WO2002042365A1 - Air and moisture vapor breathable biodegradable films and method of manufacture - Google Patents

Air and moisture vapor breathable biodegradable films and method of manufacture Download PDF

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Publication number
WO2002042365A1
WO2002042365A1 PCT/US2001/020299 US0120299W WO0242365A1 WO 2002042365 A1 WO2002042365 A1 WO 2002042365A1 US 0120299 W US0120299 W US 0120299W WO 0242365 A1 WO0242365 A1 WO 0242365A1
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WO
WIPO (PCT)
Prior art keywords
film
lactic acid
biodegradable
group
polymer
Prior art date
Application number
PCT/US2001/020299
Other languages
French (fr)
Inventor
Pai-Chuan Wu
Thomas R. Ryle
Original Assignee
Clopay Plastic Products Company, 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 Clopay Plastic Products Company, Inc. filed Critical Clopay Plastic Products Company, Inc.
Priority to BR0115472-9A priority Critical patent/BR0115472A/en
Priority to KR10-2003-7006811A priority patent/KR20030060943A/en
Priority to MXPA03004503A priority patent/MXPA03004503A/en
Priority to AU2001270168A priority patent/AU2001270168B9/en
Priority to AU7016801A priority patent/AU7016801A/en
Priority to JP2002545077A priority patent/JP2004514756A/en
Priority to PL36102201A priority patent/PL361022A1/en
Priority to EP01948724A priority patent/EP1335948A1/en
Priority to HU0400310A priority patent/HUP0400310A2/en
Publication of WO2002042365A1 publication Critical patent/WO2002042365A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/005Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07Flat, e.g. panels
    • B29C48/08Flat, e.g. panels flexible, e.g. films
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/88Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911Cooling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/12Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/88Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911Cooling
    • B29C48/9135Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16Fillers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/0059Degradable
    • B29K2995/006Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00Ancillary operations in connection with laminating processes
    • B32B38/0012Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028Stretching, elongating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00Condition, form or state of the layers or laminate
    • B32B2305/10Fibres of continuous length
    • B32B2305/20Fibres of continuous length in the form of a non-woven mat
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00Condition, form or state of the layers or laminate
    • B32B2305/30Fillers, e.g. particles, powders, beads, flakes, spheres, chips
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/716Degradable
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/724Permeability to gases, adsorption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/726Permeability to liquids, absorption
    • B32B2307/7265Non-permeable
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state

Definitions

  • the present invention relates to air and moisture vapor
  • thermoplastic film which was made by incrementally stretching the
  • the film may include fillers.
  • Polymer films of polycaprolactone (PCL) and PCL polycaprolactone
  • amorphous polypropylene phase is first embossed prior to biaxially
  • microvoids to enhance the permeability of the otherwise imperforate film
  • the continuous film matrix of a crystallizable polymer may
  • inorganic filler such as clay, titanium dioxide, calcium
  • European patent 141592 discloses the use of a polyolefin
  • EVA ethylene vinyl acetate
  • Patents Nos. 4,452,845 and 4,596,738 also disclose stretched
  • thermoplastic films where the dispersed phase may be a polyethylene
  • thermoplastic copolyester films having improved properties
  • Biodegradable and/or compostable products help preserve
  • compostability is particularly important in disposable, high use products
  • Thermoplastic films that are biodegradable and/or
  • the film can be stretched to form a breathable film.
  • This invention is directed to a biodegradable film which is
  • MVTRs moisture vapor transmission rates
  • MVTRs having MVTRs, preferably on the order of about 1200 to about
  • nonwoven substrates were also disclosed.
  • This invention is directed to further improvements in
  • biodegradable films and laminates which are both permeable to air and
  • the biodegradable film in a broad form of the invention, the biodegradable film
  • thermoplastic polymer comprises a blend of a biodegradable thermoplastic polymer and a
  • laminate is activated upon stretching, preferably incremental stretching
  • biodegradable polymers such as polycaprolactone (PCL) blended with PCL
  • starch polymers or polyvinylalcohol (PVA) that may be film-formed are examples of starch polymers or polyvinylalcohol (PVA) that may be film-formed.
  • biodegradable polymers include polylactides (PLA), PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA, PMMA
  • polyesters and copolyesters The biodegradable films and laminates can be used for diaper
  • the biodegradable film is especially suitable for
  • MVTR greater than about 1000 gms per m 2 per day and 100°F and 95%
  • RH relative humidity
  • thermoplastic film having these breathable properties of
  • the biodegradable film composition can be achieved by:
  • the film may be
  • Calcium carbonate, barium sulfate, silica, and zeolite particles are the most common fillers. As developed
  • microvoids are produced to provide breathability and
  • an inorganic filler particles for example, calcium carbonate, zeolite, silica,
  • composition with other additives into a nip of rollers to form a film at a
  • melt blended More particularly, in preferred form, the melt blended
  • composition consists essentially of about 60% to about 75% of a
  • polyester such as aliphatic-aromatic copolyesters which are described in
  • thermoplastic copolyesters may comprise at least one
  • At least one aliphatic diol having from 4 to about 12 carbon atoms.
  • thermoplastic copolyester may comprise at least one
  • aromatic dicarboxylic acid at least one aliphatic diol and a polyalkylene
  • the aliphatic dicarboxylic acid is selected from the group consisting of:
  • At least one of said aromatic dicarboxylic acids is selected from
  • naphthalenedicarboxylic acid and mixtures thereof; and at least one of
  • said aliphatic diols is selected from the group consisting of
  • thermoplastic copolyester may comprise various combinations
  • polymers include ester-ether polyester (Hytrel and
  • PVA polyvinyl alcohol
  • PCL polycaprolactone
  • PLA polylactide
  • polyesters such as polyhydroxy(butyrate) (PHB), polyhydroxy(valerate) (PHV); and mixtures
  • sulfate or zeolite, having an average particle size of about 1 to about
  • the biodegradable nonwovens may be laminated to the films
  • melt-stable lactide polymers of the type
  • biodegradable and/or compostable include cotton nonwovens
  • melt-blended composition is slot-
  • cooling zone substantially parallel to the web surface are used.
  • stretching force is applied to the film or the laminate at high speeds along
  • the flat films are produced according to the principles of this
  • the stretching process may be conducted at
  • the microporous film may be obtained with nonwoven fibrous webs.
  • the microporous laminate employs a film
  • the film thickness will vary and, most preferably, in
  • disposable applications is the order of about 0.25 to 2 mils in thickness.
  • the nonwoven fibrous webs of the laminated sheet normally have a weight of about 5 gms/yd 2 to 75 gms/yd 2 , preferably about 20 to about
  • the composite or laminate can be incrementally stretched
  • CD cross direction
  • CD stretching may be followed by stretching in the machine
  • microporous film or laminate may be any suitable material. As indicated above, the microporous film or laminate may be any suitable material.
  • microporous-formable film are microporous-formable film. These laminates of nonwoven carded fibrous
  • webs of staple fibers or nonwoven spun-bonded fibrous webs may be
  • the diagonal intermeshing stretcher consists of a pair of left
  • shafts are disposed between two machine side plates, the lower shaft
  • the slidable members are adjustable in the vertical direction by wedge shaped elements operable by
  • Micrometers mounted to the side frames are operable
  • Air cylinders are employed to hold the slidable members in
  • cylinders may also be retracted to disengage the upper and lower
  • a drive means is typically utilized to drive the stationery
  • intermeshing teeth is avoided. If the intermeshing rolls are to remain in
  • the upper intermeshing roll typically need not be driven. Drive may be accomplished by the driven intermeshing roll
  • the intermeshing rolls closely resemble fine pitch helical
  • the rolls have 5.935" diameter, 45°
  • the teeth are not designed to transmit
  • the CD intermeshing stretching equipment is identical to the
  • intermeshing elements are capable of large engagement depths, it is
  • a gear resides on each end of this shaft and operates in
  • the drive for the CD intermeshing stretcher must operate
  • the drive need not be antibacklash, however, because a ' small
  • the CD intermeshing elements are machined from solid
  • CD intermeshing element configuration would have a 0.100" pitch.
  • the MD intermeshing stretching equipment is identical to the
  • the MD intermeshing rolls closely resemble fine pitch spur gears.
  • the rolls have a 5.933" diameter, 0.100"
  • stretchers may be employed to produce the incrementally stretched film
  • microporous film products of this invention form the microporous film products of this invention.
  • stretching operation may be employed on an extrusion laminate of a
  • nonwoven fibrous web of staple fibers or spun-bonded filaments are nonwoven fibrous web of staple fibers or spun-bonded filaments and
  • microporous-formable thermoplastic film in one of the unique aspects
  • filaments may be incrementally stretched to provide a very soft fibrous
  • fibrous web and microporous-formable film is incrementally stretched using, for instance, the CD and/or MD intermeshing stretcher with one
  • microporous film and laminates of this invention are microporous film and laminates of this invention.
  • FIG. 1 is a microphotograph of the film surface of
  • FIG. 2 is a microphotograph of a cross-section of
  • Example 1 A film at 2000X.
  • FIG. 3 is a microphotograph of the film surface of
  • Example 1 B at 1000X in the unstretched area due to intermeshing.
  • FIG. 4 is a microphotograph of the film surface of
  • FIG. 5 is a microphotograph of a cross-section of
  • Example 1 B film at 2000X through the stretched surface area.
  • a biodegradable copolyester of an aromatic-aliphatic type is provided.
  • melt temperatures on the order of about 425°F-475°F.
  • FIG. 1 microphotograph of such a film surface is shown in FIG. 1 , and a cross-
  • FIG. 2 The film was tested and found not to be air
  • Example 1 A when incrementally stretched at a
  • the MVTR increased from 939 g/m 2 /day (Example 1 A) to
  • Example 1 B The air permeability of the film having originally zero permeability (Example 1 A), became 570 cc of air/cm 2 /min
  • Examples 1 A and 1 B did show the embedded inorganic particles (see
  • FIGS. 1 -5 The high MVTR and air-permeable biodegradable film of this
  • Example 1 A film (see FIG. 2, cross-section), there were no pore
  • Example 1 A film The mechanical properties of Example 1 A film are as
  • the biodegradable film of Example 1 B is suitable for diaper
  • Example 1 A type as employed in Example 1 A are extruded into a film in a similar manner
  • biodegradable films as indicated below.
  • biodegradable polymers such as the polylactides,
  • polycaprolactones, starch, polyvinylalcohols, polyesters, and copolyesters, can be processed with inorganic filler particles to provide

Abstract

Biodegradable films permeable to moisture vapor and air which act as barriers to liquid are made by a high speed method. The films have high moisture vapor transmission rates (MVTRs) on the order of about 1000 to about 4500 g/m2/day according to ASTM E96E and air breathability of about 30 to about 2000 cc/cm2/min at 90 psi air pressure.

Description

AIR AND MOISTURE VAPOR BREATHABLE BIODEGRADABLE FILMS AND METHOD OF MANUFACTURE
RELATED APPLICATIONS
This application is a continuation-in-part application of
Application Serial No. 09/480,374, filed January 10, 2000, which is, in
turn, a continuation-in-part application of Application Serial
No. 09/080,063, filed May 15, 1998, now U.S. Patent No. 6,013,1 51 ,
and Application Serial No. 09/395,627, filed on September 14, 1999.
All of the above applications are incorporated herein in their entireties by
reference.
FIELD OF THE INVENTION
The present invention relates to air and moisture vapor
breathable biodegradable plastic films and to processes for their
manufacture.
BACKGROUND OF THE INVENTION
Methods of making plastic film date back many years. For
example, more than thirty years ago U. S. Patent No. 3,484,835 (1968) issued to Trounstine, et al., and it is directed to embossed plastic film
having desirable handling characteristics and fabricating useful articles
such as diapers. Since that time, many patents have issued in the field.
U. S. Patent No. 4,376,147 (1983) discloses an embossed cross
direction (CD) and machine direction (MD) film. U. S. Patents
Nos. 5,202,173 (1993) and 5,296,184 (1994) teach an ultra-soft
thermoplastic film which was made by incrementally stretching the
embossed film and the formation of perforations to achieve breathability.
The film may include fillers. Polymer films of polycaprolactone (PCL) and
starch polymer or polyvinyl alcohol (PVOH) upon incremental stretching
also produce breathable products, as disclosed in U. S. Patents
Nos. 5,200,247 and 5,407,979. More recently, U. S. Patent
No. 5,865,926 issued for a method of making a cloth-like microporous
laminate of a nonwoven fibrous web and thermoplastic film having air and
moisture vapor permeabilities with liquid-barrier properties.
Methods of making microporous film products have also
been known for some time. For example, U. S. Patent No. 3,832,267,
to Liu, teaches the melt-embossing of a polyolefin film containing a
dispersed amorphous polymer phase prior to stretching or orientation to
improve gas and moisture vapor transmission of the film. According to
the Liu '267 patent, a film of crystalline polypropylene having a dispersed
amorphous polypropylene phase is first embossed prior to biaxially
drawing (stretching) to produce an oriented imperforate film having greater permeability. The dispersed amorphous phase serves to provide
microvoids to enhance the permeability of the otherwise imperforate film
to improve moisture vapor transmission (MVT).
In 1976, Schwarz published a paper which described
polymer blends and compositions to produce microporous substrates
(Eckhard CA. Schwartz (Biax-Fiberfilm), "New Fibrillated Film Structures,
Manufacture and Uses", Pap. Synth. Conf. (TAPPI). 1976, pages 33-39).
According to this paper, a film of two or more incompatible polymers,
where one polymer forms a continuous phase and a second polymer
forms a discontinuous phase, upon being stretched will phase separate
thereby leading to voids in the polymer matrix and increasing the porosity
of the film. The continuous film matrix of a crystallizable polymer may
also be filled with inorganic filler such as clay, titanium dioxide, calcium
carbonate, etc., to provide microporosity in the stretched polymeric
substrate.
Many other patents and publications disclose the
phenomenon of making microporous thermoplastic film products. For
example, European patent 141592 discloses the use of a polyolefin,
particularly ethylene vinyl acetate (EVA) containing a dispersed
polystyrene phase which, when stretched, produces a voided film which
improves the moisture vapor permeability of the film. This EP '592
patent also discloses the sequential steps of embossing the EVA film with
thick and thin areas followed by stretching to first provide a film having voids which, when further stretched, produces a net-like product. U. S.
Patents Nos. 4,452,845 and 4,596,738 also disclose stretched
thermoplastic films where the dispersed phase may be a polyethylene
filled with calcium carbonate to provide the microvoids upon stretching.
U. S. Patents Nos. 3,137,746; 4,777,073; 4,814, 124; and 4,921 ,653
disclose the same processes described by the above-mentioned
publications involving the steps of first embossing a polyolefin film
containing a filler and then stretching that film to provide a microporous
product. Other patent publications have issued, including WO 98/23673,
which are directed to thermoplastic copolyester films having improved
moisture vapor transmission rates and are made by mixing a copolyester
resin and an inorganic filler.
Biodegradable and/or compostable products help preserve
environmental resources and prevent generation of additional waste.
Both manufacturers and consumers are aware of the finite amount of
space in landfills and other disposal sites and may affirmatively seek
biodegradable and/or compostable products over nonbiodegradable and/or
noncompostable products. The need for biodegradability and/or
compostability is particularly important in disposable, high use products
such as baby diapers, feminine hygiene products, hospital drapes, and the
like.
Thermoplastic films that are biodegradable and/or
compostable are known in the prior art. The above-mentioned U.S. Patent No. 5,407,979 discloses a biodegradable thermoplastic film
composed of three components: an alkanoyl polymer, destructured
starch, and an ethylene copolymer. The components can be extruded and
the film can be stretched to form a breathable film. U.S. Patent
No. 5,200,247 discloses a biodegradable thermoplastic film containing an
alkanoyl polymer/polyvinyl alcohol (PVA) blend. U.S. Patent
No. 5,196,247 discloses a compostable polymeric composite sheet and
method of making or composting.
Totally biodegradable and/or compostable soft cloth-like
composites are disclosed in U.S. Patent No. 5,851 ,937. The composites
are made by incrementally stretching one or more plies of totally
biodegradable and/or compostable nonwoven webs and plastic films to
provide a soft cloth-like feel.
There still remain drawbacks to the production of breathable
films and laminates which are liquid barriers. It is difficult to obtain a
liquid barrier film of sufficient strength while maintaining the properties
of biodegradability, air breathability and moisture vapor transmission.
SUMMARY OF THE INVENTION
This invention is directed to a biodegradable film which is
both air and moisture vapor breathable, and is a barrier to liquid. These
films have moisture vapor transmission rates (MVTRs) greater than about
1000 grams (gms) per m2 per day and 100°F and 95% relative humidity (RH) according to ASTM E96E and air permeabilities greater than about
30 cc/cm2/min at 90 psi air pressure.
In the above-identified patent applications serial
nos. 09/080,063 and 09/480,374, incrementally stretched films were
disclosed having high MVTRs. These applications were directed to
improvements in incrementally stretched embossed and unembossed films
having MVTRs, preferably on the order of about 1200 to about
4500 gms/m2/per day. Breathable laminates of these films with
nonwoven substrates were also disclosed.
This invention is directed to further improvements in
biodegradable films and laminates which are both permeable to air and
moisture vapor. In a broad form of the invention, the biodegradable film
comprises a blend of a biodegradable thermoplastic polymer and a
mechanical pore forming agent such as inorganic fillers of calcium
carbonate, silica and zeolite. The pore forming agent in the film or
laminate is activated upon stretching, preferably incremental stretching,
to form a microporous film or laminate of a fibrous web and film. The
biodegradable polymers such as polycaprolactone (PCL) blended with
starch polymers or polyvinylalcohol (PVA) that may be film-formed are
suitable. Other biodegradable polymers include polylactides (PLA),
polyesters and copolyesters. The biodegradable films and laminates can be used for diaper
backsheets, sanitary napkins and pads, and other medical, packaging and
garment applications. The biodegradable film is especially suitable for
these and other similar applications because of its air breathability,
moisture vapor breathability and water impermeability. The benefits and
properties of the biodegradable film of this invention and its method of
manufacture will be further understood with reference to the following
detailed description.
DETAILED DESCRIPTION OF THE INVENTION
It is the primary objective of this invention to produce an air
and moisture vapor breathable biodegradable film having an air
permeability of at least about 30 cc/cm2/min at 90 psi air pressure and a
MVTR greater than about 1000 gms per m2 per day and 100°F and 95%
relative humidity (RH) according to ASTM E96E. It is the further
objective of this invention to produce an incrementally stretched
biodegradable thermoplastic film having these breathable properties of
regular gauge, uniform porosity and without breakage.
A. Biodegradable Film and Laminate Materials
The biodegradable film composition can be achieved by
formulating a biodegradable thermoplastic polymer with suitable additives
and pore forming fillers to provide an extrudate or film. The film may be
laminated with a nonwoven web. Calcium carbonate, barium sulfate, silica, and zeolite particles are the most common fillers. As developed
above, it is known to provide biodegradable films with different polymer
phases in the film so that when the film is stretched at ambient or room
temperature, microvoids are produced to provide breathability and
moisture vapor transmission. These methods are described in U.S.
Patents Nos. 5,200,247, and 5,407,979. In contrast, this invention is
directed to the use of inorganic fillers to provide high air permeabilities
and high MVTRs with liquid barrier properties in biodegradable films.
As developed above, these and other objectives are achieved
in a preferred form of the invention by first melt blending a composition
of (a) about 40% to about 75% by weight of a biodegradable polymer of
the type identified above, and (b) about 25% to about 60% by weight of
an inorganic filler particles, for example, calcium carbonate, zeolite, silica,
talc, barium sulfate, mica, and the like, then extruding said melt blended
composition with other additives into a nip of rollers to form a film at a
speed on the order of at least about 550 fpm to about 1200 fpm without
draw resonance, and applying an incremental stretching force to said film
at said speed along lines substantially and uniformly across the film and
throughout its depth to provide a biodegradable microporous film.
More particularly, in preferred form, the melt blended
composition consists essentially of about 60% to about 75% of a
polyester such as aliphatic-aromatic copolyesters which are described in
WO 98/23673 and that description is incorporated herein by reference. ln particular, these thermoplastic copolyesters may comprise at least one
aliphatic dicarboxylic acid, at least one aromatic dicarboxylic acid, and at
least one aliphatic diol having from 4 to about 12 carbon atoms.
Alternatively, the thermoplastic copolyester may comprise at least one
aromatic dicarboxylic acid, at least one aliphatic diol and a polyalkylene
ether. The aliphatic dicarboxylic acid is selected from the group
consisting of adipic acid, glutaric acid, cyciohexanoic acid, and mixtures
thereof; at least one of said aromatic dicarboxylic acids is selected from
the group consisting of terephthalic acid, isophthalic acid,
naphthalenedicarboxylic acid, and mixtures thereof; and at least one of
said aliphatic diols is selected from the group consisting of
1 ,4-butanediol, cyclohexanedimethanol, a polyalkylene ether compound
selected from the group consisting of poly(ethylene glycol),
poly(tetramethylene glycol) and poly(propylene glycol), and mixtures
thereof. The thermoplastic copolyester may comprise various
combinations of aromatic dicarboxylic acid, aliphatic diols, cyclicaliphatic
dicarboxylic acids, polyalkylene ethers, and the like, all described in the
WO 98/23673 publication as examples of copolyesters within the scope
of this invention.
Other polymers include ester-ether polyester (Hytrel and
Armtel); nylon-ether polyester (Pebax); polyethylene terephthalate (PET);
polyvinyl alcohol (PVA); polycaprolactone (PCL); starch; polylactide (PLA);
a blend of starch and PVA, PCL, or PLA; polyesters such as polyhydroxy(butyrate) (PHB), polyhydroxy(valerate) (PHV); and mixtures
thereof. Preferably, about 25-40% of calcium carbonate, silica, barium
sulfate, or zeolite, having an average particle size of about 1 to about
10 / is used.
The biodegradable nonwovens may be laminated to the films
and they include preferably melt-stable lactide polymers of the type
disclosed in U.S. Patent No. 5,539,081 , that is, polylactide nonwovens
(PLA). All the filaments of the nonwoven are made entirely of a polymer
or a mixture of polymers derived from lactic acid, that is L lactic acid,
D lactic acid, or a mixture of L and D lactic acids. Other nonwovens
which are biodegradable and/or compostable include cotton nonwovens,
cellulosic nonwovens, aliphatic-aromatic copolyesters, and their blends.
In the above method, the melt-blended composition is slot-
die extruded as a web through a cooling zone provided by an air knife,
then into a nip of rollers to form a film at high speeds. Embossed or flat
(non-embossed) films can be produced. Use of the air knife, as developed
above, assists in the elimination of draw resonance, as is known, for
example, by reference to U. S. Patent No. 4,626,574. In addition, as
described in pending U. S. Application Serial No. 09/395,627, filed
September 14, 1999, which is incorporated herein in its entirety by
reference, devices for directing a stream of cooling gas to flow in the
cooling zone substantially parallel to the web surface are used. For
example, devices as shown in U. S. Patents Nos. 4,718,178 and 4,779,355 may be used and the entire disclosures of these patents are
also incorporated herein by reference. After cooling, an incremental
stretching force is applied to the film or the laminate at high speeds along
lines substantially uniformly across the film and throughout its depth to
provide the incrementally stretched embossed or fiat film having a high
MVTR and air permeability.
The flat films are produced according to the principles of this
invention upon extrusion of a web into a nip of rollers which provide a
polished chrome surface to form a flat film. The flat film, upon
incremental stretching, at high speeds, produces microporous film
products having a high MVTR of greater than 1000 gms/m2/day. It has
been found that flat film can be incrementally stretched more uniformly
than embossed film. The stretching process may be conducted at
ambient temperature, room temperature, or at an elevated temperature,
as understood in the art. As also understood in the art, "ambient" means
surrounding temperature or atmosphere which could be whatever process
conditions exist surrounding the film. As described above, laminates of
the microporous film may be obtained with nonwoven fibrous webs.
In a preferred form, the microporous laminate employs a film
having a gauge or a thickness between about 0.25 and 10 mils and,
depending upon use, the film thickness will vary and, most preferably, in
disposable applications is the order of about 0.25 to 2 mils in thickness.
The nonwoven fibrous webs of the laminated sheet normally have a weight of about 5 gms/yd2 to 75 gms/yd2, preferably about 20 to about
40 gms/yd2. The composite or laminate can be incrementally stretched
in the cross direction (CD) to form a CD stretched composite.
Furthermore, CD stretching may be followed by stretching in the machine
direction (MD) to form a composite which is stretched in both CD and MD
directions. As indicated above, the microporous film or laminate may be
used in many different applications such as baby diapers, baby training
pants, catamenial pads and garments, and the like where moisture vapor
and air transmission properties, as well as fluid barrier properties, are
needed.
B. Stretchers for the Microporous Film and Laminates
A number of different stretchers and techniques may be
employed to stretch the film or laminate of a nonwoven fibrous web and
microporous-formable film. These laminates of nonwoven carded fibrous
webs of staple fibers or nonwoven spun-bonded fibrous webs may be
stretched with the stretchers and techniques described as follows:
1. Diagonal Intermeshing Stretcher
The diagonal intermeshing stretcher consists of a pair of left
hand and right hand helical gear-like elements on parallel shafts. The
shafts are disposed between two machine side plates, the lower shaft
being located in fixed bearings and the upper shaft being located in
bearings in vertically slidable members. The slidable members are adjustable in the vertical direction by wedge shaped elements operable by
adjusting screws. Screwing the wedges out or in will move the vertically
slidable member respectively down or up to further engage or disengage
the gear-like teeth of the upper intermeshing roll with the lower
intermeshing roll. Micrometers mounted to the side frames are operable
to indicate the depth of engagement of the teeth of the intermeshing roll.
Air cylinders are employed to hold the slidable members in
their lower engaged position firmly against the adjusting wedges to
oppose the upward force exerted by the material being stretched. These
cylinders may also be retracted to disengage the upper and lower
intermeshing rolls from each other for purposes of threading material
through the intermeshing equipment or in conjunction with a safety circuit
which would open all the machine nip points when activated.
A drive means is typically utilized to drive the stationery
intermeshing roll. If the upper intermeshing roll is to be disengageable for
purposes of machine threading or safety, it is preferable to use an
antibacklash gearing arrangement between the upper and lower
intermeshing rolls to assure that upon reengagement the teeth of one
intermeshing roll always fall between the teeth of the other intermeshing
roll and potentially damaging physical contact between addenda of
intermeshing teeth is avoided. If the intermeshing rolls are to remain in
constant engagement, the upper intermeshing roll typically need not be driven. Drive may be accomplished by the driven intermeshing roll
through the material being stretched.
The intermeshing rolls closely resemble fine pitch helical
gears. In the preferred embodiment, the rolls have 5.935" diameter, 45°
helix angle, a 0.100" normal pitch, 30 diametral pitch, 141/2° pressure
angle, and are basically a long addendum topped gear. This produces a
narrow, deep tooth profile which allows up to about 0.090" of
intermeshing engagement and about 0.005" clearance on the sides of the
tooth for material thickness. The teeth are not designed to transmit
rotational torque and do not contact metal-to-metal in normal
intermeshing stretching operation.
2. Cross Direction Intermeshing Stretcher
The CD intermeshing stretching equipment is identical to the
diagonal intermeshing stretcher with differences in the design of the
intermeshing rolls and other minor areas noted below. Since the CD
intermeshing elements are capable of large engagement depths, it is
important that the equipment incorporate a means of causing the shafts
of the two intermeshing rolls to remain parallel when the top shaft is
raising or lowering. This is necessary to assure that the teeth of one
intermeshing roll always fall between the teeth of the other intermeshing
roll and potentially damaging physical contact between intermeshing teeth
is avoided. This parallel motion is assured by a rack and gear arrangement wherein a stationary gear rack is attached to each side frame
in juxtaposition to the vertically slidable members. A shaft traverses the
side frames and operates in a bearing in each of the vertically slidable
members. A gear resides on each end of this shaft and operates in
engagement with the racks to produce the desired parallel motion.
The drive for the CD intermeshing stretcher must operate
both upper and lower intermeshing rolls except in the case of
intermeshing stretching of materials with a relatively high coefficient of
friction. The drive need not be antibacklash, however, because a' small
amount of machine direction misalignment or drive slippage will cause no
problem. The reason for this will become evident with a description of
the CD intermeshing elements.
The CD intermeshing elements are machined from solid
material but can best be described as an alternating stack of two different
diameter disks. In the preferred embodiment, the intermeshing disks
would be 6" in diameter, 0.031 " thick, and have a full radius on their
edge. The spacer disks separating the intermeshing disks would be 5
1 /2" in diameter and 0.069" in thickness. Two rolls of this configuration
would be able to be intermeshed up to 0.231 " leaving 0.019" clearance
for material on all sides. As with the diagonal intermeshing stretcher, this
CD intermeshing element configuration would have a 0.100" pitch. 3. Machine Direction Intermeshing Stretcher
The MD intermeshing stretching equipment is identical to the
diagonal intermeshing stretch except for the design of the intermeshing
rolls. The MD intermeshing rolls closely resemble fine pitch spur gears.
In the preferred embodiment, the rolls have a 5.933" diameter, 0.100"
pitch, 30 Diametral pitch, 14%° pressure angle, and are basically a long
addendum, topped gear. A second pass was taken on these rolls with
the gear hob offset 0.01 0" to provide a narrowed tooth with more
clearance. With about 0.090" of engagement, this configuration will
have about 0.01 0" clearance on the sides for material thickness.
4. Incremental Stretching Technique
The above described diagonal, CD or MD intermeshing
stretchers may be employed to produce the incrementally stretched film
or laminate of nonwoven fibrous web and microporous-formable film to
form the microporous film products of this invention. For example, the
stretching operation may be employed on an extrusion laminate of a
nonwoven fibrous web of staple fibers or spun-bonded filaments and
microporous-formable thermoplastic film. In one of the unique aspects
of this invention a laminate of a nonwoven fibrous web of spun-bonded
filaments may be incrementally stretched to provide a very soft fibrous
finish to the laminate that looks like cloth. The laminate of nonwoven
fibrous web and microporous-formable film is incrementally stretched using, for instance, the CD and/or MD intermeshing stretcher with one
pass through the stretcher with a depth of roller engagement at about
0.060 inch to 0.120 inch at speeds from about 550 fpm to 1200 fpm or
faster. The results of such incremental or intermesh stretching produces
laminates that have excellent breathability and liquid-barrier properties,
yet provide superior bond strengths and soft cloth-like textures.
The following examples illustrate the method of making
microporous film and laminates of this invention. In light of these
examples and this further detailed description, it is apparent to a person
of ordinary skill in the art that variations thereof may be made without
departing from the scope of this invention.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a microphotograph of the film surface of
Example 1 A at 1000X.
FIG. 2 is a microphotograph of a cross-section of
Example 1 A film at 2000X.
FIG. 3 is a microphotograph of the film surface of
Example 1 B at 1000X in the unstretched area due to intermeshing.
FIG. 4 is a microphotograph of the film surface of
Example 1 B at 1000X in the stretched area due to intermeshing
stretching. FIG. 5 is a microphotograph of a cross-section of
Example 1 B film at 2000X through the stretched surface area.
Examples 1A and 1 B
A biodegradable copolyester of an aromatic-aliphatic type,
as fully described in the examples of WO 98/23673, is employed in these
examples. More specifically, a film having representative biodegradable
copolyesters described in the examples of this publication, containing
about 25% to about 40% zeolite or calcium carbonate, are extruded by
using a conventional slot die cast film extrusion technique which is well
known to a person of ordinary skill in the art. In particular, films having
thicknesses of about 2 mil (50 grams per square meter) are extruded at
melt temperatures on the order of about 425°F-475°F. A
microphotograph of such a film surface is shown in FIG. 1 , and a cross-
section is shown in FIG. 2. The film was tested and found not to be air
permeable, but had a MVTR (moisture vapor transmission rate) of 939
g/m2/day according to the ASTM E96E test method.
The film of Example 1 A, when incrementally stretched at a
temperature of about 72°F with CD engagement of 0.070 inch followed
with MD engagement of 0.050 inch, with apparatus described above,
became air breathable and had an increased moisture vapor transmission
rate. The MVTR increased from 939 g/m2/day (Example 1 A) to
2350 g/m2/day (Example 1 B). The air permeability of the film having originally zero permeability (Example 1 A), became 570 cc of air/cm2/min
under 90 psi air pressure (Example 1 B).
Microphotographs of the film surfaces and cross-sections of
Examples 1 A and 1 B did show the embedded inorganic particles (see
FIGS. 1 -5). The high MVTR and air-permeable biodegradable film of this
invention did have the pore formation around the inorganic particles upon
incremental stretching (see FIGs. 4 and 5). Yet, the unstretched area did
not show pore formation (see FIG 3). The cross-section of Example 1 B
film (see FIG. 5) clearly indicated that pores are connected to allow air
flow. In Example 1 A film (see FIG. 2, cross-section), there were no pore
connections to allow air to flow through.
The mechanical properties of Example 1 A film are as
follows:
Figure imgf000020_0001
The biodegradable film of Example 1 B is suitable for diaper
backsheets, sanitary napkins, and health care garment applications where
air flow (ventilation), high moisture vapor transmission, and liquid barrier
properties are needed for skin care and comfort while wearing.
Examples 2A-2H
In these Examples, copolyesters of the aromatic-aliphatic
type as employed in Example 1 A are extruded into a film in a similar
fashion. These films of Examples 2A-2H are CD and/or MD stretched at
room temperature to become air and moisture vapor breathable
biodegradable films, as indicated below.
Figure imgf000021_0001
Other biodegradable polymers such as the polylactides,
polycaprolactones, starch, polyvinylalcohols, polyesters, and copolyesters, can be processed with inorganic filler particles to provide
air and moisture breathable films in view of the above description.
In view of the above detailed description, it will be
understood that variations will occur in employing the principles of this
invention depending upon materials and conditions, as will be understood
to those of ordinary skill in the art.
WHAT IS CLAIMED IS:

Claims

1 . An air and moisture breathable biodegradable thermoplastic
film comprising
a biodegradable thermoplastic polymer containing a
dispersed phase of inorganic filler particles,
said film having a liquid impermeable thickness with
stretched areas to provide microporosity in the film having a moisture
vapor transmission rate MVTR greater than about 1000 g/m2/day
according to ASTM E96E and air breathability of greater than about
30 cc/cm2/min at 90 psi air pressure.
2. The film of claim 1 wherein the biodegradable thermoplastic
polymer is selected from the group consisting of polycaprolactone, starch,
polyvinylalcohol, polylactide, polyester, and copolyester, and mixtures
thereof.
3. The film of claim 1 wherein said filler is selected from the
group consisting of calcium carbonate, silica, talc, barium sulfate, zeolite,
and mica, and mixtures thereof.
4. The film of claim 1 laminated to a biodegradable fibrous
web.
5. The film of claim 4 wherein the fibers of said fibrous web are
selected from the group consisting of a cellulosic polymer, polyester,
copolyester, a polymer of entirely L lactic acid, a polymer of entirely
D lactic acid, a copolymer of L lactic acid and D lactic acid and a blend of
polymers of L lactic acid and D lactic acid.
6. The film of claim 1 wherein the biodegradable thermoplastic
polymer is selected from the group consisting of polyvinyl alcohol (PVA),
polycaprolactone (PCL), polylactide (PLA), starch, a blend of starch and
PVA, PCL or PLA, polyhydroxy(butyrate) (PHB), polyhydroxy(valerate)
(PHV), and aliphatic-aromatic copolyesters, and mixtures thereof.
7. The film of claim 1 wherein the microporous film has a
thickness on the order of about 0.25 to about 10 mils.
8. The film of claim 1 wherein the microporous film has a
thickness on the order of about 0.25 to about 2 mils.
9. The film of claim 1 wherein the moisture vapor transmission
rate (MVTR) is about 2000 to about 4500 grams per m2 per day
according to ASTM E96E and air permeability is about 200 to about
1600 cc/min/cm2 at 90 psi air pressure.
10. The film of claim 1 wherein said inorganic filler is selected
from the group consisting of calcium carbonate, barium sulfate, mica,
talc, silica and zeolite.
1 1. A high speed method of making an air and moisture
breathable biodegradable thermoplastic film having liquid barrier properties
comprising
melt blending about 40% to about 75% by weight of a
biodegradable thermoplastic polymer and about 25% to about 60% by
weight of inorganic filler particles to form a biodegradable thermoplastic
polymer composition,
extruding a web of said molten thermoplastic composition
from a slot die through a cooling zone into a nip of rollers to form a film
having a thickness of about 0.25 to about 10 mils at a speed on the
order of at least about 550 fpm to about 1200 fpm without draw
resonance,
applying an incremental stretching force to said film at said
speeds along the lines substantially and uniformly across said film and
throughout its depth to provide a biodegradable microporous film with an
MVTR greater than about 1000 g/m2/day according to ASTM E96E, and
air breathability greater than about 30 cc/cm2/min at 90 psi air pressure.
12. The method of claim 1 1 wherein the MVTR is on the order
of about 2000 to about 4500 g/m2/day according to ASTM E96E and air
permeability is about 200 to about 1600 cc/min/cm2 at 90 psi air
pressure.
13. The method of claim 1 1 comprising introducing a
biodegradable nonwoven fibrous web into said nip of rollers and
controlling the compressive force to bond the web to the film and
stretching to form a laminated biodegradable film.
14. The method of claim 1 1 wherein the biodegradable
thermoplastic polymer is selected from the group consisting of
polycaprolactone, starch, polyvinylaicohol, polylactide, polyester,
copolyester, and mixtures thereof.
1 5. The method of claim 1 1 said filler is selected from the group
consisting of calcium carbonate, silica, talc, barium sulfate, zeolite, and
mica, and mixtures thereof.
16. The method of claim 1 1 wherein the fibers of said fibrous
web are selected from the group consisting of a cellulosic polymer,
polyester, copolyester, a polymer of entirely L lactic acid, a polymer of
entirely D lactic acid, a copolymer of L lactic acid and D lactic acid and
a blend of polymers of L lactic acid and D lactic acid.
17. The method of claim 1 1 wherein the biodegradable
thermoplastic polymer is selected from the group consisting of polyvinyl
alcohol (PVA), polycaprolactone (PCL), polylactide (PLA), starch, a blend
of starch and PVA, PCL or PLA, polyhydroxy(butyrate) (PHB),
polyhydroxy(valerate) (PHV), and aliphatic-aromatic copolyesters, and
mixtures thereof.
18. The method of claim 1 1 wherein the microporous film has
a thickness on the order of about 0.25 to about 10 mils.
19. The method of claim 1 1 wherein the microporous film has
a thickness on the order of about 0.25 to about 2 mils.
20. The method of claim 1 1 wherein the moisture vapor
transmission rate (MVTR) is on the order of about 2000 to about
4500 grams per m2 per day according to ASTM E96E.
21 . The method of claim 1 1 wherein said inorganic filler has an
average particle size of about 1 to about 10 microns and is selected from
the group consisting of calcium carbonate, barium sulfate, silica and
zeolite.
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