through an annular die. The bubble is then collapsed and collected in flat film form.
  • a gas e.g., air
  • Processes for producing blown films are described, for instance, in U.S. Patent Nos. 3,354,506 to Ralev; 3,650,649 to Schippers; and 3,801 ,429 to Schrenk et al., as well as U.S.
  • the film is formed using a casting technique.
  • a method for forming a cast film is shown.
  • the raw materials may be supplied to a melt blending device, either separately or as a blend.
  • the thermoplastic starch may be formed in the manner described above as the film is cast.
  • the thermoplastic starch may be pre-formed and thereafter supplied to the melt blending device for formation of the film.
  • the compounded material (not shown) is supplied to an extrusion apparatus 80 and cast onto a casting roll 90 to form a single-layered precursor film 10a. If a multilayered film is to be produced, the multiple layers are co-extruded together onto the casting roll 90.
  • the casting roll 90 may optionally be provided with embossing elements to impart a pattern to the film.
  • the casting roll 90 is kept at temperature sufficient to solidify and quench the sheet 10a as it is formed, such as from about 20 to 60 0 C.
  • a vacuum box may be positioned adjacent to the casting roll 90 to help keep the precursor film 10a close to the surface of the roll 90.
  • air knives or electrostatic pinners may help force the precursor film 10a against the surface of the casting roll 90 as it moves around a spinning roll.
  • An air knife is a device known in the art that focuses a stream of air at a very high flow rate to pin the edges of the film.
  • the film 10a may then be optionally oriented in one or more directions to further improve film uniformity and reduce thickness. Orientation may also form micropores in a film containing a filler, thus providing breathability to the film.
  • the film may be immediately reheated to a temperature below the melting point of one or more polymers in the film, but high enough to enable the composition to be drawn or stretched.
  • the "softened” film is drawn by rolls rotating at different speeds of rotation such that the sheet is stretched to the desired draw ratio in the longitudinal direction (machine direction). This "uniaxially" oriented film may then be laminated to a fibrous web.
  • the uniaxially oriented film may also be oriented in the cross-machine direction to form a "biaxially oriented" film.
  • the film may be clamped at its lateral edges by chain clips and conveyed into a tenter oven. In the tenter oven, the film may be reheated and drawn in the cross-machine direction to the desired draw ratio by chain clips diverged in their forward travel.
  • a film- orientation unit 100 or machine direction orienter such as commercially available from Marshall and Willams, Co. of Buffalo, Rhode Island.
  • the MDO has a plurality of stretching rolls (such as from 5 to 8) which progressively stretch and thin the film in the machine direction, which is the direction of travel of the film through the process as shown in Fig. 1. While the MDO 100 is illustrated with eight rolls, it should be understood that the number of rolls may be higher or lower, depending on the level of stretch that is desired and the degrees of stretching between each roll.
  • the film may be stretched in either single or multiple discrete stretching operations. It should be noted that some of the rolls in an MDO apparatus may not be operating at progressively higher speeds. If desired, some of the rolls of the MDO 100 may act as preheat rolls. If present, these first few rolls heat the film 10a above room temperature (e.g., to 125 0 F). The progressively faster speeds of adjacent rolls in the MDO act to stretch the film 10a. The rate at which the stretch rolls rotate determines the amount of stretch in the film and final film weight.
  • the resulting film 10b may then be wound and stored on a take-up roll 60. While not shown here, various additional potential processing and/or finishing steps known in the art, such as slitting, treating, aperturing, printing graphics, or lamination of the film with other layers (e.g., nonwoven web materials), may be performed without departing from the spirit and scope of the invention.
  • the thickness of the resulting melt-extruded substrate may generally vary depending upon the desired use. Nevertheless, the substrate typically has a thickness of about 150 micrometers or less, in some embodiments from about 10 to about 100 micrometers, and in some embodiments, from about 5 to about 80 micrometers. Despite having such a small thickness, the substrate is nevertheless able to retain good dry mechanical properties during use.
  • One parameter that is indicative of the relative dry strength is the ultimate tensile strength, which is equal to the peak stress obtained in a stress-strain curve.
  • the substrate exhibits an ultimate tensile strength in the machine direction ("MD") of from about 5 to about 80 Megapascals (MPa), in some embodiments from about 10 to about 60 MPa, and in some embodiments, from about 15 to about 50 MPa, and an ultimate tensile strength in the cross-machine direction (“CD") of from about 1 to about 40 Megapascals (MPa), in some embodiments from about 2 to about 40 MPa, and in some embodiments, from about 5 to about 30 MPa.
  • MD machine direction
  • CD cross-machine direction
  • Young's modulus of elasticity is equal to the ratio of the tensile stress to the tensile strain and is determined from the slope of a stress-strain curve.
  • the substrate typically exhibits a Young's modulus in the machine direction ("MD") of from about 20 to about 800 Megapascals (“MPa”), in some embodiments from about 50 to about 500 MPa, and in some embodiments, from about 100 to about 500 MPa, and a Young's modulus in the cross-machine direction (“CD”) of from about 5 to about 250 Megapascals (“MPa”), in some embodiments from about 10 to about 200 MPa, and in some embodiments, from about 20 to about 150 MPa.
  • MD machine direction
  • CD Young's modulus in the cross-machine direction
  • the MD and CD elongation of the substrate may also be about 100% or more, in some embodiments about 200% or more, and in some embodiments, about 300% or more.
  • the substrate may also be water-sensitive (e.g., water-soluble, water-dispersible, etc.) in that it loses integrity over time in the presence of water.
  • the melt-extruded substrate of the present invention may be used in a wide variety of applications.
  • the substrate may be used in an absorbent article.
  • An "absorbent article” generally refers to any article capable of absorbing water or other fluids. Examples of some absorbent articles include, but are not limited to, personal care absorbent articles, such as diapers, training pants, absorbent underpants, incontinence articles, feminine hygiene products (e.g., sanitary napkins, pantiliners, etc.), swim wear, baby wipes, and so forth; medical absorbent articles, such as garments, fenestration materials, underpads, bedpads, bandages, absorbent drapes, and medical wipes; food service wipers; clothing articles; and so forth.
  • personal care absorbent articles such as diapers, training pants, absorbent underpants, incontinence articles, feminine hygiene products (e.g., sanitary napkins, pantiliners, etc.), swim wear, baby wipes, and so forth
  • medical absorbent articles such as garment
  • the absorbent article may be provided with adhesives (e.g., pressure-sensitive adhesives) that help removably secure the article to the crotch portion of an undergarment and/or wrap up the article for disposal.
  • adhesives e.g., pressure-sensitive adhesives
  • Suitable pressure-sensitive adhesives may include acrylic adhesives, natural rubber adhesives, tackified block copolymer adhesives, polyvinyl acetate adhesives, ethylene vinyl acetate adhesives, silicone adhesives, polyurethane adhesives, thermosettable pressure-sensitive adhesives, such as epoxy acrylate or epoxy polyester pressure-sensitive adhesives, etc.
  • pressure-sensitive adhesives are known in the art and are described in the Handbook of Pressure Sensitive Adhesive Technology, Satas (Donatas), 1989, 2 nd edition, Van Nostrand Reinhold.
  • the pressure sensitive adhesives may also include additives such as cross-linking agents, fillers, gases, blowing agents, glass or polymeric microspheres, silica, calcium carbonate fibers, surfactants, and so forth.
  • the additives are included in amounts sufficient to affect the desired properties.
  • the location of the adhesive on the absorbent article is not critical and may vary widely depending on the intended use of the article.
  • certain feminine hygiene products e.g., sanitary napkins
  • the flaps may be provided with an adhesive (e.g., pressure-sensitive adhesive) for affixing the flaps to the underside of the wearer's panties.
  • a release liner may be employed to cover the adhesive, thereby protecting it from dirt, drying out, and premature sticking prior to use.
  • the release liner may contain a release coating that enhances the ability of the liner to be peeled from an adhesive.
  • the release coating contains a release agent, such as a hydrophobic polymer.
  • exemplary hydrophobic polymers include, for instance, silicones (e.g., polysiloxanes, epoxy silicones, etc.), perfluoroethers, fluorocarbons, polyurethanes, and so forth. Examples of such release agents are described, for instance, in U.S. Patent Nos.
  • One particularly suitable release agent is an amorphous polyolefin having a melt viscosity of about 400 to about 10,000 cps at 190 0 C, such as made by the U.S. Rexene Company under the tradename
  • the release coating may also contain a detackifier, such as a low molecular weight, highly branched polyolefin.
  • a detackifier such as a low molecular weight, highly branched polyolefin.
  • VYBAR® 253 is made by the Petrolite Corporation.
  • Other additives may also be employed in the release coating, such as compatibilizers, processing aids, plasticizers, tackifiers, slip agents, and antimicrobial agents, and so forth.
  • the release coating may be applied to one or both surfaces of the liner, and may cover all or only a portion of a surface.
  • Solvent-based coatings are typically applied to the release liner by processes such as roll coating, knife coating, curtain coating, gravure coating, wound rod coating, and so forth.
  • the solvent e.g., water
  • Solventless coatings may include solid compositions, such as silicones or epoxy silicones, which are coated onto the liner and then cured by exposure to ultraviolet light.
  • Optional steps include priming the liner before coating or surface modification of the liner, such as with corona treatment.
  • Hot melt coatings such as polyethylenes or perfluoroethers
  • Hot melt coatings may be heated and then applied through a die or with a heated knife. Hot melt coatings may be applied by co-extruding the release agent with the release liner in blown film or sheet extruder for ease of coating and for process efficiency.
  • the release liner may be formed from a melt-extruded substrate (e.g., film) in accordance with the present invention.
  • a melt-extruded substrate e.g., film
  • the absorbent article 20 includes a main body portion 22 containing a topsheet 40, an outer cover or backsheet 42, an absorbent core 44 positioned between the backsheet 42 and the topsheet 40, and a pair of flaps 24 extending from each longitudinal side 22a of the main body portion 22.
  • the topsheet 40 defines a bodyfacing surface of the absorbent article 20.
  • the absorbent core 44 is positioned inward from the outer periphery of the absorbent article 20 and includes a body-facing side positioned adjacent the topsheet 40 and a garment-facing surface positioned adjacent the backsheet 42.
  • the topsheet 40 is generally designed to contact the body of the user and is liquid-permeable.
  • the topsheet 40 may surround the absorbent core 44 so that it completely encases the absorbent article 20.
  • the topsheet 40 and the backsheet 42 may extend beyond the absorbent core 44 and be peripherally joined together, either entirely or partially, using known techniques.
  • the topsheet 40 and the backsheet 42 are joined by adhesive bonding, ultrasonic bonding, or any other suitable joining method known in the art.
  • the topsheet 40 is sanitary, clean in appearance, and somewhat opaque to hide bodily discharges collected in and absorbed by the absorbent core 44.
  • the topsheet 40 further exhibits good strike-through and rewet characteristics permitting bodily discharges to rapidly penetrate through the topsheet 40 to the absorbent core 44, but not allow the body fluid to flow back through the topsheet 40 to the skin of the wearer.
  • suitable materials that may be used for the topsheet 40 include nonwoven materials, perforated thermoplastic films, or combinations thereof.
  • a nonwoven fabric made from polyester, polyethylene, polypropylene, bicomponent, nylon, rayon, or like fibers may be utilized.
  • a white uniform spunbond material is particularly desirable because the color exhibits good masking properties to hide menses that has passed through it.
  • U.S. Patent No. 4,801 ,494 to Datta, et al. and U.S. Patent No. 4,908,026 to Sukiennik, et al. teach various other cover materials that may be used in the present invention.
  • the topsheet 40 may also contain a plurality of apertures (not shown) formed therethrough to permit body fluid to pass more readily into the absorbent core 44.
  • the apertures may be randomly or uniformly arranged throughout the topsheet 40, or they may be located only in the narrow longitudinal band or strip arranged along the longitudinal axis X--X of the absorbent article 20.
  • the apertures permit rapid penetration of body fluid down into the absorbent core 44.
  • the size, shape, diameter and number of apertures may be varied to suit one's particular needs.
  • the absorbent article also includes a backsheet 42.
  • the backsheet 42 is generally liquid-impermeable and designed to face the inner surface, i.e., the crotch portion of an undergarment (not shown).
  • the backsheet 42 may permit a passage of air or vapor out of the absorbent article 20, while still blocking the passage of liquids.
  • Any liquid-impermeable material may generally be utilized to form the backsheet 42.
  • one suitable material that may be utilized is a microembossed polymeric film, such as polyethylene or polypropylene.
  • a polyethylene film is utilized that has a thickness in the range of about 0.2 mils to about 5.0 mils, and particularly between about 0.5 to about 3.0 mils.
  • the absorbent article 20 also contains an absorbent core 44 positioned between the topsheet 40 and the backsheet 42.
  • the absorbent core 44 may be formed from a single absorbent member or a composite containing separate and distinct absorbent members. It should be understood, however, that any number of absorbent members may be utilized in the present invention.
  • the absorbent core 44 may contain an intake member (not shown) positioned between the topsheet 40 and a transfer delay member (not shown).
  • the intake member may be made of a material that is capable of rapidly transferring, in the z-direction, body fluid that is delivered to the topsheet 40.
  • the intake member may generally have any shape and/or size desired.
  • the intake member has a rectangular shape, with a length equal to or less than the overall length of the absorbent article 20, and a width less than the width of the absorbent article 20.
  • a length of between about 150 mm to about 300 mm and a width of between about 10 mm to about 60 mm may be utilized.
  • the material may be synthetic, cellulosic, or a combination of synthetic and cellulosic materials.
  • airlaid cellulosic tissues may be suitable for use in the intake member.
  • the airlaid cellulosic tissue may have a basis weight ranging from about 10 grams per square meter (gsm) to about 300 gsm, and in some embodiments, between about 100 gsm to about 250 gsm. In one embodiment, the airlaid cellulosic tissue has a basis weight of about 200 gsm.
  • the airlaid tissue may be formed from hardwood and/or softwood fibers.
  • the airlaid tissue has a fine pore structure and provides an excellent wicking capacity, especially for menses.
  • a transfer delay member (not shown) may be positioned vertically below the intake member.
  • the transfer delay member may contain a material that is less hydrophilic than the other absorbent members, and may generally be characterized as being substantially hydrophobic.
  • the transfer delay member may be a nonwoven fibrous web composed of a relatively hydrophobic material, such as polypropylene, polyethylene, polyester or the like, and also may be composed of a blend of such materials.
  • a material suitable for the transfer delay member is a spunbond web composed of polypropylene, multi- lobal fibers.
  • suitable transfer delay member materials include spunbond webs composed of polypropylene fibers, which may be round, tri-lobal or poly-lobal in cross-sectional shape and which may be hollow or solid in structure. Typically the webs are bonded, such as by thermal bonding, over about 3% to about 30% of the web area.
  • suitable materials that may be used for the transfer delay member are described in U.S. Patent No. 4,798,603 to Meyer, et al. and U.S. Patent No. 5,248,309 to Portugalk, et al.. which are incorporated herein in their entirety by reference thereto for all purposes.
  • the transfer delay member may also be treated with a selected amount of surfactant to increase its initial wettability.
  • the transfer delay member may generally have any size, such as a length of about 150 mm to about 300 mm. Typically, the length of the transfer delay member is approximately equal to the length of the absorbent article 20.
  • the transfer delay member may also be equal in width to the intake member, but is typically wider. For example, the width of the transfer delay member may be from between about 50 mm to about 75 mm, and particularly about 48 mm.
  • the transfer delay member typically has a basis weight less than that of the other absorbent members. For example, the basis weight of the transfer delay member is typically less than about 150 grams per square meter (gsm), and in some embodiments, between about 10 gsm to about 100 gsm. In one particular embodiment, the transfer delay member is formed from a spunbonded web having a basis weight of about 30 gsm.
  • the absorbent core 44 may aiso include a composite absorbent member (not shown), such as a coform material.
  • a composite absorbent member such as a coform material.
  • fluids may be wicked from the transfer delay member into the composite absorbent member.
  • the composite absorbent member may be formed separately from the intake member and/or transfer delay member, or may be formed simultaneously therewith.
  • the composite absorbent member may be formed on the transfer delay member or intake member, which acts a carrier during the coform process described above.
  • the absorbent article 20 typically contains an adhesive for securing to an undergarment.
  • An adhesive may be provided at any location of the absorbent article 20, such as on the lower surface of the backsheet 42.
  • the backsheet 42 carries a longitudinally central strip of garment adhesive 54 covered before use by a peelable release liner 58, which may be formed in accordance with the present invention.
  • Each of the flaps 24 may also contain an adhesive 56 positioned adjacent to the distal edge 34 of the flap 24.
  • a peelable release liner 57 which may also be formed in accordance with the present invention, may cover the adhesive 56 before use.
  • the present invention is by no means limited to release liners and the melt-extruded substrate may be incorporated into a variety of different components of an absorbent article.
  • the backsheet 42 of the napkin 20 may include the melt-extruded substrate (e.g., film) of the present invention.
  • the substrate may be used alone to form the backsheet 42 or laminated to one or more additional materials, such as a nonwoven web.
  • the melt-extruded substrate of the present invention may also be used in applications other than absorbent articles.
  • the substrate may be employed as an individual wrap, packaging pouch, or bag for the disposal of a variety of articles, such as food products, absorbent articles, etc.
  • a variety of articles such as food products, absorbent articles, etc.
  • Various suitable pouch, wrap, or bag configurations for absorbent articles are disclosed, for instance, in U.S. Patent Nos. 6,716,203 to Sorebo, et al. and 6,380,445 to Moder, et al., as well as U.S. Patent Application Publication No. 2003/0116462 to Sorebo, et al., all of which are incorporated herein in their entirety by reference thereto for all purposes.
  • Theological properties of polymer samples were determined using a Gottfert Rheograph 2003 capillary rheometer with WinRHEO version 2.31 analysis software.
  • the setup included a 2000-bar pressure transducer and a 30/1 :0/180 roundhole capillary die. Sample loading was done by alternating between sample addition and packing with a ramrod. A 2-minute melt time preceded each test to allow the polymer to completely melt at a test temperature (150 0 C or 160 0 C).
  • the capillary rheometer determined the apparent melt viscosity (Pa-s) at various shear rates, such as 100, 200, 500, 1000, 2000, and 4000 s "1 .
  • the resultant rheology curve of apparent shear rate versus apparent melt viscosity gave an indication of how the polymer would run at that temperature in an extrusion process.
  • the strip tensile strength values were determined in substantial accordance with ASTM Standard D-5034.
  • a constant-rate-of-extension type of tensile tester was employed.
  • the tensile testing system was a Sintech 1/D tensile tester, which is available from Sintech Corp. of Cary, North Carolina.
  • the tensile tester was equipped with TESTWORKS 4.08B software from MTS Corporation to support the testing.
  • An appropriate load cell was selected so that the tested value fell within the range of 10-90% of the full scale load.
  • the film samples were initially cut into dog-bone shapes with a center width of 3.0 mm before testing. The samples were held between grips having a front and back face measuring 25.4 millimeters x 76 millimeters.
  • the grip faces were rubberized, and the longer dimension of the grip was perpendicular to the direction of pull.
  • the grip pressure was pneumatically maintained at a pressure of 40 pounds per square inch.
  • the tensile test was run using a gauge length of 18.0 millimeters and a break sensitivity of 40%. Five samples were tested by applying the test load along the machine-direction and five samples were tested by applying the test load along the cross direction. During the test, samples were stretched at a crosshead speed of abut 127 millimeters per minute until breakage occurred. The modulus, peak stress, and elongation were measured in the machine direction ("MD") and cross-machine directions ("CD"). Water Disintegration Test:
  • the rate of film disintegration in tap water was tested using a "slosh box", which has a physical dimension of a 14" x 18" x 12" high plastic box on a hinged platform. One end of the platform is attached to the reciprocating cam.
  • the typical amplitude is ⁇ 2" (4" range), with sloshing occurring at 0.5 -1.5 sloshes per second.
  • the preferred action is 0.9 ⁇ 1.3 sloshes per second.
  • the slosh box rocks up and down with the water inside, "sloshing" back and forth. This action produces a wave front and intermittent motion on a sample susceptible to dispersing in water. To quantify a measurement of sample film disintegration in water, without image analysis, simply timing is sufficient.
  • thermoplastic starch containing a native starch and a plasticizer was formed as follows. Initially, 2% Excel P-40S (mono-di-glyceride, Kao Corp. of Japan) was dry mixed with native corn starch (Cargill, Inc., Minneapolis, Minnesota) in a kitchen mixer and then added to a K-Tron gravimetric feeder (Model KCL-QX4, K-Tron North America, Pitman, NY) that fed the material into a Thermo PrismTM LJSALAB 16 twin screw extruder (Thermo Electron Corp., Stone, England). The extruder had 11 zones, numbered consecutively 0-10 from the feed hopper to the die.
  • K-Tron gravimetric feeder Model KCL-QX4, K-Tron North America, Pitman, NY
  • the temperature profile of zones 1 to 10 of the extruder was 7O 0 C, 8O 0 C, 100 0 C, 140 0 C, 14O 0 C, 140°C, 120 0 C, 100°C, 80 0 C, and 6O 0 C, respectively.
  • the screw speed was set at 170 rpm to achieve a torque of between 60-75% during the processing.
  • the starch feeding rate was fixed at 15 grams per minute at 20 rpm with an agitator. The starch was fed to the feed throat of the extruder (un-heated, before zone 1 of the extruder).
  • Glycerol (98% purity, Cognis Corporation, Cincinnati, Ohio) was injected into zone 1 of the extruder using a plasticizer gear pump (Bodine Electric Company, Grand Island, New York). The liquid pump rate was manually fixed at 4 grams per minute at 30 rpm and 5.8 grams per minute at 40 rpm. In some cases, a vent was also opened to release steam generated. The resulting strand cooled down through a cooling belt (Minarik Electric Company, Glendale, California). A pelletizer (Emerson Industrial Controls, Grand Island, New York) was used to cut the strand to produce thermoplastic starch pellets containing 30 wt.% glycerol.
  • thermoplastic starch containing a native starch and a plasticizer was formed as described in Example 1 , except that a mixture of 80 wt.% glycerol (98% purity, Cognis Corp.) and 20 wt.% water was used as the plasticizer.
  • thermoplastic starch was formed from a native starch, plasticizer, and weak organic acid as follows. Initially, 2% Excel P-40S was dry mixed with native corn starch (Cargill, Inc., Minneapolis, Minnesota) in a kitchen mixer and then added to a K-T ron gravimetric feeder (Model KCL-QX4, K-Tron) that fed the material into a Thermo PrismTM USALAB 16 twin screw extruder. The temperature profile of zones 1 to 10 of the extruder was 70 0 C, 8O 0 C, 100 0 C, 140°C, 140°C, 140°C, 12O 0 C, 100°C, 80°C, and 60 0 C, respectively.
  • the screw speed was set at 170 rpm to achieve a torque of between 60-75% during the processing.
  • the starch feeding rate was fixed at 15 grams per minute at 20 rpm with an agitator.
  • the starch was fed to the feed throat of the extruder (un-heated, before zone 1 of the extruder).
  • a mixture of 50 wt.% glycerol and 50 wt.% lactic acid (85% in water, Sigma-Aldrich, St. Louis, Missouri) was injected into zone 1 of the extruder using a plasticizer gear pump (Bodine Electric Company, Grand Island, New York).
  • the liquid pump rate was manually fixed at 4 grams per minute at 30 rpm and 5.8 grams per minute at 40 rpm.
  • a vent was also opened to release steam generated.
  • the resulting strand cooled down through a cooling belt (Minarik Electric Company, Glendale, California).
  • a pelletizer (Emerson Industrial Controls, Grand island, New York) was used to cut the strand to produce thermoplastic starch pellets containing 10 wt.% glycerol and 10 wt.% lactic acid.
  • thermoplastic starch was formed as described in Example 3, except that
  • thermoplastic modified starch contained 20 wt.% lactic acid.
  • thermoplastic starch was formed as described in Example 3, except that a mixture of 25 wt.% acetic acid (Sigma-Aldrich, St. Louis, Missouri) and 75 wt.% glycerol was injected into zone 1 of the extruder rather than a mixture of 50 wt.% glycerol and 50 wt.% lactic acid.
  • the resulting thermoplastic modified starch contained 5 wt.% acetic acid and 15 wt.% glycerol.
  • thermoplastic starch was formed as described in Example 3, except that a mixture of 50 wt.% formic acid (Sigma-Aldrich, St. Louis, Missouri) and 50 wt.% glycerol was injected into zone 1 of the extruder rather than a mixture of 50 wt.% glycerol and 50 wt.% lactic acid.
  • the resulting thermoplastic modified starch contained 10 wt.% formic acid and 10 wt.% glycerol.
  • thermoplastic starch containing a native starch and a plasticizer was formed as follows. Initially, 2% Excel P-40S was dry mixed with native potato starch (Penford Food Ingredients Co., Englewood, Colorado) in a kitchen mixer and then added to a K-T ron gravimetric feeder (Model KCL-QX4, K-T ron) that fed the material into a Thermo PrismTM USALAB 16 twin screw extruder. The temperature profile of zones 1 to 10 of the extruder was 9O 0 C, 100°C, 12O 0 C, 130 0 C, 12O 0 C, 115°C, 110°C, 100 0 C, 9O 0 C, and 60 0 C, respectively.
  • the screw speed was set at 170 rpm to achieve a torque of between 55-65% during the processing.
  • the starch feeding rate was fixed at 15 grams per minute at 20 rpm with an agitator.
  • the starch was fed to the feed throat of the extruder (un-heated, before zone 1 of the extruder).
  • a mixture of 80 wt.% glycerol and 20 wt.% water was injected into zone 1 of the extruder using a plasticizer gear pump (Bodine Electric Company, Grand Island, New York).
  • the liquid pump rate was manually fixed at 4 grams per minute at 30 rpm and 5.8 grams per minute at 40 rpm. In some cases, a vent was also opened to release steam generated.
  • the resulting strand cooled down through a cooling belt (Minarik Electric Company, Glendale, California).
  • a pelletizer (Emerson Industrial Controls, Grand Island, New York) was used to cut the strand to produce thermoplastic starch pellets containing 30 wt.% glycerol.
  • thermoplastic starch was formed from a native starch, plasticizer, and weak organic acid as follows. Initially, 2% Excel P-40S was dry mixed with native potato starch (Penford Food Ingredients Co., Englewood, Colorado) in a kitchen mixer and then added into a K-T ron gravimetric feeder (Model KCL-QX4, K-T ron) that fed the material into a Thermo PrismTM USALAB 16 twin screw extruder. The temperature profile of zones 1 to 10 of the extruder was 90 0 C, 100 0 C, 120°C, 130 0 C, 120°C, 115°C, 110°C, 100 0 C, 90°C, and 60 0 C, respectively.
  • the screw speed was set at 170 rpm to achieve a torque of between 55-65% during the processing.
  • the starch feeding rate was fixed at 15 grams per minute at 20 rpm with an agitator.
  • the starch was fed to the feed throat of the extruder (un-heated, before zone 1 of the extruder).
  • a mixture of 50 wt.% glycerol (98% purity, Cognis Corporation, Cincinnati, Ohio) and 50 wt.% lactic acid was injected into zone 1 of the extruder using a plasticizer gear pump (Bodine Electric Company, Grand Island, New York).
  • the liquid pump rate was manually fixed at 4 grams per minute at 30 rpm and 5.8 grams per minute at 40 rpm. In some cases, a vent was also opened to release steam generated.
  • the resulting strand cooled down through a cooling belt (Minarik Electric Company, Glendale, California).
  • thermoplastic starch pellets containing 10 wt.% glycerol and 10 wt.% lactic acid.
  • thermoplastic starches of Examples 1 -8 were determined using conventional gel permeation chromatography in DMSO (dimethyl sulfoxide) at elevated temperature (100 0 C) and with dextran as the reference standard. The resulting molecular weight distribution is set forth below in Table 1. Table 1 : Molecular Weight Distribution
  • the weight average molecular weights decreased for both types of thermoplastic starches when processed with a weak organic acid and plasticizer. Quite surprisingly, however, the number average molecular weights of both the corn and potato thermoplastic starches increased after preparation.
  • thermoplastic starches of Examples 1-4 were also determined as described above. The results are set forth in Fig. 2. As indicated, the resulting viscosity values for the thermoplastic starch made using 30% glycerol/water (80/20) were identical to those made using 30% glycerol, indicating there is no change in starch molecular weight distribution. However, when lactic acid was present (Examples 3 and 4), the resulting thermoplastic starch showed a remarkable decrease in melt viscosity, indicating breakdown or hydrolysis of starch macromolecule chains due to chemical modifications during melt blending.
  • thermoplastic starches of Examples 5-6 were also determined as described above. The results are set forth in Fig. 3. As indicated, chemical modification by acetic acid was not as effective in comparison to formic acid in reducing the viscosity of the thermoplastic starch.
  • thermoplastic starches of Examples 7-8 were also determined as described above. The results are set forth in Fig. 4. As indicated, the thermoplastic starch exhibited a significant viscosity reduction, indicating that apparent melt viscosity reduces further as the acidity of the organic acid increased.
  • thermoplastic starch of Examples 2, 3, 5, 6, and 8 were compounded in a Carver Press (Carver Press, Inc., Wabash, Indiana) and formed into pressed films.
  • the set pressure was 15,000 lbs
  • pump speed was set at 100%
  • the holding time was 5 seconds.
  • the film thicknesses ranged from about 2 to about 3 mils (about 50.8 to about 76.2 micrometers). Once formed, the films were subjected to the above-described water disintegration test. The results are set forth below in Table 2.
  • thermoplastic starch of Example 3 The ability to form a cast film with the thermoplastic starch of the present invention was demonstrated.
  • the thermoplastic starch of Example 3 was dry blended in a HAAKE Rheomex 252 single screw extruder with an Ecoflex® F BX 7011 resin (BASF, Ludwigshafen, Germany) at weight percentages of 30 wt.% and 70 wt.%, respectively.
  • the screw speed was set at 50 rpm and the temperature profile of the extruder from zone 1 to 5 was 140 0 C, 150 0 C, 150°C, 146 0 C, and 137 0 C, respectively.
  • the melt temperature was 155°C.
  • the resulting cast film was then conditioned at 25°C and 50% relative humidity over a weekend.

Abstract

A meit-extruded substrate (e.g., fiim, nonwoven web, etc.) that contains a thermoplastic starch formed from a starch and plasticizer is provided. The starch and plasticizer are melt blended together in the presence of a weak organic acid (e.g., lactic acid, formic acid, acetic acid, etc.). By selectively controlling certain parameters of the melt blending process (e.g., extrusion temperature, content of the components, etc.), the present inventors have discovered that the starch may be hydrolyzed in a highly efficient manner to form compositions having a comparably lower weight average molecular weight, polydispersity index, and viscosity, which are particularly suitable for use in the formation of melt-extruded substrates.

Description

THERMOPLASTIC STARCH FOR USE IN MELT-EXTRUDED SUBSTRATES
Background of the Invention
Thermoplastic starches, either alone or in combination with other polymers, are often used in the manufacture of articles for which water or biological degradation are considered important. The thermoplastic starch is typically formed by plasticizing a native starch with a functional plasticizer or mixture of plasticizers, such as polyfunctional alcohols (e.g., ethylene glycol, propylene glycol, or glycerol). Conventional thermoplastic starches, however, are often problematic in that they absorb moisture and age during storage, exhibit processing problems, and lack the requisite mechanical strength, ductility and toughness for many applications. Various techniques were thus developed in an attempt to improve the properties of thermoplastic starch. U.S. Patent No. 6,933,335 to Berger, et al., for instance, describes a technique that involves extruding a mixture of a thermoplastic starch and at least one hydrophobic polymer with the addition of a hydrolysis component based on polyvinyl acetate, lower functional alcohols and/or water, and an acidic catalyst (e.g., dibutyl tin oxide). According to Berqer, et al., the acidic catalyst enhances the transesterification or crosslinking of the starch, the hydrophobic polymer, and hydrolysis component. For this reason, the starch component of the blend has a molecular weight that is only minimally reduced relative to native starch.
Despite the techniques developed, it has still proven problematic to form melt-extruded substrates (e.g., nonwoven webs, films, etc.) from thermoplastic starches. Films, for example, typically require polymers of appropriate molecular weights and suitable melt viscosity for processing. It is often difficult, however, to achieve both mechanical strength and water/biological degradation from such polymers. As such, a need currently exists for a thermoplastic starch that exhibits good mechanical properties and is capable of water and/or biological degradation.
Summary of the Invention In accordance with one embodiment of the present invention, a melt- extruded substrate is disclosed that comprises a thermoplastic starch formed from about 30 wt. % to about 95 wt.% of at least one starch, from about 1 wt.% to about 35 wt.% of at least one plasticizer, and from about 1 wt.% to about 35 wt.% of at least one weak organic acid. The thermoplastic starch has a weight average molecular weight of from about 1 ,000,000 to about 5,000,000, polydispersity index of from about 0.5 to about 20, and apparent meit viscosity of from about 50 to about 800 Pascal-seconds, determined at a temperature of 1500C and a shear rate of 100 sec"1. In accordance with another embodiment of the present invention, a method for forming a substrate is disclosed. The method comprises melt blending a composition comprising from about 30 wt.% to about 95 wt.% of at least one starch, from about 1 wt.% to about 35 wt.% of at least one plasticizer, and from about 1 wt.% to about 35 wt.% of at least one weak organic acid to form a thermoplastic starch. The thermoplastic starch has a weight average molecular weight of from about 1 ,000,000 to about 5,000,000, polydispersity index of from about 0.5 to about 20, and apparent melt viscosity of from about 50 to about 800 Pascal-seconds, determined at a temperature of 1500C and a shear rate of 100 sec"1. The thermoplastic starch is extruded onto a surface to form a substrate. Other features and aspects of the present invention are discussed in greater detail below.
Brief Description of the Drawings
A full and enabling disclosure of the present invention, including the best mode thereof, directed to one of ordinary skill in the art, is set forth more particularly in the remainder of the specification, which makes reference to the appended figures in which:
Fig. 1 is a schematic illustration of one embodiment of a method for forming a melt-extruded substrate in accordance with the present invention;
Fig. 2 is a graphical representation of the apparent melt viscosity (Pa-s) of the thermoplastic starches of Examples 1-4 versus shear rate (s"1);
Fig. 3 is a graphical representation of the apparent melt viscosity (Pa-s) of the thermoplastic starches of Examples 5-6 versus shear rate (s"1);
Fig. 4 is a graphical representation of the apparent melt viscosity (Pa-s) of the thermoplastic starches of Examples 7-8 versus shear rate (s"1); and Fig. 5 is a top view of an absorbent article that may be formed in accordance with one embodiment of the present invention. Repeat use of references characters in the present specification and drawings is intended to represent same or analogous features or elements of the invention.
Detailed Description of Representative Embodiments Definitions
As used herein the term "nonwoven web" generally refers to a web having a structure of individual fibers or threads which are interlaid, but not in an identifiable manner as in a knitted fabric. Examples of suitable nonwoven fabrics or webs include, but are not limited to, meltblown webs, spunbond webs, bonded carded webs, airlaid webs, coform webs, hydraulically entangled webs, and so forth.
As used herein, the term "meltblown web" generally refers to a nonwoven web that is formed by a process in which a molten thermoplastic material is extruded through a plurality of fine, usually circular, die capillaries as molten fibers into converging high velocity gas (e.g., air) streams that attenuate the fibers of molten thermoplastic material to reduce their diameter, which may be to microfiber diameter. Thereafter, the meltblown fibers are carried by the high velocity gas stream and are deposited on a collecting surface to form a web of randomly dispersed meltblown fibers. Such a process is disclosed, for example, in U.S. Patent No. 3,849,241 to Butin, et al., which is incorporated herein in its entirety by reference thereto for all purposes. Generally speaking, meltblown fibers may be microfibers that are substantially continuous or discontinuous, generally smaller than 10 micrometers in diameter, and generally tacky when deposited onto a collecting surface.
As used herein, the term "spunbond web" generally refers to a web containing small diameter substantially continuous fibers. The fibers are formed by extruding a molten thermoplastic material from a plurality of fine, usually circular, capillaries of a spinnerette with the diameter of the extruded fibers then being rapidly reduced as by, for example, eductive drawing and/or other well-known spunbonding mechanisms. The production of spunbond webs is described and illustrated, for example, in U.S. Patent Nos. 4,340,563 to Appel, et al.. 3,692,618 to Dorschner, et al.. 3,802,817 to Matsuki, et al., 3,338,992 to Kinney, 3,341 ,394 to Kinnev, 3,502,763 to Hartman, 3,502,538 to Levy, 3,542,615 to Dobo, et al., and 5,382,400 to Pike, et al., which are incorporated herein in their entirety by reference thereto for all purposes. Spunbond fibers are generally not tacky when they are deposited onto a collecting surface. Spunbond fibers may sometimes have diameters less than about 40 micrometers, and are often between about 5 to about 20 micrometers. Detailed Description
Reference now will be made in detail to various embodiments of the invention, one or more examples of which are set forth below. Each example is provided by way of explanation of the invention, not limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations may be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, may be used on another embodiment to yield a still further embodiment. Thus, it is intended that the present invention covers such modifications and variations as come within the scope of the appended claims and their equivalents.
Generally speaking, the present invention is directed to a melt-extruded substrate (e.g., film, nonwoven web, etc.) that contains a thermoplastic starch formed from a starch and plasticizer. The starch and plasticizer are melt blended together in the presence of a weak organic acid (e.g., lactic acid, formic acid, acetic acid, etc.). By selectively controlling certain parameters of the melt blending process (e.g., extrusion temperature, content of the components, etc.), the present inventors have discovered that the starch may be hydrolyzed in a highly efficient manner to form compositions having a comparably lower weight average molecular weight, polydispersity index, and viscosity, which are particularly suitable for use in the formation of melt-extruded substrates. In this regard, various embodiments of the present invention will now be described in more detail. I. Thermoplastic Starch
Starch is a natural polymer composed of amylose and amylopectin. Amylose is essentially a linear polymer having a molecular weight in the range of 100,000-500,000, whereas amylopectin is a highly branched polymer having a molecular weight of up to several million. Although starch is produced in many plants, typical sources includes seeds of cereal grains, such as corn, waxy corn, wheat, sorghum, rice, and waxy rice; tubers, such as potatoes; roots, such as tapioca (i.e., cassava and manioc), sweet potato, and arrowroot; and the pith of the sago paim. Broadly speaking, native (unmodified) and/or modified starches may be employed in the present invention. Modified starches, for instance, may be employed that have been chemically modified by typical processes known in the art (e.g., esterification, etherification, oxidation, enzymatic hydrolysis, etc.). Starch ethers and/or esters may be particularly desirable, such as hydroxyalkyl starches, carboxymethyl starches, etc. The hydroxyalkyl group of hydroxylalkyl starches may contain, for instance, 2 to 10 carbon atoms, in some embodiments from 2 to 6 carbon atoms, and in some embodiments, from 2 to 4 carbon atoms. Representative hydroxyalkyl starches such as hydroxyethyl starch, hydroxypropyl starch, hydroxybutyl starch, and derivatives thereof. Starch esters, for instance, may be prepared using a wide variety of anhydrides (e.g., acetic, propionic, butyric, and so forth), organic acids, acid chlorides, or other esterification reagents. The degree of esterification may vary as desired, such as from 1 to 3 ester groups per glucosidic unit of the starch.
Regardless of whether it is in a native or modified form, the starch may contain different percentages of amylose and amylopectin, different size starch granules and different polymeric weights for amylose and amylopectin. High amylose starches contain greater than about 50% by weight amylose and low amylose starches contain less than about 50% by weight amylose. Although not required, low amylose starches having an amylose content of from about 10% to about 40% by weight, and in some embodiments, from about 15% to about 35% by weight, are particularly suitable for use in the present invention. Examples of such low amylose starches include corn starch and potato starch, both of which have an amylose content of approximately 20% by weight. Such low amylose starches typically have a number average molecular weight ("Mn") ranging from about 50,000 to about 1 ,000,000 grams per mole, in some embodiments from about 75,000 to about 800,000 grams per mole, and in some embodiments, from about 100,000 to about 600,000 grams per mole, as well as a weight average molecular weight ("Mw") ranging from about 5,000,000 to about 25,000,000 grams per mole, in some embodiments from about 5,500,000 to about 15,000,000 grams per mole, and in some embodiments, from about 6,000,000 to about 12,000,000 grams per mole. The ratio of the weight average molecular weight to the number average molecular weight ("Mw/Mn"). i-β-, the "polydispersity index", is also relatively high. For example, the poiydispersity index may range from about 20 to about 100. The weight and number average molecular weights may be determined by methods known to those skilled in the art. A plasticizer is also employed in the thermoplastic starch to help render the starch melt-processible. Starches, for instance, normally exist in the form of granules that have a coating or outer membrane that encapsulates the more water-soluble amylose and amylopectin chains within the interior of the granule. When heated, plasticizers may soften and penetrate the outer membrane and cause the inner starch chains to absorb water and swell. This swelling will, at some point, cause the outer shell to rupture and result in an irreversible destructurization of the starch granule. Once destructurized, the starch polymer chains containing amylose and amylopectin polymers, which are initially compressed within the granules, will stretch out and form a generally disordered intermingling of polymer chains. Upon resolidification, however, the chains may reorient themselves to form crystalline or amorphous solids having varying strengths depending on the orientation of the starch polymer chains. Because the starch is thus capable of melting and resolidifying at certain temperatures, it is generally considered a "thermoplastic starch." Suitable plasticizers may include, for instance, polyhydric alcohol plasticizers, such as sugars (e.g., glucose, sucrose, fructose, raffinose, maltodextrose, galactose, xylose, maltose, lactose, mannose, and erythrose), sugar alcohols (e.g., erythritol, xylitol, malitol, mannitol, and sorbitol), polyols (e.g., ethylene glycol, glycerol, propylene glycol, dipropylene glycol, butylene glycol, and hexane triol), etc. Also suitable are hydrogen bond forming organic compounds which do not have hydroxy! group, including urea and urea derivatives; anhydrides of sugar alcohols such as sorbitan; animal proteins such as gelatin; vegetable proteins such as sunflower protein, soybean proteins, cotton seed proteins; and mixtures thereof. Other suitable plasticizers may include phthalate esters, dimethyl and diethylsuccinate and related esters, glycerol triacetate, glycerol mono and diacetates, glycerol mono, di, and tripropionates, butanoates, stearates, lactic acid esters, citric acid esters, adipic acid esters, stearic acid esters, oleic acid esters, and other acid esters. Aliphatic acids may also be used, such as copolymers of ethylene and acrylic acid, polyethylene grafted with maleic acid, polybutadiene-co-acryiic acid, poiybutadiene-co-maieic acid, poiypropylene-co- acrylic acid, polypropylene-co-maleic acid, and other hydrocarbon based acids. A low molecular weight plasticizer is preferred, such as less than about 20,000 g/mol, preferably less than about 5,000 g/mol and more preferably less than about 1 ,000 g/mol.
In the present invention, the starch is hydrolyzed into lower molecular weight carbohydrates in the presence of a weak organic acid, which acts as a chain scission catalyst by splitting primarily the α-1 ,4 glycosidic bonds in the starch macromolecule. Particularly suitable organic acids that may be used in the present invention include organophosphoric acids; organosulfuric acids; organoboric acids; carboxylic acids, such as acrylic acid, methacrylic acid, malonic acid, succinic acid, salicylic acid, sulfosalicylic acid, adipic acid, maleic acid, malic acid, oleic acid, gallic acid, tartaric acid, citric acid, formic acid, acetic acid, glycolic acid, oxalic acid, tartaric acid (e.g., dextotartaric acid, mesotartaric acid, etc.), propionic acid, phthalic acid, isophthalic acid, glutaric acid, gluconic acid, lactic acid, aspartic acid, glutaminic acid, itaconic acid, trifluoroacetic acid, barbituric acid, cinnamic acid, benzoic acid, 4-hydroxybenzoic acid, aminobenzoic acid, etc.; phenols, such as pyrogallol (benzene-1 ,2,3-triol), pyrocatechol (benezenediol), etc.; blends thereof, and so forth. Anhydrides (e.g., maleic anhydride) and salts of organic acids may also be employed. Particularly suitable organic acids for use in the present invention are those having an acid dissociation constant (pKa) ranging from 0 to about 8, in some embodiments from about 1 to about 5, and in some embodiments, from about 2 to about 4, determined at 250C, such as lactic acid (pKa of 3.85), formic acid (pKa of 3.75), and acetic acid (pKa of 4.76).
The relative amount of starch, weak organic acid, and plasticizer employed in the thermoplastic starch may vary depending on a variety of factors, such as the desired molecular weight, the type of starch, the affinity of the plasticizer for the starch, etc. Typically, however, the native starch constitutes from about 30 wt.% to about 95 wt.%, in some embodiments from about 40 wt.% to about 90 wt.%, and in some embodiments, from about 50 wt.% to about 85 wt.% of the thermoplastic starch. The weak organic acid may constitute from about 1 wt.% to about 35 wt.%, in some embodiments from about 2 wt.% to about 30 wt.%, and in some embodiments, from about 5 wt.% to about 25 wt.% of the thermoplastic starch. Likewise, the piasticizer typically constitutes from about i wt.% to about 35 wt.%, in some embodiments from about 2 wt.% to about 30 wt.%, and in some embodiments, from about 5 wt.% to about 25 wt.% of the thermoplastic composition. It should be understood that the weight of starch referenced herein includes any bound water that naturally occurs in the starch before mixing it with other components to form the thermoplastic starch. Starches, for instance, typically have a bound water content of about 5% to 16% by weight of the starch. Of course, other additives may also be employed in the thermoplastic starch to facilitate its use in various types of substrates. Dispersion aids, for instance, may be employed to help create a uniform dispersion of the starch/plasticizer mixture and retard or prevent separation of the thermoplastic starch into constituent phases. Likewise, the dispersion aids may also improve the water dispersibility of the substrate. When employed, the dispersion aid(s) typically constitute from about 0.01 wt.% to about 10 wt.%, in some embodiments from about 0.1 wt.% to about 5 wt.%, and in some embodiments, from about 0.5 wt.% to about 4 wt.% of the thermoplastic starch.
Although any dispersion aid may generally be employed in the present invention, surfactants having a certain hydrophilic/lipophilic balance ("HLB") may improve the long-term stability of the composition. The HLB index is well known in the art and is a scale that measures the balance between the hydrophilic and lipophilic solution tendencies of a compound. The HLB scale ranges from 1 to approximately 50, with the lower numbers representing highly lipophilic tendencies and the higher numbers representing highly hydrophilic tendencies. In some embodiments of the present invention, the HLB value of the surfactants is from about 1 to about 20, in some embodiments from about 1 to about 15 and in some embodiments, from about 2 to about 10. If desired, two or more surfactants may be employed that have HLB values either below or above the desired value, but together have an average HLB value within the desired range. One particularly suitable class of surfactants for use in the present invention are nonionic surfactants, which typically have a hydrophobic base (e.g., long chain alkyl group or an alkylated aryl group) and a hydrophilic chain (e.g., chain containing ethoxy and/or propoxy moieties). For instance, some suitable nonionic surfactants that may be used include, but are not limited to, ethoxylated alkylphenols, ethoxylated and propoxylated fatty alcohols, polyethylene glycol ethers of methyl glucose, polyethylene glycol ethers of sorbitol, ethylene oxide- propylene oxide block copolymers, ethoxylated esters of fatty (Cs -Ci8) acids, condensation products of ethylene oxide with long chain amines or amides, condensation products of ethylene oxide with alcohols, fatty acid esters, monoglyceride or diglycerides of long chain alcohols, and mixtures thereof. In one particular embodiment, the nonionic surfactant may be a fatty acid ester, such as a sucrose fatty acid ester, glycerol fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, pentaerythritol fatty acid ester, sorbitol fatty acid ester, and so forth. The fatty acid used to form such esters may be saturated or unsaturated, substituted or unsubstituted, and may contain from 6 to 22 carbon atoms, in some embodiments from 8 to 18 carbon atoms, and in some embodiments, from 12 to 14 carbon atoms. In one particular embodiment, mono- and di-glycerides of fatty acids may be employed in the present invention. II. Melt Blending
The thermoplastic starch of the present invention is formed by melt blending the components together in an extruder. The mechanical shear and heat provided by the extruder facilitates the hydrolysis of the starch and allows the components to be blended together in a highly efficient manner. Batch and/or continuous melt blending techniques may be employed in the present invention. For example, a mixer/kneader, Banbury mixer, Farrel continuous mixer, single-screw extruder, twin-screw extruder, roll mill, etc., may be utilized. One particularly suitable melt- blending device is a co-rotating, twin-screw extruder (e.g., USALAB twin-screw extruder available from Thermo Electron Corporation of Stone, England or an extruder available from Werner-Pfreiderer from Ramsey, New Jersey). Such extruders may include feeding and venting ports and provide high intensity distributive and dispersive mixing. For example, a starch may be initially fed to a feeding port of the twin-screw extruder. Thereafter, a plasticizer and weak organic acid may be injected into the starch. Alternatively, the components may be simultaneously fed to the feed throat of the extruder or separately at a different point along its length.
Regardless, the materials are blended under high shear/pressure and heat to ensure sufficient mixing. For example, melt blending typically occurs at a temperature of from about 4O0C to about 16O0C, in some embodiments, from about 5O0C to about 1500C, and in some embodiments, from about 600C to about 1400C. Likewise, the apparent shear rate during melt blending may range from about 100 seconds"1 to about 10,000 seconds"1, in some embodiments from about 500 seconds"1 to about 5000 seconds"1, and in some embodiments, from about 800 seconds"1 to about 1200 seconds"1. The apparent shear rate is equal to 4Q/πR3, where Q is the volumetric flow rate ("m3/s") of the polymer melt and R is the radius ("m") of the capillary (e.g., extruder die) through which the melted polymer flows. Due to the hydrolysis of the starch in the presence of the weak organic acid and plasticizer during melt blending, the weight average molecular weight, polydispersity index, and viscosity of the resulting thermoplastic starch may be substantially reduced in comparison to native starches, thereby rending it more suitable for many applications. For example, the thermoplastic starch may have a weight average molecular weight ranging from about 1 ,000,000 to about 5,000,000 grams per mole, in some embodiments from about 1 ,500,000 to about 4,000,000 grams per mole, and in some embodiments, from about 2,000,000 to about 3,500,000 grams per mole. Likewise, the thermoplastic starch may have a number average molecular weight ranging from about 50,000 to about 1 ,000,000 grams per mole, in some embodiments from about 75,000 to about 800,000 grams per mole, and in some embodiments, from about 100,000 to about 600,000 grams per mole. The polydispersity index may be from about 0.5 to about 20, in some embodiments from about 1 to about 15, and in some embodiments, from about 2 to about 10. The thermoplastic starch may also have an apparent melt viscosity of from about 50 to about 800 Pascal seconds (Pa-s), in some embodiments from about 100 to about 700 Pa-s, and in some embodiments, from about 200 to about 600 Pa-s, as determined at a temperature of 1500C and a shear rate of 100 sec"1. The melt flow index of the thermoplastic starch may range from about 0.1 to about 30 grams per 10 minutes, in some embodiments from about 0.5 to about 10 grams per 10 minutes, and in some embodiments, from about 1 to about 5 grams per 10 minutes. The melt flow index is the weight of a polymer (in grams) that may be forced through an extrusion rheometer orifice (0.0825-inch diameter) when subjected to a load of 2160 grams in 10 minutes at a certain temperature (e.g., 1700C), measured in accordance with ASTM Test Method D1238-E. Of course, the meit flow index of the thermoplastic starch will ultimately depend upon the selected forming process. For example, when extruded as a cast film, higher melt flow index polymers are typically desired, such as about 4 grams per 10 minutes or more, in some embodiments, from about 5 to about 12 grams per 10 minutes, and in some embodiments, from about 7 to about 9 grams per 10 minutes. Likewise, when formed as a blown film, lower melt flow index polymers are typically desired, such as less than about 12 grams per 10 minutes or less, in some embodiments from about 1 to about 7 grams per 10 minutes, and in some embodiments, from about 2 to about 5 grams per 10 minutes. III. Melt-Extruded Substrates
The thermoplastic starch of the present invention may be incorporated into any known melt-extruded substrate, such as films, nonwoven webs (e.g., spunbond webs, meltblown webs, and so forth), etc. The substrate may contain a single layer or multiple layers and may also contain additional materials such that it is considered a composite. Regardless, in certain embodiments, the thermoplastic starch may constitute at least about 50 wt.%, in some embodiments from about 60 wt.% to about 99 wt.%, and in some embodiments, from about 75 to about 95 wt.% of the polymer content of the substrate. In other embodiments, other polymer(s) may be employed to impart certain properties to the substrate (e.g., strength, solubility, etc.). In such cases, the thermoplastic starch may constitute from about 10 wt.% to about 80 wt.%, in some embodiments from about 20 wt.% to about 70 wt.%, and in some embodiments, from about 30 to about 60 wt.% of the polymer content of the substrate, while such additional polymer(s) typically constitute from about 10 wt.% to about 80 wt.%, in some embodiments from about 20 wt.% to about 70 wt.%, and in some embodiments, from about 30 to about 60 wt.% of the polymer content of the substrate.
In one embodiment, for example, the substrate may include one or more bioldegradable polyesters. The term "biodegradable" generally refers to a material that degrades from the action of naturally occurring microorganisms, such as bacteria, fungi, and algae; environmental heat; moisture; or other environmental factors, such as determined according to ASTM Test Method 5338.92. The biodegradable polyesters employed in the present invention typically have a relatively low glass transition temperature ("T9") to reduce stiffness of the substrate and improve the processability of the polymers. For example, the T9 may be about 25°C or less, in some embodiments about 00C or less, and in some embodiments, about -1 O0C or less. Likewise, the melting point of the biodegradable polyesters is also relatively low to improve the rate of biodegradation. For example, the melting point is typically from about 500C to about 18O0C, in some embodiments from about 800C to about 16O0C, and in some embodiments, from about 1000C to about 14O0C. The melting temperature and glass transition temperature may be determined using differential scanning calorimetry ("DSC") in accordance with ASTM D-3417 as is well known in the art. Such tests may be employed using a DSC Q100 Differential Scanning Calorimeter (outfitted with a liquid nitrogen cooling accessory) and with a THERMAL ADVANTAGE (release 4.6.6) analysis software program, which are available from T.A. Instruments Inc. of New Castle, Delaware. The biodegradable polyesters may also have a number average molecular weight ("Mn") ranging from about 40,000 to about 120,000 grams per mole, in some embodiments from about 50,000 to about 100,000 grams per mole, and in some embodiments, from about 60,000 to about 85,000 grams per mole. Likewise, the polyesters may also have a weight average molecular weight ("Mw") ranging from about 70,000 to about 300,000 grams per mole, in some embodiments from about 80,000 to about 200,000 grams per mole, and in some embodiments, from about 100,000 to about 150,000 grams per mole. The ratio of the weight average molecular weight to the number average molecular weight ("Mw/Mn"), i.e., the "polydispersity index", is also relatively low. For example, the polydispersity index typically ranges from about 1.0 to about 4.0, in some embodiments from about 1.2 to about 3.0, and in some embodiments, from about 1.4 to about 2.0.
Examples of suitable biodegradable polyesters include aliphatic polyesters, such as polycaprolactone, polyesteramides, modified polyethylene terephthalate, polylactic acid (PLA) and its copolymers, terpolymers based on polylactic acid, polyglycolic acid, polyalkylene carbonates (such as polyethylene carbonate), polyhydroxyalkanoates (PHA), poly-3-hydroxybutyrate (PHB), poly-Shi yd roxy valerate (PHV), poiy-3-hydroxybutyrate-co-4-hydroybutyrate, poly-3- hydroxybutyrate-co-3-hydroxyvalerate copolymers (PHBV), poly-3- hydroxybutyrate-co-3-hydroxyhexanoate, ρoly-3-hydroxybutyrate-co-3- hydroxyoctanoate, poly-S-hydroxybutyrate-co-S-hydroxydecanoate, poly-3- hydroxybutyrate-co-3-hydroxyoctadecanoate, and succinate-based aliphatic polymers (e.g., polybutylene succinate, polybutylene succinate adipate, polyethylene succinate, etc.); aromatic polyesters and modified aromatic polyesters; and aliphatic-aromatic copolyesters. In one particular embodiment, the biodegradable polyester is an aliphatic-aromatic copolyester (e.g., block, random, graft, etc.). The aliphatic-aromatic copolyester may be synthesized using any known technique, such as through the condensation polymerization of a polyol in conjunction with aliphatic and aromatic dicarboxylic acids or anhydrides thereof. The polyols may be substituted or unsubstituted, linear or branched, polyols selected from polyols containing 2 to about 12 carbon atoms and polyalkylene ether glycols containing 2 to 8 carbon atoms. Examples of polyols that may be used include, but are not limited to, ethylene glycol, diethylene glycol, propylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, 2,2-dimethyl-1 ,3-propanediol, 1 ,2- butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,2-pentanediol, 1 ,5-pentanediol, 1 ,6- hexanediol, polyethylene glycol, diethylene glycol, 2,2,4-trimethyl-1 ,6-hexanediol, thiodiethanol, 1 ,3-cyclohexanedimethanol, 1 ,4-cyclohexanedimethanol, 2,2,4,4- tetramethyl-1 ,3-cyclobutanediol, cyclopentanediol, triethylene glycol, and tetraethylene glycol. Preferred polyols include 1 ,4-butanediol; 1 ,3-propanediol; ethylene glycol; 1 ,6-hexanediol; diethylene glycol; and 1 ,4-cyclohexanedimethanol.
Representative aliphatic dicarboxylic acids that may be used include substituted or unsubstituted, linear or branched, non-aromatic dicarboxylic acids selected from aliphatic dicarboxylic acids containing 1 to about 10 carbon atoms, and derivatives thereof. Non-limiting examples of aliphatic dicarboxylic acids include malonic, malic, succinic, oxalic, glutaric, adipic, pimelic, azelaic, sebacic, fumaric, 2,2-dimethyl glutaric, suberic, 1 ,3-cyclopentanedicarboxylic, 1 ,4- cyclohexanedicarboxylic, 1 ,3-cyclohexanedicarboxylic, diglycolic, itaconic, maleic, and 2,5-norbomanedicarboxylic. Representative aromatic dicarboxylic acids that may be used include substituted and unsubstituted, linear or branched, aromatic dicarboxylic acids selected from aromatic dicarboxylic acids containing 8 or more carbon atoms, and derivatives thereof. Non-limiting examples of aromatic dicarboxylic acids include terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, 2,6-napthalene dicarboxyiic acid, dimethyi-2,6- naphthalate, 2,7-naphthalenedicarboxylic acid, dimethyl-2,7-naphthalate, 3,4'- diphenyl ether dicarboxylic acid, dimethyl-3,4'diphenyl ether dicarboxylate, 4,4'- diphenyl ether dicarboxylic acid, dimethyl-4,4'-diphenyl ether dicarboxylate, 3,4'- diphenyl sulfide dicarboxylic acid, dimethyl-3,4'-diphenyl sulfide dicarboxylate, 4,4'- diphenyl sulfide dicarboxylic acid, dimethyl-4,4'-diphenyl sulfide dicarboxylate, 3,4'- diphenyl sulfone dicarboxylic acid, dimethyl-3,4'-diphenyl sulfone dicarboxylate, 4,4'-diphenyl sulfone dicarboxylic acid, dimethyl-4,4'-diphenyl sulfone dicarboxylate, 3,4'-benzophenonedicarboxylic acid, dimethyl-3,4'- benzophenonedicarboxylate, 4,4'-benzophenonedicarboxylic acid, dimethyl-4,4'- benzophenonedicarboxylate, 1 ,4-naphthalene dicarboxylic acid, dimethyl-1 ,4- naphthalate, 4,4'-methylene bis(benzoic acid), dimethyl-4,4'- methylenebis(benzoate), etc., and mixtures thereof. The polymerization may be catalyzed by a catalyst, such as a titanium- based catalyst (e.g., tetraisopropyltitanate, tetraisopropoxy titanium, dibutoxydiacetoacetoxy titanium, or tetrabutyltitanate). If desired, a diisocyanate chain extender may be reacted with the copolyester to increase its molecular weight. Representative diisocyanates may include toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthylene-1 ,5- diisocyanate, xylylene diisocyanate, methylene diphenyl isocyanate ("MDI"), hexamethylene diisocyanate ("HMDI"), isophorone diisocyanate and methylenebis(2-isocyanatocyclohexane). Trifunctional isocyanate compounds may also be employed that contain isocyanurate and/or biurea groups with a functionality of not less than three, or to replace the diisocyanate compounds partially by tri-or polyisocyanates. The preferred diisocyanate is hexamethylene diisocyanate. The amount of the chain extender employed is typically from about 0.3 to about 3.5 wt.%, in some embodiments, from about 0.5 to about 2.5 wt.% based on the total weight percent of the polymer. The copolyesters may either be a linear polymer or a long-chain branched polymer. Long-chain branched polymers are generally prepared by using a low molecular weight branching agent, such as a polyol, polycarboxylic acid, hydroxy acid, and so forth. Representative low molecular weight polyols that may be employed as branching agents include glycerol, trimethylolpropane, trimethyioiethane, polyethertriols, 1 ,2,4-butanetrioi, pentaerythritol, 1 ,2,6- hexanetriol, sorbitol, 1 ,1 ,4,4,-tetrakis (hydroxymethyl) cyclohexane, tris(2- hydroxyethyl) isocyanurate, and dipentaerythritol. Representative higher molecular weight polyols (molecular weight of 400 to 3000) that may be used as branching agents include triols derived by condensing alkylene oxides having 2 to 3 carbons, such as ethylene oxide and propylene oxide with polyol initiators. Representative polycarboxylic acids that may be used as branching agents include hemimellitic acid, trimellitic (1 ,2,4-benzenetricarboxylic) acid and anhydride, trimesic (1 ,3,5-benzenetricarboxylic) acid, pyromellitic acid and anhydride, benzenetetracarboxylic acid, benzophenone tetracarboxylic acid, 1 ,1 ,2,2-ethane- tetracarboxylic acid, 1 ,1 ,2-ethanetricarboxylic acid, 1 ,3,5-pentanetricarboxylic acid, and 1 ,2,3,4-cyclopentanetetracarboxylic acid. Representative hydroxy acids that may be used as branching agents include malic acid, citric acid, tartaric acid, 3- hydroxyglutaric acid, mucic acid, trihydroxyglutaric acid, 4-carboxyphthalic anhydride, hydroxyisophthalic acid, and 4-(beta-hydroxyethyl)phthalic acid. Such hydroxy acids contain a combination of 3 or more hydroxyl and carboxyl groups. Especially preferred branching agents include trimellitic acid, trimesic acid, pentaerythritol, trimethylol propane and 1 ,2,4-butanetriol. The aromatic dicarboxylic acid monomer constituent may be present in the copolyester in an amount of from about 10 mole% to about 40 mole%, in some embodiments from about 15 mole% to about 35 mole%, and in some embodiments, from about 15 mole% to about 30 mole%. The aliphatic dicarboxylic acid monomer constituent may likewise be present in the copolyester in an amount of from about 15 mole% to about 45 mole%, in some embodiments from about 20 mole% to about 40 mole%, and in some embodiments, from about 25 mole% to about 35 mole%. The polyol monomer constituent may also be present in the aliphatic-aromatic copolyester in an amount of from about 30 mole% to about 65 mole%, in some embodiments from about 40 mole% to about 50 mole%, and in some embodiments, from about 45 mole% to about 55 mole%.
In one particular embodiment, for example, the aliphatic-aromatic copolyester may comprise the following structure: O— (CH2)m— O—
Figure imgf000018_0001
wherein, m is an integer from 2 to 10, in some embodiments from 2 to 4, and in one embodiment, 4; n is an integer from 0 to 18, in some embodiments from 2 to 4, and in one embodiment, 4; p is an integer from 2 to 10, in some embodiments from 2 to 4, and in one embodiment, 4; x is an integer greater than 1 ; and y is an integer greater than 1. One example of such a copolyester is polybutylene adipate terephthalate, which is commercially available under the designation ECOFLEX® F BX 7011 from BASF Corp. Another example of a suitable copolyester containing an aromatic terephtalic acid monomer constituent is available under the designation ENPOL™ 8060M from IRE Chemicals (South Korea). Other suitable aliphatic-aromatic copolyesters may be described in U.S. Patent Nos. 5,292,783; 5,446,079; 5,559,171 ; 5,580,911 ; 5,599,858; 5,817,721 ; 5,900,322; and 6,258,924, which are incorporated herein in their entirety by reference thereto for all purposes.
If desired, the substrate may also include one or more water-soluble polymers. Such polymers may be formed from monomers such as vinyl pyrrolidone, hydroxyethyl acrylate or methacrylate (e.g., 2-hydroxyethyl methacrylate), hydroxypropyl acrylate or methacrylate, acrylic or methacrylic acid, acrylic or methacrylic esters or vinyl pyridine, acrylamide, vinyl acetate, vinyl alcohol (hydrolyzed from vinyl acetate), ethylene oxide, derivatives thereof, and so forth. Other examples of suitable monomers are described in U.S. Patent No.
4,499,154 to James, et al., which is incorporated herein in its entirety by reference thereto for all purposes. The resulting polymers may be homopolymers or interpolymers (e.g., copolymer, terpolymer, etc.), and may be nonionic, anionic, cationic, or amphoteric. In addition, the polymer may be of one type (i.e., homogeneous), or mixtures of different polymers may be used (i.e., heterogeneous). In one particular embodiment, the water-soluble polymer contains a repeating unit having a functional hydroxyl group, such as polyvinyl alcohol ("PVOH"), copolymers of polyvinyl alcohol (e.g., ethylene vinyl alcohol copolymers, methyl methacrylate vinyl alcohol copolymers, etc.), etc. Vinyl alcohol polymers, for instance, have at least two or more vinyl alcohol units in the molecule and may be a homopolymer of vinyl alcohol, or a copolymer containing other monomer units. Vinyl alcohol homopolymers may be obtained by hydrolysis of a vinyl ester polymer, such as vinyl formate, vinyl acetate, vinyl propionate, etc. Vinyl alcohol copolymers may be obtained by hydrolysis of a copolymer of a vinyl ester with an olefin having 2 to 30 carbon atoms, such as ethylene, propylene, 1- butene, etc.; an unsaturated carboxylic acid having 3 to 30 carbon atoms, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, etc., or an ester, salt, anhydride or amide thereof; an unsaturated nitrile having 3 to 30 carbon atoms, such as acrylonitrile, methacrylonitrile, etc.; a vinyl ether having 3 to 30 carbon atoms, such as methyl vinyl ether, ethyl vinyl ether, etc.; and so forth. The degree of hydrolysis may be selected to optimize solubility, etc., of the polymer. For example, the degree of hydrolysis may be from about 60 mole% to about 95 mole%, in some embodiments from about 80 mole% to about 90 mole%, and in some embodiments, from about 85 mole% to about 89 mole%. Examples of suitable partially hydrolyzed polyvinyl alcohol polymers are available under the designation CELVOL™ 203, 205, 502, 504, 508, 513, 518, 523, 530, or 540 from Celanese Corp. Other suitable partially hydrolyzed polyvinyl alcohol polymers are available under the designation ELVANOL™ 50-14, 50-26, 50-42, 51-03, 51-04, 51-05, 51-08, and 52-22 from DuPont.
In addition to the components noted above, still other additives may also be incorporated into the substrate of the present invention, such as dispersion aids, melt stabilizers, processing stabilizers, heat stabilizers, light stabilizers, antioxidants, heat aging stabilizers, whitening agents, antiblocking agents, bonding agents, lubricants, fillers, etc. Dispersion aids, such as described above, may be employed to help create a uniform dispersion of a thermoplastic starch and other polymers and retard or prevent separation into constituent phases. Likewise, the dispersion aids may also improve the water dispersibility of the substrate. When employed, the dispersion aid(s) typically constitute from about 0.01 wt.% to about 15 wt.%, in some embodiments from about 0.1 wt.% to about 10 wt.%, and in some embodiments, from about 0.5 wt.% to about 5 wt.% of the substrate.
Fillers may aiso be employed in the substrate of the present invention. Fillers are particulates or other forms of material that may be added to the substrate polymer extrusion blend and that will not chemically interfere with the extruded substrate, but which may be uniformly dispersed throughout the substrate. Fillers may serve a variety of purposes, including enhancing opacity and/or breathability (i.e., vapor-permeable and substantially liquid-impermeable). For instance, filled films may be made breathable by stretching, which causes the polymer to break away from the filler and create microporous passageways. Breathable microporous films are described, for example, in U.S. Patent Nos.
5,997,981 ; 6,015,764; and 6,111 ,163 to McCormack, et al.; 5,932,497 to Morman, et al.; 6,461 ,457 to Taylor, et al., which are incorporated herein in their entirety by reference thereto for all purposes. Further, hindered phenols are commonly used as an antioxidant in the production of substrates. Some suitable hindered phenols include those available from Ciba Specialty Chemicals under the trade name "Irganox®", such as Irganox® 1076, 1010, or E 201. Moreover, bonding agents may also be added to the substrate to facilitate bonding of the substrate to additional materials (e.g., nonwoven webs). Examples of such bonding agents include hydrogenated hydrocarbon resins. Other suitable bonding agents are described in U.S. Patent Nos. 4,789,699 to Kieffer et al. and 5,695,868 to
McCormack, which are incorporated herein in their entirety by reference thereto for all purposes.
Various known techniques may be employed to form the melt-extruded substrate of the present invention. For example, a film may be formed by blowing, casting, flat die extruding, etc., a compounded material as is known in the art. In one particular embodiment, the film may be formed by a blown process in which a gas (e.g., air) is used to expand a bubble of the extruded polymer blend through an annular die. The bubble is then collapsed and collected in flat film form. Processes for producing blown films are described, for instance, in U.S. Patent Nos. 3,354,506 to Ralev; 3,650,649 to Schippers; and 3,801 ,429 to Schrenk et al., as well as U.S. Patent Application Publication Nos. 2005/0245162 to McCormack, et al. and 2003/0068951 to Boggs, et al., all of which are incorporated herein in their entirety by reference thereto for all purposes. In yet another embodiment, however, the film is formed using a casting technique.
Referring to Fig. 1 , for instance, one embodiment of a method for forming a cast film is shown. The raw materials may be supplied to a melt blending device, either separately or as a blend. If desired, the thermoplastic starch may be formed in the manner described above as the film is cast. Alternatively, the thermoplastic starch may be pre-formed and thereafter supplied to the melt blending device for formation of the film. In the particular embodiment of Fig. 1 , the compounded material (not shown) is supplied to an extrusion apparatus 80 and cast onto a casting roll 90 to form a single-layered precursor film 10a. If a multilayered film is to be produced, the multiple layers are co-extruded together onto the casting roll 90. The casting roll 90 may optionally be provided with embossing elements to impart a pattern to the film. Typically, the casting roll 90 is kept at temperature sufficient to solidify and quench the sheet 10a as it is formed, such as from about 20 to 600C. If desired, a vacuum box may be positioned adjacent to the casting roll 90 to help keep the precursor film 10a close to the surface of the roll 90. Additionally, air knives or electrostatic pinners may help force the precursor film 10a against the surface of the casting roll 90 as it moves around a spinning roll. An air knife is a device known in the art that focuses a stream of air at a very high flow rate to pin the edges of the film. Once cast, the film 10a may then be optionally oriented in one or more directions to further improve film uniformity and reduce thickness. Orientation may also form micropores in a film containing a filler, thus providing breathability to the film. For example, the film may be immediately reheated to a temperature below the melting point of one or more polymers in the film, but high enough to enable the composition to be drawn or stretched. In the case of sequential orientation, the "softened" film is drawn by rolls rotating at different speeds of rotation such that the sheet is stretched to the desired draw ratio in the longitudinal direction (machine direction). This "uniaxially" oriented film may then be laminated to a fibrous web. In addition, the uniaxially oriented film may also be oriented in the cross-machine direction to form a "biaxially oriented" film. For example, the film may be clamped at its lateral edges by chain clips and conveyed into a tenter oven. In the tenter oven, the film may be reheated and drawn in the cross-machine direction to the desired draw ratio by chain clips diverged in their forward travel. Referring again to Fig. 1 , for instance, one method for forming a uniaxially oriented film is shown, As illustrated, the precursor film 10a is directed to a film- orientation unit 100 or machine direction orienter ("MDO"), such as commercially available from Marshall and Willams, Co. of Providence, Rhode Island. The MDO has a plurality of stretching rolls (such as from 5 to 8) which progressively stretch and thin the film in the machine direction, which is the direction of travel of the film through the process as shown in Fig. 1. While the MDO 100 is illustrated with eight rolls, it should be understood that the number of rolls may be higher or lower, depending on the level of stretch that is desired and the degrees of stretching between each roll. The film may be stretched in either single or multiple discrete stretching operations. It should be noted that some of the rolls in an MDO apparatus may not be operating at progressively higher speeds. If desired, some of the rolls of the MDO 100 may act as preheat rolls. If present, these first few rolls heat the film 10a above room temperature (e.g., to 1250F). The progressively faster speeds of adjacent rolls in the MDO act to stretch the film 10a. The rate at which the stretch rolls rotate determines the amount of stretch in the film and final film weight.
The resulting film 10b may then be wound and stored on a take-up roll 60. While not shown here, various additional potential processing and/or finishing steps known in the art, such as slitting, treating, aperturing, printing graphics, or lamination of the film with other layers (e.g., nonwoven web materials), may be performed without departing from the spirit and scope of the invention.
The thickness of the resulting melt-extruded substrate may generally vary depending upon the desired use. Nevertheless, the substrate typically has a thickness of about 150 micrometers or less, in some embodiments from about 10 to about 100 micrometers, and in some embodiments, from about 5 to about 80 micrometers. Despite having such a small thickness, the substrate is nevertheless able to retain good dry mechanical properties during use. One parameter that is indicative of the relative dry strength is the ultimate tensile strength, which is equal to the peak stress obtained in a stress-strain curve. Desirably, the substrate exhibits an ultimate tensile strength in the machine direction ("MD") of from about 5 to about 80 Megapascals (MPa), in some embodiments from about 10 to about 60 MPa, and in some embodiments, from about 15 to about 50 MPa, and an ultimate tensile strength in the cross-machine direction ("CD") of from about 1 to about 40 Megapascals (MPa), in some embodiments from about 2 to about 40 MPa, and in some embodiments, from about 5 to about 30 MPa. Although possessing good strength, it is also desirable that the substrate is not too stiff. One parameter that is indicative of the relative stiffness of the substrate (when dry) is Young's modulus of elasticity, which is equal to the ratio of the tensile stress to the tensile strain and is determined from the slope of a stress-strain curve. For example, the substrate typically exhibits a Young's modulus in the machine direction ("MD") of from about 20 to about 800 Megapascals ("MPa"), in some embodiments from about 50 to about 500 MPa, and in some embodiments, from about 100 to about 500 MPa, and a Young's modulus in the cross-machine direction ("CD") of from about 5 to about 250 Megapascals ("MPa"), in some embodiments from about 10 to about 200 MPa, and in some embodiments, from about 20 to about 150 MPa. The MD and CD elongation of the substrate may also be about 100% or more, in some embodiments about 200% or more, and in some embodiments, about 300% or more. Furthermore, the substrate may also be water-sensitive (e.g., water-soluble, water-dispersible, etc.) in that it loses integrity over time in the presence of water.
The melt-extruded substrate of the present invention may be used in a wide variety of applications. For example, as indicated above, the substrate may be used in an absorbent article. An "absorbent article" generally refers to any article capable of absorbing water or other fluids. Examples of some absorbent articles include, but are not limited to, personal care absorbent articles, such as diapers, training pants, absorbent underpants, incontinence articles, feminine hygiene products (e.g., sanitary napkins, pantiliners, etc.), swim wear, baby wipes, and so forth; medical absorbent articles, such as garments, fenestration materials, underpads, bedpads, bandages, absorbent drapes, and medical wipes; food service wipers; clothing articles; and so forth. Several examples of such absorbent articles are described in U.S. Patent Nos. 5,649,916 to DiPalma, et al.; 6,1 10,158 to Kielpikowski; 6,663,611 to Blaney, et al., which are incorporated herein in their entirety by reference thereto for all purposes. Still other suitable articles are described in U.S. Patent Application Publication No. 2004/0060112 A1 to Fell, et aL, as well as U.S. Patent Nos. 4,886,512 to Damico, et al.; 5,558,659 to Sherrod et al.; 6,888,044 to Fell, et al.; and 6,511 ,465 to Freiburqer et al.. all of which are incorporated herein in their entirety by reference thereto for all purposes. Materials and processes suitable for forming such absorbent articles are well known to those skilled in the art.
As is well known in the art, the absorbent article may be provided with adhesives (e.g., pressure-sensitive adhesives) that help removably secure the article to the crotch portion of an undergarment and/or wrap up the article for disposal. Suitable pressure-sensitive adhesives, for instance, may include acrylic adhesives, natural rubber adhesives, tackified block copolymer adhesives, polyvinyl acetate adhesives, ethylene vinyl acetate adhesives, silicone adhesives, polyurethane adhesives, thermosettable pressure-sensitive adhesives, such as epoxy acrylate or epoxy polyester pressure-sensitive adhesives, etc. Such pressure-sensitive adhesives are known in the art and are described in the Handbook of Pressure Sensitive Adhesive Technology, Satas (Donatas), 1989, 2nd edition, Van Nostrand Reinhold. The pressure sensitive adhesives may also include additives such as cross-linking agents, fillers, gases, blowing agents, glass or polymeric microspheres, silica, calcium carbonate fibers, surfactants, and so forth. The additives are included in amounts sufficient to affect the desired properties.
The location of the adhesive on the absorbent article is not critical and may vary widely depending on the intended use of the article. For example, certain feminine hygiene products (e.g., sanitary napkins) may have wings or flaps that laterally from a central absorbent core and are intended to be folded around the edges of the wearer's panties in the crotch region. The flaps may be provided with an adhesive (e.g., pressure-sensitive adhesive) for affixing the flaps to the underside of the wearer's panties.
Regardless of the particular location of the adhesive, however, a release liner may be employed to cover the adhesive, thereby protecting it from dirt, drying out, and premature sticking prior to use. The release liner may contain a release coating that enhances the ability of the liner to be peeled from an adhesive. The release coating contains a release agent, such as a hydrophobic polymer. Exemplary hydrophobic polymers include, for instance, silicones (e.g., polysiloxanes, epoxy silicones, etc.), perfluoroethers, fluorocarbons, polyurethanes, and so forth. Examples of such release agents are described, for instance, in U.S. Patent Nos. 6,530,910 to Pomplun, et al.; 5,985,396 to Kerins, et ai.; and 5,981 ,012 to Pomplun, et ai., which are incorporated herein in their entirety by reference thereto for all purposes. One particularly suitable release agent is an amorphous polyolefin having a melt viscosity of about 400 to about 10,000 cps at 1900C, such as made by the U.S. Rexene Company under the tradename
REXTAC® (e.g., RT2315, RT2535 and RT2330). The release coating may also contain a detackifier, such as a low molecular weight, highly branched polyolefin. A particularly suitable low molecular weight, highly branched polyolefin is VYBAR® 253, which is made by the Petrolite Corporation. Other additives may also be employed in the release coating, such as compatibilizers, processing aids, plasticizers, tackifiers, slip agents, and antimicrobial agents, and so forth. The release coating may be applied to one or both surfaces of the liner, and may cover all or only a portion of a surface. Any suitable technique may be employed to apply the release coating, such as solvent-based coating, hot melt coating, solventless coating, etc. Solvent-based coatings are typically applied to the release liner by processes such as roll coating, knife coating, curtain coating, gravure coating, wound rod coating, and so forth. The solvent (e.g., water) is then removed by drying in an oven, and the coating is optionally cured in the oven. Solventless coatings may include solid compositions, such as silicones or epoxy silicones, which are coated onto the liner and then cured by exposure to ultraviolet light. Optional steps include priming the liner before coating or surface modification of the liner, such as with corona treatment. Hot melt coatings, such as polyethylenes or perfluoroethers, may be heated and then applied through a die or with a heated knife. Hot melt coatings may be applied by co-extruding the release agent with the release liner in blown film or sheet extruder for ease of coating and for process efficiency.
To facilitate its ability to be easily disposed, the release liner may be formed from a melt-extruded substrate (e.g., film) in accordance with the present invention. In this regard, one particular embodiment of a sanitary napkin that may employ the substrate of the present invention will now be described in more detail. For purposes of illustration only, an absorbent article 20 is shown in Fig. 5 as a sanitary napkin for feminine hygiene. In the illustrated embodiment, the absorbent article 20 includes a main body portion 22 containing a topsheet 40, an outer cover or backsheet 42, an absorbent core 44 positioned between the backsheet 42 and the topsheet 40, and a pair of flaps 24 extending from each longitudinal side 22a of the main body portion 22. The topsheet 40 defines a bodyfacing surface of the absorbent article 20. The absorbent core 44 is positioned inward from the outer periphery of the absorbent article 20 and includes a body-facing side positioned adjacent the topsheet 40 and a garment-facing surface positioned adjacent the backsheet 42.
The topsheet 40 is generally designed to contact the body of the user and is liquid-permeable. The topsheet 40 may surround the absorbent core 44 so that it completely encases the absorbent article 20. Alternatively, the topsheet 40 and the backsheet 42 may extend beyond the absorbent core 44 and be peripherally joined together, either entirely or partially, using known techniques. Typically, the topsheet 40 and the backsheet 42 are joined by adhesive bonding, ultrasonic bonding, or any other suitable joining method known in the art. The topsheet 40 is sanitary, clean in appearance, and somewhat opaque to hide bodily discharges collected in and absorbed by the absorbent core 44. The topsheet 40 further exhibits good strike-through and rewet characteristics permitting bodily discharges to rapidly penetrate through the topsheet 40 to the absorbent core 44, but not allow the body fluid to flow back through the topsheet 40 to the skin of the wearer. For example, some suitable materials that may be used for the topsheet 40 include nonwoven materials, perforated thermoplastic films, or combinations thereof. A nonwoven fabric made from polyester, polyethylene, polypropylene, bicomponent, nylon, rayon, or like fibers may be utilized. For instance, a white uniform spunbond material is particularly desirable because the color exhibits good masking properties to hide menses that has passed through it. U.S. Patent No. 4,801 ,494 to Datta, et al. and U.S. Patent No. 4,908,026 to Sukiennik, et al. teach various other cover materials that may be used in the present invention.
The topsheet 40 may also contain a plurality of apertures (not shown) formed therethrough to permit body fluid to pass more readily into the absorbent core 44. The apertures may be randomly or uniformly arranged throughout the topsheet 40, or they may be located only in the narrow longitudinal band or strip arranged along the longitudinal axis X--X of the absorbent article 20. The apertures permit rapid penetration of body fluid down into the absorbent core 44. The size, shape, diameter and number of apertures may be varied to suit one's particular needs.
As stated above, the absorbent article also includes a backsheet 42. The backsheet 42 is generally liquid-impermeable and designed to face the inner surface, i.e., the crotch portion of an undergarment (not shown). The backsheet 42 may permit a passage of air or vapor out of the absorbent article 20, while still blocking the passage of liquids. Any liquid-impermeable material may generally be utilized to form the backsheet 42. For example, one suitable material that may be utilized is a microembossed polymeric film, such as polyethylene or polypropylene. In particular embodiments, a polyethylene film is utilized that has a thickness in the range of about 0.2 mils to about 5.0 mils, and particularly between about 0.5 to about 3.0 mils.
The absorbent article 20 also contains an absorbent core 44 positioned between the topsheet 40 and the backsheet 42. The absorbent core 44 may be formed from a single absorbent member or a composite containing separate and distinct absorbent members. It should be understood, however, that any number of absorbent members may be utilized in the present invention. For example, in one embodiment, the absorbent core 44 may contain an intake member (not shown) positioned between the topsheet 40 and a transfer delay member (not shown). The intake member may be made of a material that is capable of rapidly transferring, in the z-direction, body fluid that is delivered to the topsheet 40. The intake member may generally have any shape and/or size desired. In one embodiment, the intake member has a rectangular shape, with a length equal to or less than the overall length of the absorbent article 20, and a width less than the width of the absorbent article 20. For example, a length of between about 150 mm to about 300 mm and a width of between about 10 mm to about 60 mm may be utilized.
Any of a variety of different materials may be used for the intake member to accomplish the above-mentioned functions. The material may be synthetic, cellulosic, or a combination of synthetic and cellulosic materials. For example, airlaid cellulosic tissues may be suitable for use in the intake member. The airlaid cellulosic tissue may have a basis weight ranging from about 10 grams per square meter (gsm) to about 300 gsm, and in some embodiments, between about 100 gsm to about 250 gsm. In one embodiment, the airlaid cellulosic tissue has a basis weight of about 200 gsm. The airlaid tissue may be formed from hardwood and/or softwood fibers. The airlaid tissue has a fine pore structure and provides an excellent wicking capacity, especially for menses. If desired, a transfer delay member (not shown) may be positioned vertically below the intake member. The transfer delay member may contain a material that is less hydrophilic than the other absorbent members, and may generally be characterized as being substantially hydrophobic. For example, the transfer delay member may be a nonwoven fibrous web composed of a relatively hydrophobic material, such as polypropylene, polyethylene, polyester or the like, and also may be composed of a blend of such materials. One example of a material suitable for the transfer delay member is a spunbond web composed of polypropylene, multi- lobal fibers. Further examples of suitable transfer delay member materials include spunbond webs composed of polypropylene fibers, which may be round, tri-lobal or poly-lobal in cross-sectional shape and which may be hollow or solid in structure. Typically the webs are bonded, such as by thermal bonding, over about 3% to about 30% of the web area. Other examples of suitable materials that may be used for the transfer delay member are described in U.S. Patent No. 4,798,603 to Meyer, et al. and U.S. Patent No. 5,248,309 to Serbiak, et al.. which are incorporated herein in their entirety by reference thereto for all purposes. To adjust the performance of the invention, the transfer delay member may also be treated with a selected amount of surfactant to increase its initial wettability.
The transfer delay member may generally have any size, such as a length of about 150 mm to about 300 mm. Typically, the length of the transfer delay member is approximately equal to the length of the absorbent article 20. The transfer delay member may also be equal in width to the intake member, but is typically wider. For example, the width of the transfer delay member may be from between about 50 mm to about 75 mm, and particularly about 48 mm. The transfer delay member typically has a basis weight less than that of the other absorbent members. For example, the basis weight of the transfer delay member is typically less than about 150 grams per square meter (gsm), and in some embodiments, between about 10 gsm to about 100 gsm. In one particular embodiment, the transfer delay member is formed from a spunbonded web having a basis weight of about 30 gsm.
Besides the above-mentioned members, the absorbent core 44 may aiso include a composite absorbent member (not shown), such as a coform material. In this instance, fluids may be wicked from the transfer delay member into the composite absorbent member. The composite absorbent member may be formed separately from the intake member and/or transfer delay member, or may be formed simultaneously therewith. In one embodiment, for example, the composite absorbent member may be formed on the transfer delay member or intake member, which acts a carrier during the coform process described above. Regardless of its particular construction, the absorbent article 20 typically contains an adhesive for securing to an undergarment. An adhesive may be provided at any location of the absorbent article 20, such as on the lower surface of the backsheet 42. In this particular embodiment, the backsheet 42 carries a longitudinally central strip of garment adhesive 54 covered before use by a peelable release liner 58, which may be formed in accordance with the present invention. Each of the flaps 24 may also contain an adhesive 56 positioned adjacent to the distal edge 34 of the flap 24. A peelable release liner 57, which may also be formed in accordance with the present invention, may cover the adhesive 56 before use. Thus, when a user of the sanitary absorbent article 20 wishes to expose the adhesives 54 and 56 and secure the absorbent article 20 to the underside of an undergarment, the user simply peels away the liners 57 and 58 and disposed them in a water-based disposal system (e.g., in a toilet).
Although various configurations of a release liner have been described above, it should be understood that other release liner configurations are also included within the scope of the present invention. Further, the present invention is by no means limited to release liners and the melt-extruded substrate may be incorporated into a variety of different components of an absorbent article. For example, referring again to Fig. 5, the backsheet 42 of the napkin 20 may include the melt-extruded substrate (e.g., film) of the present invention. In such embodiments, the substrate may be used alone to form the backsheet 42 or laminated to one or more additional materials, such as a nonwoven web. The melt-extruded substrate of the present invention may also be used in applications other than absorbent articles. For example, the substrate may be employed as an individual wrap, packaging pouch, or bag for the disposal of a variety of articles, such as food products, absorbent articles, etc. Various suitable pouch, wrap, or bag configurations for absorbent articles are disclosed, for instance, in U.S. Patent Nos. 6,716,203 to Sorebo, et al. and 6,380,445 to Moder, et al., as well as U.S. Patent Application Publication No. 2003/0116462 to Sorebo, et al., all of which are incorporated herein in their entirety by reference thereto for all purposes.
The present invention may be better understood with reference to the following examples.
Test Methods Apparent Melt Viscosity:
The Theological properties of polymer samples were determined using a Gottfert Rheograph 2003 capillary rheometer with WinRHEO version 2.31 analysis software. The setup included a 2000-bar pressure transducer and a 30/1 :0/180 roundhole capillary die. Sample loading was done by alternating between sample addition and packing with a ramrod. A 2-minute melt time preceded each test to allow the polymer to completely melt at a test temperature (1500C or 1600C). The capillary rheometer determined the apparent melt viscosity (Pa-s) at various shear rates, such as 100, 200, 500, 1000, 2000, and 4000 s"1. The resultant rheology curve of apparent shear rate versus apparent melt viscosity gave an indication of how the polymer would run at that temperature in an extrusion process. Tensile Properties:
The strip tensile strength values were determined in substantial accordance with ASTM Standard D-5034. A constant-rate-of-extension type of tensile tester was employed. The tensile testing system was a Sintech 1/D tensile tester, which is available from Sintech Corp. of Cary, North Carolina. The tensile tester was equipped with TESTWORKS 4.08B software from MTS Corporation to support the testing. An appropriate load cell was selected so that the tested value fell within the range of 10-90% of the full scale load. The film samples were initially cut into dog-bone shapes with a center width of 3.0 mm before testing. The samples were held between grips having a front and back face measuring 25.4 millimeters x 76 millimeters. The grip faces were rubberized, and the longer dimension of the grip was perpendicular to the direction of pull. The grip pressure was pneumatically maintained at a pressure of 40 pounds per square inch. The tensile test was run using a gauge length of 18.0 millimeters and a break sensitivity of 40%. Five samples were tested by applying the test load along the machine-direction and five samples were tested by applying the test load along the cross direction. During the test, samples were stretched at a crosshead speed of abut 127 millimeters per minute until breakage occurred. The modulus, peak stress, and elongation were measured in the machine direction ("MD") and cross-machine directions ("CD"). Water Disintegration Test:
The rate of film disintegration in tap water was tested using a "slosh box", which has a physical dimension of a 14" x 18" x 12" high plastic box on a hinged platform. One end of the platform is attached to the reciprocating cam. The typical amplitude is ± 2" (4" range), with sloshing occurring at 0.5 -1.5 sloshes per second. The preferred action is 0.9 ~ 1.3 sloshes per second. During a test, the slosh box rocks up and down with the water inside, "sloshing" back and forth. This action produces a wave front and intermittent motion on a sample susceptible to dispersing in water. To quantify a measurement of sample film disintegration in water, without image analysis, simply timing is sufficient. Three liters of tap water were added into the slosh box and resulted in ~ 5.5" water depth in the box. A frequency of 3.5 was selected for the testing. Each film sample was cut into 1"x 3" size. Three pieces were dropped into the slosh box. The time to disintegrate the sample under the defined conditions was recorded twice for each sample. The average of the time to the sample disintegration is then reported. Generally, films reach an acceptable dispersion point when no piece is larger than 25 mm2 in size within 6 hours of agitation.
EXAMPLE 1 A thermoplastic starch containing a native starch and a plasticizer was formed as follows. Initially, 2% Excel P-40S (mono-di-glyceride, Kao Corp. of Japan) was dry mixed with native corn starch (Cargill, Inc., Minneapolis, Minnesota) in a kitchen mixer and then added to a K-Tron gravimetric feeder (Model KCL-QX4, K-Tron North America, Pitman, NY) that fed the material into a Thermo Prism™ LJSALAB 16 twin screw extruder (Thermo Electron Corp., Stone, England). The extruder had 11 zones, numbered consecutively 0-10 from the feed hopper to the die. The temperature profile of zones 1 to 10 of the extruder was 7O0C, 8O0C, 1000C, 1400C, 14O0C, 140°C, 1200C, 100°C, 800C, and 6O0C, respectively. The screw speed was set at 170 rpm to achieve a torque of between 60-75% during the processing. The starch feeding rate was fixed at 15 grams per minute at 20 rpm with an agitator. The starch was fed to the feed throat of the extruder (un-heated, before zone 1 of the extruder). Glycerol (98% purity, Cognis Corporation, Cincinnati, Ohio) was injected into zone 1 of the extruder using a plasticizer gear pump (Bodine Electric Company, Grand Island, New York). The liquid pump rate was manually fixed at 4 grams per minute at 30 rpm and 5.8 grams per minute at 40 rpm. In some cases, a vent was also opened to release steam generated. The resulting strand cooled down through a cooling belt (Minarik Electric Company, Glendale, California). A pelletizer (Emerson Industrial Controls, Grand Island, New York) was used to cut the strand to produce thermoplastic starch pellets containing 30 wt.% glycerol.
EXAMPLE 2 A thermoplastic starch containing a native starch and a plasticizer was formed as described in Example 1 , except that a mixture of 80 wt.% glycerol (98% purity, Cognis Corp.) and 20 wt.% water was used as the plasticizer.
EXAMPLE 3
A thermoplastic starch was formed from a native starch, plasticizer, and weak organic acid as follows. Initially, 2% Excel P-40S was dry mixed with native corn starch (Cargill, Inc., Minneapolis, Minnesota) in a kitchen mixer and then added to a K-T ron gravimetric feeder (Model KCL-QX4, K-Tron) that fed the material into a Thermo Prism™ USALAB 16 twin screw extruder. The temperature profile of zones 1 to 10 of the extruder was 700C, 8O0C, 1000C, 140°C, 140°C, 140°C, 12O0C, 100°C, 80°C, and 60 0C, respectively. The screw speed was set at 170 rpm to achieve a torque of between 60-75% during the processing. The starch feeding rate was fixed at 15 grams per minute at 20 rpm with an agitator. The starch was fed to the feed throat of the extruder (un-heated, before zone 1 of the extruder). A mixture of 50 wt.% glycerol and 50 wt.% lactic acid (85% in water, Sigma-Aldrich, St. Louis, Missouri) was injected into zone 1 of the extruder using a plasticizer gear pump (Bodine Electric Company, Grand Island, New York). The liquid pump rate was manually fixed at 4 grams per minute at 30 rpm and 5.8 grams per minute at 40 rpm. In some cases, a vent was also opened to release steam generated. The resulting strand cooled down through a cooling belt (Minarik Electric Company, Glendale, California). A pelletizer (Emerson Industrial Controls, Grand island, New York) was used to cut the strand to produce thermoplastic starch pellets containing 10 wt.% glycerol and 10 wt.% lactic acid.
EXAMPLE 4 A thermoplastic starch was formed as described in Example 3, except that
100 wt.% lactic acid was injected into zone 1 of the extruder rather than a mixture of 50 wt.% glycerol and 50 wt.% lactic acid. The resulting thermoplastic modified starch contained 20 wt.% lactic acid.
EXAMPLE 5 A thermoplastic starch was formed as described in Example 3, except that a mixture of 25 wt.% acetic acid (Sigma-Aldrich, St. Louis, Missouri) and 75 wt.% glycerol was injected into zone 1 of the extruder rather than a mixture of 50 wt.% glycerol and 50 wt.% lactic acid. The resulting thermoplastic modified starch contained 5 wt.% acetic acid and 15 wt.% glycerol. EXAMPLE 6
A thermoplastic starch was formed as described in Example 3, except that a mixture of 50 wt.% formic acid (Sigma-Aldrich, St. Louis, Missouri) and 50 wt.% glycerol was injected into zone 1 of the extruder rather than a mixture of 50 wt.% glycerol and 50 wt.% lactic acid. The resulting thermoplastic modified starch contained 10 wt.% formic acid and 10 wt.% glycerol.
EXAMPLE 7
A thermoplastic starch containing a native starch and a plasticizer was formed as follows. Initially, 2% Excel P-40S was dry mixed with native potato starch (Penford Food Ingredients Co., Englewood, Colorado) in a kitchen mixer and then added to a K-T ron gravimetric feeder (Model KCL-QX4, K-T ron) that fed the material into a Thermo Prism™ USALAB 16 twin screw extruder. The temperature profile of zones 1 to 10 of the extruder was 9O0C, 100°C, 12O0C, 1300C, 12O0C, 115°C, 110°C, 1000C, 9O0C, and 60 0C, respectively. The screw speed was set at 170 rpm to achieve a torque of between 55-65% during the processing. The starch feeding rate was fixed at 15 grams per minute at 20 rpm with an agitator. The starch was fed to the feed throat of the extruder (un-heated, before zone 1 of the extruder). A mixture of 80 wt.% glycerol and 20 wt.% water was injected into zone 1 of the extruder using a plasticizer gear pump (Bodine Electric Company, Grand Island, New York). The liquid pump rate was manually fixed at 4 grams per minute at 30 rpm and 5.8 grams per minute at 40 rpm. In some cases, a vent was also opened to release steam generated. The resulting strand cooled down through a cooling belt (Minarik Electric Company, Glendale, California). A pelletizer (Emerson Industrial Controls, Grand Island, New York) was used to cut the strand to produce thermoplastic starch pellets containing 30 wt.% glycerol.
EXAMPLE 8 A thermoplastic starch was formed from a native starch, plasticizer, and weak organic acid as follows. Initially, 2% Excel P-40S was dry mixed with native potato starch (Penford Food Ingredients Co., Englewood, Colorado) in a kitchen mixer and then added into a K-T ron gravimetric feeder (Model KCL-QX4, K-T ron) that fed the material into a Thermo Prism™ USALAB 16 twin screw extruder. The temperature profile of zones 1 to 10 of the extruder was 900C, 1000C, 120°C, 1300C, 120°C, 115°C, 110°C, 1000C, 90°C, and 60 0C, respectively. The screw speed was set at 170 rpm to achieve a torque of between 55-65% during the processing. The starch feeding rate was fixed at 15 grams per minute at 20 rpm with an agitator. The starch was fed to the feed throat of the extruder (un-heated, before zone 1 of the extruder). A mixture of 50 wt.% glycerol (98% purity, Cognis Corporation, Cincinnati, Ohio) and 50 wt.% lactic acid was injected into zone 1 of the extruder using a plasticizer gear pump (Bodine Electric Company, Grand Island, New York). The liquid pump rate was manually fixed at 4 grams per minute at 30 rpm and 5.8 grams per minute at 40 rpm. In some cases, a vent was also opened to release steam generated. The resulting strand cooled down through a cooling belt (Minarik Electric Company, Glendale, California). A pelletizer
(Emerson Industrial Controls, Grand Island, New York) was used to cut the strand to produce thermoplastic starch pellets containing 10 wt.% glycerol and 10 wt.% lactic acid.
EXAMPLE 9 The molecular weight of the thermoplastic starches of Examples 1 -8 was determined using conventional gel permeation chromatography in DMSO (dimethyl sulfoxide) at elevated temperature (1000C) and with dextran as the reference standard. The resulting molecular weight distribution is set forth below in Table 1. Table 1 : Molecular Weight Distribution
Figure imgf000035_0001
As indicated, the weight average molecular weights decreased for both types of thermoplastic starches when processed with a weak organic acid and plasticizer. Quite surprisingly, however, the number average molecular weights of both the corn and potato thermoplastic starches increased after preparation.
EXAMPLE 10
The viscosity of the thermoplastic starches of Examples 1-4 was also determined as described above. The results are set forth in Fig. 2. As indicated, the resulting viscosity values for the thermoplastic starch made using 30% glycerol/water (80/20) were identical to those made using 30% glycerol, indicating there is no change in starch molecular weight distribution. However, when lactic acid was present (Examples 3 and 4), the resulting thermoplastic starch showed a remarkable decrease in melt viscosity, indicating breakdown or hydrolysis of starch macromolecule chains due to chemical modifications during melt blending.
EXAMPLE 11
The viscosity of the thermoplastic starches of Examples 5-6 was also determined as described above. The results are set forth in Fig. 3. As indicated, chemical modification by acetic acid was not as effective in comparison to formic acid in reducing the viscosity of the thermoplastic starch.
EXAMPLE 12
The viscosity of the thermoplastic starches of Examples 7-8 was also determined as described above. The results are set forth in Fig. 4. As indicated, the thermoplastic starch exhibited a significant viscosity reduction, indicating that apparent melt viscosity reduces further as the acidity of the organic acid increased.
EXAMPLE 13
Various combinations of the thermoplastic starch of Examples 2, 3, 5, 6, and 8 were compounded in a Carver Press (Carver Press, Inc., Wabash, Indiana) and formed into pressed films. The set pressure was 15,000 lbs, pump speed was set at 100%, and the holding time was 5 seconds. The film thicknesses ranged from about 2 to about 3 mils (about 50.8 to about 76.2 micrometers). Once formed, the films were subjected to the above-described water disintegration test. The results are set forth below in Table 2.
Table 2: Pressed Films and Their Cold Water Dispersibility
Figure imgf000036_0001
EXAMPLE 14
The ability to form a cast film with the thermoplastic starch of the present invention was demonstrated. The thermoplastic starch of Example 3 was dry blended in a HAAKE Rheomex 252 single screw extruder with an Ecoflex® F BX 7011 resin (BASF, Ludwigshafen, Germany) at weight percentages of 30 wt.% and 70 wt.%, respectively. The screw speed was set at 50 rpm and the temperature profile of the extruder from zone 1 to 5 was 1400C, 1500C, 150°C, 1460C, and 1370C, respectively. The melt temperature was 155°C. The resulting cast film was then conditioned at 25°C and 50% relative humidity over a weekend.
Thereafter, the mechanical properties of the film were tested as described above. The resulting film was determined to have a MD elongation of 688%, CD elongation of 447%, MD peak stress of 21 MPa, CD peak stress of 10 MPa, and MD Young's modulus of 146 MPa, and CD Young's modulus of 76 MPa. While the invention has been described in detail with respect to the specific embodiments thereof, it will be appreciated that those skilled in the art, upon attaining an understanding of the foregoing, may readily conceive of alterations to, variations of, and equivalents to these embodiments. Accordingly, the scope of the present invention should be assessed as that of the appended claims and any equivalents thereto.

Claims

WHAT IS CLAIMED IS:
1. A meit-extruded substrate comprising a thermoplastic starch formed from about 30 wt.% to about 95 wt.% of at least one starch, from about 1 wt.% to about 35 wt.% of at least one plasticizer, and from about 1 wt.% to about 35 wt.% of at least one weak organic acid, wherein the thermoplastic starch has a weight average molecular weight of from about 1 ,000,000 to about 5,000,000, polydispersity index of from about 0.5 to about 20, and apparent melt viscosity of from about 50 to about 800 Pascal-seconds, determined at a temperature of 15O0C and a shear rate of 100 sec"1.
2. The melt-extruded substrate of claim 1 , wherein the starch is a starch ester, starch ether, or a combination thereof.
3. The melt-extruded substrate of any of the foregoing claims, wherein the starch has an amylose content of from about 10% to about 40% by weight.
4. The melt-extruded substrate of any of the foregoing claims, wherein the starch includes corn starch, potato starch, or a combination thereof.
5. The melt-extruded substrate of any of the foregoing claims, wherein the starch has a weight average molecular weight of from about 5,000,000 to about 25,000,000 grams per mole and a polydispersity index of from about 10 to about 100.
6. The melt-extruded substrate of any of the foregoing claims, wherein the weak organic acid is a carboxylic acid.
7. The melt-extruded substrate of any of the foregoing claims, wherein the weak organic acid has an acid dissociation constant of from 1 to about 5, and preferably from 2 to about 4.
8. The melt-extruded substrate of any of the foregoing claims, wherein the plasticizer is a polyol.
9. The melt-extruded substrate of any of the foregoing claims, wherein the thermoplastic starch is formed from about 50 wt.% to about 85 wt.% of at least one starch, from about 5 wt.% to about 25 wt.% of at least one plasticizer, and at least from about 5 wt.% to about 25 wt.% of at least one weak organic acid.
10. The melt-extruded substrate of any of the foregoing claims, wherein the thermoplastic starch has a weight average molecular weight of from about 2,000,000 to about 3,500,000 grams per mole.
11. The meit-extruded substrate of any of the foregoing claims, wherein the thermopiastic starch has an apparent meit viscosity of from about 200 to about 600 Pascal seconds, as determined at a temperature of 15O0C and a shear rate of 100 sec"1.
12. The melt-extruded substrate of any of the foregoing claims, wherein the substrate further comprises at least one biodegradable polyester.
13. The melt-extruded substrate of any of the foregoing claims, wherein the substrate exhibits a dry ultimate tensile strength of from about 15 to about 50 Megapascals in the machine direction and a dry modulus of elasticity of from about 100 to about 500 Megapascals in the machine direction.
14. The melt-extruded substrate of any of the foregoing claims, wherein the substrate contains a nonwoven web.
15. The melt-extruded substrate of any of the foregoing claims, wherein the substrate contains a film.
16. The melt-extruded substrate of claim 15, wherein the film is water- sensitive.
17. A release liner comprising the substrate of claim 16 and a release agent coated onto a surface thereof.
18. An absorbent article comprising the melt-extruded substrate of any of the foregoing claims, wherein the absorbent article comprises a body portion that includes a liquid permeable topsheet, a generally liquid impermeable backsheet, and an absorbent core positioned between the backsheet and the topsheet.
19. The absorbent article of claim 18, wherein the backsheet includes the substrate.
20. A method for forming a substrate, the method comprising: melt blending a composition comprising from about 30 wt.% to about 95 wt.% of at least one starch, from about 1 wt.% to about 35 wt.% of at least one plasticizer, and from about 1 wt.% to about 35 wt.% of at least one weak organic acid to form a thermoplastic starch, wherein the thermoplastic starch has a weight average molecular weight of from about 1 ,000,000 to about 5,000,000, polydispersity index of from about 0.5 to about 20, and apparent melt viscosity of from about 50 to about 800 Pascal-seconds, determined at a temperature of 15O0C and a shear rate of 100 sec"1; and extruding the thermoplastic starch onto a surface to form a substrate.
21. The method of claim 20, wherein the starch includes corn starch, potato starch, or a combination thereof.
22. The method of claim 20, wherein the weak organic acid is a carboxylic acid.
23. The method of claim 20, wherein melt blending occurs at a temperature of from about 4O0C to about 16O0C, and preferably from about 600C to about 1400C.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012077005A3 (en) * 2010-12-07 2012-08-23 Kimberly-Clark Worldwide, Inc. Melt-blended protein composition
KR20190018172A (en) * 2010-12-08 2019-02-21 킴벌리-클라크 월드와이드, 인크. Elastic film containing a renewable starch polymer
WO2020136231A1 (en) * 2018-12-28 2020-07-02 Agrana Stärke Gmbh Compound or film containing thermoplastic starch and a thermoplastic polymer

Families Citing this family (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007050770A1 (en) * 2007-10-22 2009-04-23 Biotec Biologische Naturverpackungen Gmbh & Co. Kg Polymeric material and process for its preparation
US8227658B2 (en) 2007-12-14 2012-07-24 Kimberly-Clark Worldwide, Inc Film formed from a blend of biodegradable aliphatic-aromatic copolyesters
US8147965B2 (en) 2008-05-14 2012-04-03 Kimberly-Clark Worldwide, Inc. Water-sensitive film containing thermoplastic polyurethane
US8927617B2 (en) 2008-06-30 2015-01-06 Kimberly-Clark Worldwide, Inc. Fragranced water-sensitive film
US20100159777A1 (en) * 2008-12-18 2010-06-24 Kimberly-Clark Worldwide, Inc. Thermoplastic Starch Formed from an Enzymatically Debranched Starch
FR2947557B1 (en) * 2009-07-03 2011-12-09 Ulice PROCESS FOR PRODUCING BIODEGRADABLE MATERIAL
EP2467418B1 (en) * 2009-08-18 2017-06-28 National Research Council of Canada Process of producing thermoplastic starch/polymer blends
US8466337B2 (en) * 2009-12-22 2013-06-18 Kimberly-Clark Worldwide, Inc. Biodegradable and breathable film
CN102115576B (en) * 2009-12-31 2014-09-17 金伯利-克拉克环球有限公司 Natural biological polymer thermoplastic film
US20120000480A1 (en) 2010-06-30 2012-01-05 Sebastian Andries D Biodegradable cigarette filter
US8950407B2 (en) 2010-06-30 2015-02-10 R.J. Reynolds Tobacco Company Degradable adhesive compositions for smoking articles
MX2012015187A (en) 2010-07-02 2013-05-09 Procter & Gamble Method for delivering an active agent.
MX2012015174A (en) * 2010-07-02 2013-05-09 Procter & Gamble Filaments comprising an active agent nonwoven webs and methods for making same.
CA2803636C (en) 2010-07-02 2017-05-16 The Procter & Gamble Company Detergent product and method for making same
US20120016328A1 (en) * 2010-07-19 2012-01-19 Bo Shi Biodegradable films
US8524264B2 (en) * 2010-12-07 2013-09-03 Kimberly-Clark Worldwide, Inc. Protein stabilized antimicrobial composition formed by melt processing
US9832993B2 (en) 2010-12-07 2017-12-05 Kimberly-Clark Worldwide, Inc. Melt processed antimicrobial composition
US9648874B2 (en) 2010-12-07 2017-05-16 Kimberly-Clark Worldwide, Inc. Natural, multiple use and re-use, user saturated wipes
US8574628B2 (en) 2011-12-19 2013-11-05 Kimberly-Clark Worldwide, Inc. Natural, multiple release and re-use compositions
US20130154151A1 (en) * 2011-12-20 2013-06-20 Kimberly-Clark Worldwide, Inc. Method for Forming a Thermoplastic Composition that Contains a Renewable Biopolymer
US9327438B2 (en) 2011-12-20 2016-05-03 Kimberly-Clark Worldwide, Inc. Method for forming a thermoplastic composition that contains a plasticized starch polymer
US9718258B2 (en) 2011-12-20 2017-08-01 Kimberly-Clark Worldwide, Inc. Multi-layered film containing a biopolymer
US9085677B2 (en) 2012-01-23 2015-07-21 Erica Budina Bioplastics
TWI445755B (en) 2012-06-27 2014-07-21 Ind Tech Res Inst Flame-retardant thermoplastic starch material, bio-composite and manufacturing method thereof
US10920044B2 (en) 2015-06-30 2021-02-16 BiologiQ, Inc. Carbohydrate-based plastic materials with reduced odor
US11674014B2 (en) 2015-06-30 2023-06-13 BiologiQ, Inc. Blending of small particle starch powder with synthetic polymers for increased strength and other properties
US10752759B2 (en) 2015-06-30 2020-08-25 BiologiQ, Inc. Methods for forming blended films including renewable carbohydrate-based polymeric materials with high blow up ratios and/or narrow die gaps for increased strength
US11879058B2 (en) 2015-06-30 2024-01-23 Biologiq, Inc Yarn materials and fibers including starch-based polymeric materials
US20170002184A1 (en) 2015-06-30 2017-01-05 BiologiQ, Inc. Articles Formed with Biodegradable Materials and Strength Characteristics of Same
US11674018B2 (en) 2015-06-30 2023-06-13 BiologiQ, Inc. Polymer and carbohydrate-based polymeric material blends with particular particle size characteristics
US11111355B2 (en) 2015-06-30 2021-09-07 BiologiQ, Inc. Addition of biodegradability lending additives to plastic materials
US11046840B2 (en) 2015-06-30 2021-06-29 BiologiQ, Inc. Methods for lending biodegradability to non-biodegradable plastic materials
US11926940B2 (en) 2015-06-30 2024-03-12 BiologiQ, Inc. Spunbond nonwoven materials and fibers including starch-based polymeric materials
US11926929B2 (en) 2015-06-30 2024-03-12 Biologiq, Inc Melt blown nonwoven materials and fibers including starch-based polymeric materials
US11111363B2 (en) 2015-06-30 2021-09-07 BiologiQ, Inc. Articles formed with renewable and/or sustainable green plastic material and carbohydrate-based polymeric materials lending increased strength and/or biodegradability
US10919203B2 (en) 2015-06-30 2021-02-16 BiologiQ, Inc. Articles formed with biodegradable materials and biodegradability characteristics thereof
US10995201B2 (en) 2015-06-30 2021-05-04 BiologiQ, Inc. Articles formed with biodegradable materials and strength characteristics of the same
US11149144B2 (en) 2015-06-30 2021-10-19 BiologiQ, Inc. Marine biodegradable plastics comprising a blend of polyester and a carbohydrate-based polymeric material
US11359088B2 (en) 2015-06-30 2022-06-14 BiologiQ, Inc. Polymeric articles comprising blends of PBAT, PLA and a carbohydrate-based polymeric material
TWI787246B (en) * 2017-03-30 2022-12-21 日商日本瑞翁股份有限公司 Optical film, manufacturing method thereof, polarizing plate, and liquid crystal display device
CN109735076B (en) * 2019-01-23 2021-01-22 哈尔滨知明科技有限公司 Preparation method of high-performance bio-based/polylactic acid fully-degradable material
JP7381613B2 (en) 2019-06-28 2023-11-15 ザ プロクター アンド ギャンブル カンパニー Dissolvable solid fibrous article containing anionic surfactant
WO2021195087A1 (en) 2020-03-23 2021-09-30 Bay State Milling Company Rapid high amylose wheat seed purity test
WO2022027067A1 (en) 2020-07-31 2022-02-03 The Procter & Gamble Company Water-soluble fibrous pouch containing prills for hair care
CN112895204A (en) * 2021-01-29 2021-06-04 江苏同得新材料科技有限公司 Preparation process of full-biodegradable material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020077381A (en) * 2000-01-11 2002-10-11 이. 카쇼기 인더스트리스, 엘엘씨. Thermoplastic starch compositions incorporating a particulate filler component
US6605657B1 (en) * 1999-12-27 2003-08-12 Polyvalor Societe En Commandite Polymer compositions containing thermoplastic starch
KR20040063126A (en) * 2001-10-19 2004-07-12 더 프록터 앤드 갬블 캄파니 Polyhydroxyalkanoate copolymer/starch compositions for laminates and films
JP2006505719A (en) * 2002-11-14 2006-02-16 ザ プロクター アンド ギャンブル カンパニー Bicomponent fiber with thermoplastic polymer surrounding a starch-rich core
JP2006137847A (en) * 2004-11-12 2006-06-01 Sansaara Corporation:Kk Starch composition

Family Cites Families (104)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1303005B (en) * 1961-04-03 1971-06-24
US3655129A (en) 1968-07-17 1972-04-11 Ppg Industries Inc Slow release films and methods of making same
US3655192A (en) * 1969-11-04 1972-04-11 Roger L Hall Light ray projector and target
US3963656A (en) * 1972-10-03 1976-06-15 Bayer Aktiengesellschaft Thermoplastic polyurethanes and a two-stage process for their preparation
US4209417A (en) * 1976-08-13 1980-06-24 The Procter & Gamble Company Perfumed particles and detergent composition containing same
US4174330A (en) * 1977-09-21 1979-11-13 Gulf Oil Corporation Process for dispersing additives in thermoplastic polymers
DE3781133T2 (en) * 1986-12-19 1993-06-24 Akzo Nv MANUFACTURE OF POLYMILIC ACID AND COPOLYMERS THEREOF.
GB2205323B (en) * 1987-03-09 1991-01-30 Warner Lambert Co Destructurized starch and process for making same
US5102465A (en) * 1989-01-31 1992-04-07 J. M. Huber Corporation Filler for polyester molding compound and method
US5028658A (en) * 1989-09-18 1991-07-02 Monsanto Company Sheet of polyvinyl butyral and polyurethane
US5169706A (en) 1990-01-10 1992-12-08 Kimberly-Clark Corporation Low stress relaxation composite elastic material
US5093422A (en) * 1990-04-23 1992-03-03 Shell Oil Company Low stress relaxation extrudable elastomeric composition
US5028648A (en) * 1990-07-12 1991-07-02 Air Products And Chemicals, Inc. Extrudable polyvinyl alcohol compositions containing thermoplastic polyurethane
US5292783A (en) * 1990-11-30 1994-03-08 Eastman Kodak Company Aliphatic-aromatic copolyesters and cellulose ester/polymer blends
WO1992009654A2 (en) * 1990-11-30 1992-06-11 Eastman Kodak Company Aliphatic-aromatic copolyesters and cellulose ester/polymer blends
US6326458B1 (en) 1992-01-24 2001-12-04 Cargill, Inc. Continuous process for the manufacture of lactide and lactide polymers
US5470944A (en) * 1992-02-13 1995-11-28 Arch Development Corporation Production of high molecular weight polylactic acid
JPH0842B2 (en) 1992-04-10 1996-01-10 ユニリーバー・ナームローゼ・ベンノートシヤープ Edible crisp material and method for producing the same
AT399883B (en) * 1993-07-29 1995-08-25 Markus Dipl Ing Rettenbacher MOLDED BODIES FROM OR WITH AN ENVIRONMENTALLY COMPATIBLE MATERIAL, METHOD FOR THE PRODUCTION AND USE THEREOF
US5397834A (en) * 1993-09-03 1995-03-14 Iowa State University Research Foundation, Inc. Biodegradable thermoplastic composition of aldehyde starch and protein
EP0641828A1 (en) * 1993-09-08 1995-03-08 Bayer Corporation A thermoplastic composition containing polyurethane and polypropylene
US5523293A (en) * 1994-05-25 1996-06-04 Iowa State University Research Foundation, Inc. Soy protein-based thermoplastic composition for preparing molded articles
US5569318A (en) * 1994-06-24 1996-10-29 Applied Research, Inc. Frictionizing composition
DE4440850A1 (en) * 1994-11-15 1996-05-23 Basf Ag Biodegradable polymers, processes for their production and their use for the production of biodegradable moldings
DE4440837A1 (en) * 1994-11-15 1996-05-23 Basf Ag Biodegradable polymers, processes for their production and their use for the production of biodegradable moldings
US5641562A (en) * 1994-12-30 1997-06-24 Kimberly-Clark Worldwide Inc. Water-shrinkable film
ATE242295T1 (en) * 1995-04-07 2003-06-15 Biotec Biolog Naturverpack BIODEGRADABLE POLYMER BLEND
DE19520093A1 (en) 1995-06-01 1996-12-05 Bayer Ag Polymer blends containing starch and polyurethanes
US6676984B1 (en) * 1995-06-06 2004-01-13 Iowa State University Research Foundation, Inc. Nutritional products containing modified starches
DE19520732A1 (en) * 1995-06-07 1996-12-12 Bayer Ag Thermoplastic polyurethane elastomers
US5770682A (en) * 1995-07-25 1998-06-23 Shimadzu Corporation Method for producing polylactic acid
DE69631305T2 (en) * 1995-07-25 2004-11-18 Toyota Jidosha K.K., Toyota Process for the production of polylactic acid
US5665152A (en) * 1995-11-29 1997-09-09 Midwest Grain Products Biodegradable grain protein-based solid articles and forming methods
US5747648A (en) * 1996-03-12 1998-05-05 Midwest Grain Products Modified wheat glutens and use thereof in fabrication of films
JP3588907B2 (en) * 1996-03-22 2004-11-17 トヨタ自動車株式会社 Method for producing polylactic acid
DE19646392A1 (en) * 1996-11-11 1998-05-14 Lohmann Therapie Syst Lts Preparation for use in the oral cavity with a layer containing pressure-sensitive adhesive, pharmaceuticals or cosmetics for dosed delivery
US6063866A (en) * 1996-12-31 2000-05-16 Kimberly-Clark Worldwide, Inc. Blends of polyolefin and poly(ethylene oxide) and process for making the blends
FI107930B (en) * 1996-12-31 2001-10-31 Valtion Teknillinen Hydroxyalkylated starch ester, its preparation and its use
DE19729306C2 (en) * 1997-07-09 2002-04-04 Celanese Ventures Gmbh Starch and / or modified starch and plasticizer-containing compositions, method and use
US6075118A (en) * 1997-07-31 2000-06-13 Kimberly-Clark Worldwide, Inc. Water-responsive, biodegradable film compositions comprising polylactide and polyvinyl alcohol, and a method for making the films
US5945480A (en) * 1997-07-31 1999-08-31 Kimberly-Clark Worldwide, Inc. Water-responsive, biodegradable fibers comprising polylactide modified polylactide and polyvinyl alcohol, and method for making the fibers
US6552162B1 (en) * 1997-07-31 2003-04-22 Kimberly-Clark Worldwide, Inc. Water-responsive, biodegradable compositions and films and articles comprising a blend of polylactide and polyvinyl alcohol and methods for making the same
US5910545A (en) * 1997-10-31 1999-06-08 Kimberly-Clark Worldwide, Inc. Biodegradable thermoplastic composition
US5981012A (en) * 1997-11-25 1999-11-09 Kimberly-Clark Worldwide, Inc. Flushable release liner comprising a release coating on a water-sensitive film
US5985396A (en) 1997-11-25 1999-11-16 Kimberly-Clark Worldwide, Inc. Flushable release liners and methods of making the same
US6135987A (en) * 1997-12-22 2000-10-24 Kimberly-Clark Worldwide, Inc. Synthetic fiber
US6544455B1 (en) * 1997-12-22 2003-04-08 Kimberly-Clark Worldwide, Inc. Methods for making a biodegradable thermoplastic composition
US6530910B1 (en) * 1997-12-31 2003-03-11 Kimberly-Clark Worldwide, Inc. Flushable release film with combination wiper
US5922379A (en) * 1998-05-05 1999-07-13 Natural Polymer International Corporation Biodegradable protein/starch-based thermoplastic composition
US6020425A (en) * 1998-06-01 2000-02-01 Kimberly-Clark Worldwide, Inc. Unmodified polyvinyl alcohol films and fibers and methods of making the same
US6350518B1 (en) * 1998-06-01 2002-02-26 Kimberly-Clark Worldwide, Inc. Methods of making blend compositions of an unmodified poly vinyl alcohol and a thermoplastic elastomer
US6225388B1 (en) * 1998-08-31 2001-05-01 Kimberly-Clark Worldwide, Inc. Biodegradable thermoplastic composition with improved wettability
US6686007B2 (en) * 1998-09-04 2004-02-03 Patent Holding Company Molded plastic component having enhanced surface finish
US6806353B2 (en) * 1999-05-04 2004-10-19 Iowa State University Research Foundation, Inc. Biodegradable plant protein composites and related methods
DE19938672C2 (en) * 1999-08-06 2001-11-22 Biop Biopolymer Gmbh Process for the production of a thermoplastic polymer mixture based on starch by reactive extrusion
MXPA02005021A (en) 1999-11-18 2003-01-28 Dow Global Technologies Inc Compatibilized resin blends and the preparation thereof.
KR100366484B1 (en) * 1999-12-11 2003-01-14 주식회사 이래화학 Copolyester resin composition and a process of preparation thereof
US6958371B1 (en) * 2000-06-19 2005-10-25 Kimberly-Clark Worldwide, Inc. Method of making blends of poly(vinyl alcohol) and poly(ethylene oxide)
US6767961B1 (en) * 2000-06-19 2004-07-27 Kimberly-Clark Worldwide, Inc. Blends of poly (vinyl alcohol) and poly (ethylene oxide) and articles made therewith
US7413731B2 (en) * 2000-10-27 2008-08-19 The Procter And Gamble Company Fragrance compositions
US6469099B1 (en) * 2000-11-14 2002-10-22 Dow Global Technologies Inc. Compatibilized resin blends and the preparation thereof
US7402618B2 (en) * 2000-11-23 2008-07-22 Hao Xu Biodegradable composition for the preparation of tableware, drink container, mulching film and package and method for preparing the same
IL139910A (en) * 2000-11-26 2006-08-20 Sakit Ltd Plastic films containing a fragrance and an odor barrier material within and method for their production
US20020098341A1 (en) * 2000-12-07 2002-07-25 Schiffer Daniel K. Biodegradable breathable film and laminate
US6838403B2 (en) 2000-12-28 2005-01-04 Kimberly-Clark Worldwide, Inc. Breathable, biodegradable/compostable laminates
US6552124B2 (en) * 2000-12-29 2003-04-22 Kimberly-Clark Worldwide, Inc. Method of making a polymer blend composition by reactive extrusion
US7053151B2 (en) * 2000-12-29 2006-05-30 Kimberly-Clark Worldwide, Inc. Grafted biodegradable polymer blend compositions
US6517625B2 (en) * 2001-01-03 2003-02-11 Mgp Ingredients, Inc. Protein/starch paper coating compositions and method of use thereof
US6890989B2 (en) * 2001-03-12 2005-05-10 Kimberly-Clark Worldwide, Inc. Water-responsive biodegradable polymer compositions and method of making same
US7297394B2 (en) 2002-03-01 2007-11-20 Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg Biodegradable films and sheets suitable for use as coatings, wraps and packaging materials
US6905759B2 (en) * 2001-04-23 2005-06-14 Kimberly Clark Worldwide, Inc. Biodegradable films having enhanced ductility and breathability
US6660211B2 (en) 2001-04-23 2003-12-09 Kimberly-Clark Worldwide, Inc. Methods of making biodegradable films having enhanced ductility and breathability
US6703115B2 (en) * 2001-05-01 2004-03-09 Eastman Chemical Company Multilayer films
US6946506B2 (en) * 2001-05-10 2005-09-20 The Procter & Gamble Company Fibers comprising starch and biodegradable polymers
US20020168518A1 (en) * 2001-05-10 2002-11-14 The Procter & Gamble Company Fibers comprising starch and polymers
US7235594B2 (en) * 2001-07-13 2007-06-26 Biorepla Corporation Biodegradable plastic composition
US6746705B2 (en) * 2001-08-03 2004-06-08 National Starch And Chemical Investment Holding Corporation Thermally converted starches and the method of preparation thereof
US20030099691A1 (en) * 2001-11-16 2003-05-29 Susan Lydzinski Films containing starch
US6824703B2 (en) * 2002-03-08 2004-11-30 Bayer Materialscience Llc Polyurethane elastomers having improved physical properties and a process for the production thereof
JP3742842B2 (en) * 2002-06-17 2006-02-08 独立行政法人産業技術総合研究所 Biodegradable polylactic acid resin composition
US20030232933A1 (en) 2002-06-17 2003-12-18 Didier Lagneaux Reactive blend ploymer compositions with thermoplastic polyurethane
JPWO2004005400A1 (en) 2002-07-08 2005-11-04 三菱樹脂株式会社 Biodegradable sheet, molded body using this sheet, and method for producing the molded body
US20040034149A1 (en) * 2002-08-16 2004-02-19 Garcia Rod A. Essential oils in plastic film
US20040108611A1 (en) * 2002-12-10 2004-06-10 Dennis Michael D. Injecting liquid additives into plastic extruders
US7124450B2 (en) * 2003-03-05 2006-10-24 Dennis Davidson Flushable plunger cover
US7098292B2 (en) * 2003-05-08 2006-08-29 The Procter & Gamble Company Molded or extruded articles comprising polyhydroxyalkanoate copolymer and an environmentally degradable thermoplastic polymer
US6984426B2 (en) * 2003-06-02 2006-01-10 Cortec Corporation Biodegradable bag
US20050186256A1 (en) * 2004-02-20 2005-08-25 Dihel Deborah L. Dissolvable film comprising an active ingredient and method of manufacture
US7153569B2 (en) 2004-03-19 2006-12-26 Kimberly-Clark Worldwide, Inc. Biodegradable aliphatic-aromatic copolyester films
US7776020B2 (en) * 2004-03-19 2010-08-17 Kimberly-Clark Worldwide, Inc. Absorbent articles having an aliphatic-aromatic copolyester film
JP4893885B2 (en) 2004-04-26 2012-03-07 東邦化学工業株式会社 Biodegradable resin composition
WO2005113616A2 (en) 2004-05-04 2005-12-01 Cornell Research Foundation, Inc. Starch polyester blend from reactive extrusion
CA2472420C (en) * 2004-06-23 2011-11-08 Thomas L. Inglis An improved packaging film
US7153354B2 (en) 2004-11-19 2006-12-26 Board Of Trustees Of Michigan State University Chemically modified plasticized starch compositions by extrusion processing
US7307125B2 (en) 2004-12-15 2007-12-11 Ferro Corporation Thermoplastic olefin compositions and injection molded articles made thereof
DE102004060799A1 (en) * 2004-12-17 2006-06-29 Bayer Materialscience Ag Thermoplastic polyurethanes and their use
US20060149199A1 (en) * 2004-12-30 2006-07-06 Kimberly-Clark Worldwide, Inc. Degradable breathable multilayer film with improved properties and method of making same
US20070031555A1 (en) * 2005-08-05 2007-02-08 Axelrod Glen S Direct starch molding
DE102005039933B4 (en) * 2005-08-24 2007-12-27 Bayer Materialscience Ag Process for the preparation of thermoplastically processable polyurethanes
DE102005040131A1 (en) * 2005-08-25 2007-03-01 Lanxess Deutschland Gmbh Thermoplastic polyurethanes
US20070129467A1 (en) * 2005-12-02 2007-06-07 Frederic Scheer Bio based biodegradable polymer compositions and use of same
US7993560B2 (en) * 2006-04-20 2011-08-09 Curwood, Inc. Process for introducing an additive into a polymer melt
US8592641B2 (en) * 2006-12-15 2013-11-26 Kimberly-Clark Worldwide, Inc. Water-sensitive biodegradable film
US8329977B2 (en) * 2007-08-22 2012-12-11 Kimberly-Clark Worldwide, Inc. Biodegradable water-sensitive films

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6605657B1 (en) * 1999-12-27 2003-08-12 Polyvalor Societe En Commandite Polymer compositions containing thermoplastic starch
KR20020077381A (en) * 2000-01-11 2002-10-11 이. 카쇼기 인더스트리스, 엘엘씨. Thermoplastic starch compositions incorporating a particulate filler component
KR20040063126A (en) * 2001-10-19 2004-07-12 더 프록터 앤드 갬블 캄파니 Polyhydroxyalkanoate copolymer/starch compositions for laminates and films
JP2006505719A (en) * 2002-11-14 2006-02-16 ザ プロクター アンド ギャンブル カンパニー Bicomponent fiber with thermoplastic polymer surrounding a starch-rich core
JP2006137847A (en) * 2004-11-12 2006-06-01 Sansaara Corporation:Kk Starch composition

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012077005A3 (en) * 2010-12-07 2012-08-23 Kimberly-Clark Worldwide, Inc. Melt-blended protein composition
US8445032B2 (en) 2010-12-07 2013-05-21 Kimberly-Clark Worldwide, Inc. Melt-blended protein composition
US9205152B2 (en) 2010-12-07 2015-12-08 Kimberly-Clark Worldwide, Inc. Melt-blended protein composition
AU2011340220B2 (en) * 2010-12-07 2016-04-14 Kimberly-Clark Worldwide, Inc. Melt-blended protein composition
KR101828119B1 (en) 2010-12-07 2018-03-22 킴벌리-클라크 월드와이드, 인크. Melt-blended protein composition
KR20190018172A (en) * 2010-12-08 2019-02-21 킴벌리-클라크 월드와이드, 인크. Elastic film containing a renewable starch polymer
KR101968470B1 (en) * 2010-12-08 2019-04-12 킴벌리-클라크 월드와이드, 인크. Elastic film containing a renewable starch polymer
WO2020136231A1 (en) * 2018-12-28 2020-07-02 Agrana Stärke Gmbh Compound or film containing thermoplastic starch and a thermoplastic polymer

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