CA2029617C - Low stress relaxation elastomeric nonwoven webs and fibers - Google Patents

Low stress relaxation elastomeric nonwoven webs and fibers Download PDF

Info

Publication number
CA2029617C
CA2029617C CA002029617A CA2029617A CA2029617C CA 2029617 C CA2029617 C CA 2029617C CA 002029617 A CA002029617 A CA 002029617A CA 2029617 A CA2029617 A CA 2029617A CA 2029617 C CA2029617 C CA 2029617C
Authority
CA
Canada
Prior art keywords
styrene
fibers
percent
elastic
propylene
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Fee Related
Application number
CA002029617A
Other languages
French (fr)
Other versions
CA2029617A1 (en
Inventor
L. Warren Collier, Iv
Steven R. Stopper
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kimberly Clark Worldwide Inc
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 CA2029617A1 publication Critical patent/CA2029617A1/en
Application granted granted Critical
Publication of CA2029617C publication Critical patent/CA2029617C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/903Microfiber, less than 100 micron diameter
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/601Nonwoven fabric has an elastic quality
    • Y10T442/602Nonwoven fabric comprises an elastic strand or fiber material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/637Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material

Abstract

An elastic nonwoven web is formed from elastic fibers composed of a blend of (1) a styrene-poly(ethylene-propylene)-styrene thermoplastic. elastomeric block copolymer or a mixture of a styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer and a styrene-polyethylene-butylene)-styrene elastomeric block copolymer, and (2) a tackifying resin in which the elastic nonwoven web has a stress relaxation of less than about 30 percent. the blend used to form the elastic nonwoven web and/or elastic fibers may also include a polyolefin and an extending oil.

Description

~~'~~~~.' FIELD OF THE INVENTION
The present invention is generally directed to nonwoven webs and, in particular, to nonwoven elastic webs of fibers.
BACKGROUND OF THE INVENTION
In the field of nonwoven materials, there has been a continuing need for materials having high degree of flexibility and elasticity and which may be manufactured at l0 a low cost. In particular, there is a need for an elastic material having a low initial load tension, low stress relaxation, low hysteresis and high recoverable energy.
This need has persisted in spite of the fact that such materials could readily be utilized in the manufacture of a wide variety of garments of both the disposable type, such as disposable diapers, or the durable type, such as pants, dresses, blouses and sporting wear, for example, sweatsuits. Further, such materials could also be utilized in, for example, upholstery, drapery, liner and insulation applications. The traits of low initial load tension, low stress relaxation, low hysteresis and high recoverable energy are particularly desirable characteristics for materials used in these areas because articles manufactured from such materials may be easily put on the body of the wearer or any item, such as a fixed frame, around which the materials may be wrapped. Those traits are also very useful because articles manufactured from such materials are able to closely conform to the body of a wearer or any item and repeatedly extend and retract without sagging.
Elastic nonwoven webs of fibers have been formed from blends of styrene-polyethylene-butylene)-styrene elastomeric block copolymers with other materials such as, for example, polyolefins and tackifying resins to improve processing and/or bonding. While improving the processing and/or bonding properties of the elastic webs, such additives may, in certain situations, have an adverse affect on the elastic properties of the material. For example, elastic block copolymers blended with large ~~~,~:1"~l amounts of a polyolefin and/or hydrocarbon resin may have poor stress relaxation properties and stress-strain tests of such materials show significant hysteresis.
DEFINITIONS
The term "elastic" is used herein to mean any material which, upon application of a biasing force, is stretchable, that is, elongatable, to a stretched, biased length which is at least about 160 percent of its relaxed unbiased length, and which, will recover at least 55 percent of its elongation upon release of the stretching, elongating force. A hypothetical example would be a one (1) inch sample of a material which is elongatable to at least 1.60 inches and which, upon being elongated to 1.60 inches and released, will recover to a length of not more than 1.27 inches. Many elastic materials may be elongated by much more than 60 percent (i.e., much more than 160 percent of their relaxed length), for example, elongated 100 percent or more, and many of these will recover to substantially their initial relaxed length, for example, to within 105 percent of their initial relaxed length, upon release of the stretching force.
As used herein, the term °'nonelastic" refers to any material which does not fall within the definition of "elastic," above.
As used herein, the terms "recover" and "recovery" refer to a contraction of a stretched material upon termination of a biasing force following stretching of the material by application of the biasing force. For example, if a material having a relaxed, unbiased length of one (1) inch is elongated 50 percent by stretching to a length of one and one half (1.5) inches the material would be elongated 50 percent (0.5 inch) and would have a stretched length that is 150 percent of its relaxed length. If this exemplary stretched material contracted, that is recovered to a length of one and one tenth (1.1) inches after release of the biasing and stretching force, the material would have recovered 80 percent (0.4 inch) of its one-half (0.5) A inch elongation. Recovery may be expressed as [(maximum stretch length - final sample length)/(maximum stretch length - initial sample length)] X 100.
As used herein, the term "nonwoven web" means a web having a structure of individual fibers or threads which are interlaid,~ but not in an identifiable, repeating manner. Nonwoven webs have been, in the past, formed by a variety of processes such as, for example, meltblowing processes, spunbonding processes and bonded carded web processes.
As used herein, the term "microfibers" means small diameter f fibers having an average diameter not greater than about 100 microns, for example, having an average diameter of from about 0.5 microns to about 50 microns, or more particularly, microfibers may have an average diameter of from about 4 microns to about 40 microns.
As used herein, the term "meltblown fibers" means fibers formed by extruding a molten thermoplastic material through a plurality of fine, usually circular, die capillaries as molten threads or filaments into a high velocity gas (e. g.
air) stream which attenuates the filaments 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 disbursed meltblown fibers. Such a process is disclosed, for example, in U.S. Patent No. 3,849,241 to Butin, As used herein, the term "spunbonded fibers" refers to small diameter fibers which are formed by extruding a molten thermoplastic material as filaments from a plurality of fine, usually circular, capillaries of a spinnerette with the diameter of the extruded filaments then being rapidly reduced as by, for example, eductive drawing or other well-known spun-bonding mechanisms. The production of spunbonded nonwoven webs is illustrated in patents such as, for example, in U.S. Patent No. 4,340,563 to Appel et al., and U.S. Patent No. 3,692,618 to Dorschner et al.
As used herein, the term "stress relaxation" refers to the loss of tension or load measured after a sample of an elastic material has been elongated at a specified rate of extension to a predetermined length and held at that length for a specified period of time, for example, from about 1 minute to about 30 minutes. Except where otherwise noted for the present invention, stress relaxation is expressed as a percentage loss of the initial load encountered at a specified extension of an elastic material. The stress relaxation is determined by calculating the difference between the initial load measured after elongating an elastic material at a rate of 20 inches per minute to an elongation of 300% (i.e., to 400 percent of the material's initial length) and the remaining load measured after that sample was held at that length for 20 minutes divided by the initial load at that length. Testing may be performed on an InstronT"~Model 1122 Universal Test Machine using a 100 mm by 3 inch sample attached to j aw faces that have a width of 3 inches and a height of 1 inch. Stress relaxation after 20 minutes at, for example, an elongation of 300%
(i.e., to 400% of the material's initial length - from 100 mm to 400 mm) may be expressed as a percentage utilizing the following equation:
stress relaxation = (peak load300X ' yak load300X°~0 min)/(peak load300X)t~00 As used herein, the term "average molecular weight"
refers to the number average molecular weight of a polymer or polymer fragment as determined by gel permeation chromatography. Molecular weight information for the styrene-poly(ethylene-propylene)-styrene elastomeric block copolymers and the styrene-polyethylene-butylene)-styrene elastomeric. block copolymers was obtained from the Shell Chemical Company.

~~~~~~~~1 As used herein, the term "melt flow rate" refers to the amount of material under a pressure or load that flows through an orifice at a given temperature over a measured period of time. The melt flow rate is expressed in units 5 of weight divided by time (i.e., grams/l0 minutes). The melt flow rate was determined by measuring the weight of a polymer under a 2.160 kg loaa'l that flowed through an orifice diameter of 2.0995 ~ 0.0051 mm during a measured time period such as, for example, 10 minutes at a specified temperature such as, for example, 190°C as determined in accordance with ASTM Test Method D1238-82, "Standard Test Method for Flow Rates of Thermoplastic By Extrusion Plastometer," using a Model VE 4-78 Extrusion Plastometer (Tinius Olsen Testing Machine Co., Willow Grove, Pennsylvania).
As used herein, the term "superabsorbent" refers to absorbent materials capable of absorbing at least 10 grams of aqueous liquid (e.g. distilled water) per gram of absorbent material while immersed in the liquid for 4 hours and holding substantialy all of the absorbed liquid while under a compression force of up to about 1.5 psi.
As used herein, the term "polymer" generally includes, but is not limited to, homopolymers, copolymers, such as, for example, block, graft, random and alternating copolymers, terpolymers, etc. and blends and modifications thereof. Furthermore, unless otherwise specifically limited, the term "polymer" shall include all possible geometrical configurations of the material. These configurations include, but are not limited to, isotactic, 3o syndiotactic and random symmetries.
As used herein, the term "consisting essentially of"
does not exclude the presence of additional materials which do not significantly affect the desired characteristics of a given composition or product. Exemplary materials of this sort would include, without limitation, pigments, antioxidants, stabilizers, surfactants, waxes, flow ~,,. ,z ~.~~
promoters, particulates and materials added to enhance processability of the composition.
As used herein, the term "compatible" refers to the relationship of one polymeric material to another with respect to the extrusion process and extrudates. To be compatible, two different polymeric materials should, for example, be capable of blending into a substantially homogeneous miscible mixture.
SUl~iMARy OF THE INVENTION
The present invention addresses problems of the prior art by providing an elastic nonwoven web of fibers formed from a blend including: (1) a styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer or a mixture of styrene-poly(ethylene-propylene)-styrene and styrene-poly(ethylene-butylene)-styrene elastomeric block copolymers; and (2) a tackifying resin, in which the nonwoven elastic web has a stress relaxation of less than about 30 percent. The styrene-polyethylene-propylene)-styrene thermoplastic elastomeric block copolymer component of the blend used to form the elastic web has a general formula of:
(-CH-CH2-)m-(-CH2-CH-CH2-CH2)n-(-CH-CH2-)m wherein m is an integer of at least about 38, for example, from about 38 to about 337; and n is an integer of at least about 500, for example, from about 500 to about 1860; and R is a benzyl group. The elastomeric block copolymer typically has an average molecular weight ranging from about 50,000 to about 90,000 and an average molecular weight ratio of polystyrene endblocks to poly(ethylene-propylene) midblocks ranging from about 10:90 to about 25:75. For example, one particularly useful elastomeric block copolymer has an average molecular weight of about 62,000 with polystyrene endblocks each having an average molecular weight of about 6200 and an average molecular ~~~~:1~~
weight ratio of polystyrene endblocks to poly(ethylene-propylene) midblocks of about 21.7:78.3.
In some situations, it may be desirable to blend the styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer with another elastomeri.c block copolymer such as, for example, a styrene-polyethylene-butylene)-styrene block copolymer to form an elastomeric block copolymer mixture. Such a mixture may be used in place of a substantially pure styrene-poly(et:hylene-propylene)-styrene l0 elastomeric block copolymer and still achieve the desired stress-relaxation properties.
The tackifying resin component of the blend may be for example, hydrogenated hydrocarbon resins and/or terpene hydrocarbon resins. The blend may also contain a polyolefin and/or an extending oil. The polyolefin component of the blend may be selected from, for example, polyethylene, polypropylene, polybutylene, polyethylene copolymers, polypropylene copolymers, polybutylene copolymers and mixtures thereof. The extending oil may be a mineral oil such as, for example, a white mineral oil.
The blend may contain from about 50 to about 80 percent, by weight, of the styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer or mixture of styrene-poly(ethylene-propylene)-styrene and styrene-poly(ethylene-butylene)-styrene elastomeric block copolymers, from about 15 to about 28 percent by weight of the tackifying resin, from about 3 to about 23 percent by weight of the polyolefin, and from about 0 to about 15 percent by weight of the extending oil.
The elastic nonwoven web of fibers may be a web of meltblown fibers or spunbonded fibers. The meltblown fibers may be microfibers. The elastic nonwoven web may also include at least one type of nonelastic fibers and/or particulate materials, far example nonelastic microfibers, which are distributed within or upon the matrix. The nonelastic fibers may be generally uniformly distributed throughout the matrix. Random and gradient distributions are also envisioned.
The nonelastic fibers, which may be microfibers, may be selected from the group including polyester fibers, polyamide fibers, glass fibers, polyolefin fibers, cellulosic derived fibers, multi~-component fibers, natural fibers or electrically conductive fibers or blends of two or more nonelastic fibers. If the nonelastic fibers are natural fibers, the natural fibEers may be selected from, for example, cotton fibers, woo:L fibers and silk fibers.
If the nonelastic fibers are polyolefin fibers, the polyolefin fibers may be selected from, for example, polyethylene fibers or polypropylene fibers. If the nonela tic fibers are cellulosic derived fibers, the cellulosic derived fibers may be selected from, for example, rayon fibers or wood fibers. Exemplary wood fibers are wood pulp fibers. If the nonelastic fibers are polyamide fibers, the polyamide fibers may be nylon fibers.
If the nonelastic fibers are multi-component fibers, the multi-component fibers may be sheath-core fibers or side-by-side fibers. The nonelastic fibers may be absorbent or superabsorbent fibers.
If nonelastic fibers are present in the elastic nonwoven web, the elastic nonwoven web may generally include from about 20 percent, by weight, to about 99 percent, by weight, of fibers formed from the styrene-poly(ethylene-propylene)-styrene blend and from about 1 percent, by weight to 80 percent, by weight, of the nonelastic fibers.
For example, the elastic nonwoven web may include from about 50 percent, by weight to about 99 percent, by weight, of fibers formed from the styrene-polyethylene-propylene)-styrene blend and from about 1 percent, by weight, to about 50 percent, by weight, of the nonelastic fibers. In certain applications, particulate materials may be substituted for the nonelastic fibers. Alternatively, the elastic nonwoven web may have both nonelastic fibers and particulate materials incorporated into the matrix styrene-poly(ethylene-propylene)-styrene fibers. In such a three component system, the elastic nonwoven web may contain from about 50 percent, by weight, to about 98 percent, by weight, of the styrene-poly(ethylene-propylene)-styrene blend fibers, from about 1 percent, by weight, to about 49 percent, by weight, of nonelastic fibers and from about 1 percent, by weight, to about 4'9 percent, by weight, of particulate materials. Exemplary particulate materials are activated charcoal and superabsorbent materials such as, for example, hydrocolloids.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of an apparatus, including a meltblowing die, which may be utilized to form the elastic nonwoven web of the present invention.
FIG. 2 is an exemplary stress-strain curve for an elastic nonwoven web of meltblown fibers formed from a styrene-poly(ethylene-propylene)-styrene thermoplastic elastomeric block copolymer blend.
FIG. 3 is an exemplary stress-strain curve for an elastic nonwoven web of meltblown fibers formed from a styrene-polyethylene-butylene)-styrene thermoplastic elastomeric block copolymer blend.
FIG. 4 is an exemplary stress-strain curve for an elastic nonwoven web of meltblown fibers formed from a modified styrene-polyethylene-butylene)-styrene thermoplastic elastomeric block copolymer blend.
FIG. 5 is a bottom view of the die of Figure 1 with the die having been rotated 90 degrees for clarity.
FIG. 6 is a cross-sectional view of the die of Figure 1 taken along line 3-3 of Figure 5.
FIG. 7 is a schematic illustration of an apparatus which may be utilized to form the embodiment of the present invention where nonelastic fibers are incorporated into the matrix of meltblown fibers.

.a to DETAILED DESORIPTION OF THE I~NTION
The elastic nonwoven web (e.g., a film, porous film or fibrous nonwoven web) may be formed by a variety of extrusion techniques. One particularly useful extrusion technique is to form a fibrous elastic nonwoven web by meltblowing.
Turning now to the figures a;nd, in particular, to FIG.
1, wherein like reference numerals represent the same or equivalent structure, it can be seen that an apparatus for forming the elastic nonwoven web of the present invention is schematically generally represented by reference numeral 10. In forming the elastic no;nwoven web of the present invention pellets or chips, etc.(not shown) of a blend material are introduced into a pellet hopper 12 of an extruder 14.
The elastic nonwoven web of fibers of the present invention is formed from (1) a blend of an elastic styrene-poly(ethylene-propylene)-styrene (SEPS) block copolymer or a mixture of styrene-poly(ethylene-propylene)-styrene and styrene-polyethylene-butylene)-styrene elastomeric block copolymers and (2) a tackifying resin. The blend may further include a polyolefin and an extending oil. The styrene-poly(ethylene-propylene)-styrene thermoplastic elastomeric block copolymer component has a general formula of:
(°~H-CH2-)m-(-CH2-iH-CH2-CH2)n-(-CH-CH2-)m wherein m has a value of at least about 38, for example, from about 38 to about 337; and n has a value of at least about 500, for example, from about 500 to about 1860; and R is a benzyl group. Particularly useful values for m range from about 48 to about 87 resulting in a polystyrene endblock having an average molecular weight from about 5,000 to about 10,000. Particularly useful values for n rednge from about 570 to about 1000 resulting 6a G~ ~ ~~ .
in a polyethylene-propylene) midblock having an average molecular weight from about 40, 000 to about 70, 000. The total molecular weight of the polymer may be, for example, from about 50,000 to about 90,000. Such rubbery block copolymers may have an average molecular weight ratio of polystyrene endblocks to polyethylene-propylene) midblocks from about 10:90 to about 25:75. For example, one styrene-poly(ethylene-propylene)--styrene(SEPS) elastomeric block copolymer useful in the present invention is l0 available from the Shell Chemical Company and has an average molecular weight of about 62,000 with polystyrene endblocks each having an average molecular weight of about 6200 and an average molecular weight ratio of polystyrene endblocks to polyethylene-propylene) midblocks of about 21.7:78.3. Exemplary properties of that SEPS polymer are given in Table 1.
STYRENE-POLY(ETHYLENE-PROPYLENE,j-STYRENE ~SEPS) BLOCK COPOLYMER
Physical Properties Tensile Strength', psi 2260 300% Modulus', psi Elongation at Break', % 550 Stress Relaxation2, % 23 Hysteresis Properties3:
Recoverable Energy4, Sets, fo 'Determined in accordance with ASTM D-412 using 3mm wide (approximately 0.1 inch) and 0.020 inches thick dumbbell samples that are cut from films cast from toluene solution.
ZSample was elongated at 20 inches/minute to 160 percent elongation and held at 160 percent elongation for 30 minutes. Stress relaxation is the ratio determined by dividing the load after 30 minutes at 160 percent elongation by the peak load at 160 percent elongation and multiplying by 100.
3Determined by elongating the sample at 1 inch/minute to 150 percent elongation and cycling back to zero load for 1 hysteresis loop.
4Determined by dividing the area under the retraction curve of the first hysteresis loop by the area under the elongation curve of the first hysteresis loop and then multiplying by 100.
SDetermined by dividing the zero load extension after 1 cycle by the initial sample gauge length and then multiplying by 100. The zero load extension is the distance that the jaws of the tensile test equipment move at the beginning of the second cycle before a load is registered by the tensile test equipment.
In some situations, it may be desirable to blend the styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer with another elastomeric block copolymer such as, for example, a styrene-polyethylene-butylene)-styrene block copolymer to form an elastomeric block copolymer mixture. Such a mixture may be used in the present invention in place of a substantially pure styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer and still achieve the desired stress-relaxation properties. Useful elastomeric block copolymer mixtures may contain up to about 60 parts by weight of styrene-poly(ethylene-butylene)-styrene elastomeric block copolymer per 100 parts of elastomeric block copolymer and down to about 40 parts by weight of styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer per 100 parts of elastomeric block copolymer. One useful styrene-poly(ethylene-butylene)-styrene elastomeric block copolymer has an average molecular weight of about 50,000 with polystyrene endblocks having an average molecular weight of about 7200 and an average molecular weight ratio of polystyrene endblocks to polyethylene-butylene) midblocks of about 30:70. Such a styrene-polyethylene-butylene)-styrene block copolymer may be obtained from the Shell Chemical Company under the trade designation IUtATONs G-1652.
Various tackifying resins may be used in the present invention. In particular, the purpose of the tackifying resin is to provide an elastic web that can act as a pressure sensitive adhesive, e.g., to bond the elastic sheet to a gatherable web. Of course, various tackifying resins are known, and are discussed, e.g., in U.S. Patent Nos. 4,789,699, 4,294,936 and 3,783,072, Any tackifier resin can be used which is compatible with the elastic polymer and the polyolefin, and can withstand the high processing (e. g., extrusion) temperatures. Generally, hydrogenated hydrocarbon resins are preferred tackifying resins, because of their better temperature stability. Tn the following paragraphs are disclosed information on three specific tackifying resins, two of which (REGALREZ'~ and ARKON~P
series tackifiers) are examples of hydrogenated hydrocarbon resins, and the ZONATAC~501 lite being a terpene hydrocarbon. Of course, while the three tackifying resins are specifically discussed, the present invention is not limited to use of such three tackifying resins, and other tackifying resins which are compatible with the other components of the composition and can withstand the high processing temperatures, and can achieve the objectives of the present invention, can also be used.
REGALREZ~ hydrocarbon resins, a product of Hercules, Incorporated, are fully hydrogenated a-methyl styrene-type low molecular weight hydrocarbon resins, produced by polymerization and hydrogenation of pure monomer hydrocarbon feed stocks. Grades 1094, 3102, 6108 and 1126 are highly stable, light-colored low molecular weight, nonpolar resins suggested for use in plastics modification, adhesives, coatings, sealants and caulks. The resins are compatible with a wide variety of oils, waxes, alkyds, plastics and elastomers and are soluble in common organic solvents.
ZONATAC~501 lite resin, a product of Arizona Chemical Co., has a softening point of 105° C., a Gardner color 1963 (50% in heptane) of 1 -- and a Gardener color neat (pure) of 2+; a color (approximate Gardner color equal to 1 --(50% in heptane); APHA color - 70) of water white, a specific gravity (25°/25° C.) of 1.02 and.a flash point (closed cup, °F.) of 480°F.
The polyolefin which may be utilized in the extrudable composition must be one which, when blended with the elastic block copolymer or a mixture of elastomeric block copolymers and subjected to an appropriate combination of elevated pressure and elevated temperature conditions, is extrudable, in blended form, with the elastomeric block copolymer or mixture of elastomeric block copolymers. In particular, useful polyolefin materials include polyethylene, polypropylene and polybutylene, including polyethylene copolymers, polypropylene copolymers and 5 polybutylene copolymers. Blends of two or more of the polyolefins may be utilized.
One particular polyethylene may be, obtained from U.S.I.
Chemical Company under the trade-mark Petrothene NA
601 (also referred to herein as PE NA 601) . Information 10 obtained from U.S.I. Chemical Company states that PE NA 601 is a low molecular weight, low density polyethylene for application in the areas of hot melt adhesives and coatings. U.S.I. has also stated that PE NA 601 has the following nominal values: (1) a Brookfield viscosity, cP at 15 150 degrees Centigrade of 8,500 and at 190 degrees Centigrade of 3,300 when measured in accordance with ASTM
D 3236; (2) a density of 0.903 grams per cubic centimeter when measured in accordance with ASTM D 1505; (3) an equivalent Melt index of 2,000 grams per 10 minutes when measured in accordance with ASTM D 1238: (4) a ring and ball softening point of 102 degrees Centigrade when measured in accordance with ASTM E 28; (5) a tensile strength of 850 pounds per square inch when measured in accordance with ASTM D 638: (6) an elongation of 90% when measured in accordance with ASTM D 638; (7) a modulus of rigidity, Tf(45,000) of -34 degrees Centigrade; and (8) a penetration hardness (tenths of mm) at 77 degrees Fahrenheit of 3.6.
Of course, the present invention is not limited to use of such specific polyolefins described herein. In this regard, note the polyolefins as described in U.S. Patent Nos. 4,663,220 and 4,789,699. More generally, and noting the specific purpose of the polyolefin, as described in the U.S.
Patent No. 4,663,220, various polyolefins which can be utilized in the present invention can easily be determined.
Extending oils which may be used in the blend should be " capable of being melt-processed with the other components of the blend without degrading. An exemplary extending oil is a white mineral oil available under the trade-mark Drakeol 34 from the Pennzoil company.
Drakeol 34 has a specific gravity of .864-.878 at 60'F, a flash point 460°F and viscosity of 370-420 SUS at 100'F
(other physical properties). Suitable vegetable oils, animal oils and their derivatives may also be used as the extending oil.
The components of the composition of the present invention can be utilized over broad ranges of the amounts of each component. As a guide, the best results have been obtained when utilizing a four-component blend of a styrene-poly(ethylene-propylene)-styrene(SEPS)elastomeric block copolymer or a mixture of styrene-poly(ethylene-propylene)-styrene (SEPS) and styrene-poly(ethylene-butylene)-styrene (SEES) elastomeric block copolymers, a polyolefin, a tackifier and an extending oil. The following ranges, as shown in Table 2, are exemplary. It is emphasized that these ranges are merely illustrative, serving as a guide for amounts of the various components in the composition.

Weight SEPS elastomeric block copolymer or mixture of 50-80 SEPS and SEBS elastomeric block copolymers Tackifier 15-28 Polyolefin 3-23 Extending Oil 0-15 ~~~~:~'l Elastic nonwoven webs formed from blends containing the recited levels of additives such as, for example, 57.7 percent, by weight, Shell Chemical Co., styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer (molecular weight 62,000) available from the Shell Chemical Company; 18.3 percent, by weight, REGALREZ~
1126 (hydrocarbon tackifying resin); 18.2 percent, by weight, Petrothene NA 601 (polyethylene); and 5.8 percent, by weight, Drakeol 34 (mineral oil) had a flatter stress-strain hysteresis loop and less stress relaxation at 300 elongation than the conventional styrene-poly(ethylene-butylene)-styrene blend as can be seen from Figures 2-4.
Specifically, FIG. 2 is an exemplary stress-strain curve for a 53.3 gsm meltblown web formed from the above described styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer blend. FIG. 3 is an exemplary stress-strain curve for a 64.8 gem meltblown web formed from a blend of about 63 percent, by weight, styrene polyethylene-butylene)-styrene elastomeric block copolymer (KRATON~ G-1657); 17 percent, by weight, REGALREZ~ 1126;
and 20 percent, by weight, Petrothene NA 601. FIG. 4 is an exemplary stress-strain curve for a 85.6 gem meltblown web formed from a blend of about 63 percent, by weight, styrene-polyethylene-butylene)-styrene elastomeric block copolymer mixture (the mixture being a combination of about 42.2 percent, by weight, KRATON~ G-1652 and about 2?.3 percent, by weight KRATON~ G-1657); about 22.1 percent, by weight, REGALREZ~ 1126; about 4.4 percent, by weight, Petrothene NA 601; and about 10.5 percent, by weight, Drakeol 34 oil.
As stated previously, while the extrudable elastomeric composition used to form the elastic sheet has been discussed in terms of a four-component extrudable composition of (1) styrene-poly(ethylene-propylene)-styrene elastomeric polymer or mixture of styrene-poly(ethylene-propylene)-styrene and styrene-polyethylene-butylene)-styrene elastomeric block copolymers; (2) polyolefin; (3) tackifying resin; and (4) extending oil; the polyolefin, which functions as a flow promoter for the composition can be substituted by other compatible flow promoters or processing aids, or can be eliminated altogether where the tackifying resin can also act as the flow promoter and/or extending oil. The extending oil, which functions as a processing aid, may also be substituted by other compatible processing aids or can be eliminated altogether where the tackifying resin can also act a:a the extending oil. For example, low molecular weight hydrocarbon resins such as REGALREZ~ tackifier can also act as the viscosity reducer and/or the extending oil, whereby the extrudable composition may contain the elastomeric block copolymers) and the tackifying resin (e. g., REGALREZ~ tackifier).
While the principal components of the blend have been described in the foregoing, such extrudable composition is not limited thereto, and can include other components not adversely affecting the composition attaining the stated objectives. The blend used to form the elastic nonwoven web may be mixed with other appropriate materials, such as, for example, pigments, antioxidants, stabilizers, surfactant , waxes, flow promoters, solvents, particulates and materials added to enhance processability of the composition prior to or after its introduction into the hopper 12.
Referring again to FIG. 1, the extruder 14 has an extrusion screw (not shown) which is driven by a conventional drive motor (not shown). As the elastic block copolymer advances through the extruder 14, due to rotation of the extrusion screw by the drive motor, it is progressively heated to a molten state. Heating of the elastic block copolymer to the molten state may be accomplished in a plurality of discrete steps with its temperature being gradually elevated as it advances through discrete heating zones of the extruder 14 toward a meltblowing die 16. The die 16 may be yet another heating s , ~~8~~~~v~
zone where the temperature of the thermoplastic resin is maintained at an elevated level for extrusion. The temperature which will be required to heat the elastic block copolymer to a molten state will vary somewhat depending upon which grade of elastic block copolymer is utilized and can be readily determined by those in the art.
However, generally speaking, the elastic block copolymer may be extruded within the temperature range of from about 450 degrees Fahrenheit to about 550 degrees Fahrenheit.
For example, the extrusion may be accomplished within a temperature range of from about 475 degrees Fahrenheit to about 500 degrees Fahrenheit. Heating of the various zones of the extruder 14 and the meltblowing die 16 may be achieved by any of a variety of conventional heating arrangements (not shown).
FIG. 5 illustrates that the lateral extent 18 of the die 16 is provided with a plurality of orifices 20 which are usually circular in cross-section and are linearly arranged along the extent 18 of the tip 22 of the die 16. The orifices 20 of the die 16 may have diameters that range from about 0.01 of an inch to about 0.02 of an inch and a length which may range from about 0.05 inches to about 0.20 inches. For example, the orifices may have a diameter of about 0.0145 inches and a length of about 0.113 inches.
From about 5 to about 50 orifices may be provided per inch of the lateral extent 18 of the tip 22 of the die 16 with the die 16 extending from about 30 inches to about 60 inches or more. FIG. 1 illustrates that the molten elastic block copolymer emerges from the orifices 20 of the die 16 as molten strands or threads 24.
FIG. 6, which is a cross-sectional view of the die of FIG. 5 taken along line 3-3, illustrates that the die 16 preferably includes attenuating gas inlets 26 and 28 which are provided with heated, pressurized attenuating gas (not shown) by attenuating gas sources 30 and 32. (See FIGS. 1 and 5). The heated, pressurized attenuating gas enters the die 16 at the inlets 26 and 28 and follows a path generally designated by the arrows 34 and 36 throucJh the two chambers 38 and 40 and on through the two narrow passageways or gaps 42 and 44 so as to contact the extruded threads 24 as they exit the orifices 20 of the die 16. The chambers 38 and 40 are designed so that the heated attenuating gas passes through the chambers 38 and 40 and exits the gaps 42 and 44 to form a stream (not shown) of attenuating gas which exits the die 16 on both sides of the threads 24. The temperature and pressure of the heated stream of attenuating gas can vary widely. For example, the heated attenuating gas can be applied at a temperature of from about 470 degrees Fahrenheit to about 580 degrees Fahrenheit, more particularly, from about 500 degrees Centigrade to about 550 degrees Centigrade. The heated attenuating gas may generally be applied at a pressure of from about 0.5 pounds per square inch, gauge to about 20 pounds per square inch, gauge. More particularly, from about 1 pound per square inch, gauge to about 5 pounds per square inch, gauge.
The position of air plates 46 and 48 which, in conjunction with a die portion 50 define the chambers 38 and 40 and the gaps 42 and 44, may be adjusted relative to the die portion 50 to increase or decrease the width of the attenuating gas passageways 42 and 44 so that the volume of attenuating gas passing through the air passageways 42 and 44 during a given time period can be varied without varying the velocity of the attenuating gas. Furthermore, the air plates 46 and 48 may be adjusted to effect a °'recessed"' die-tip configuration as illustrated in FIG. 3 or a positive die-tip 22 stick-out where the tip of die portion 50 protrudes beyond the plane formed by the plates 48.
Generally speaking, a positive die-tip stick-out configuration and attenuating gas pressures of less than 5 pounds per square inch, gauge are used in conjunction with air passageway widths, which axe usually the same and are no greater in width than about 0.110 inches. bower attenuating gas; velocities and wider air passageway gaps are generally preferred if substantially continuous meltblown fibers or microfibers 24 are to be produced.
The two streams of attenuating gas converge to form a stream of gas which entrains and attenuates the molten threads 24, as they exit the orifices 20, into fibers or, depending upon the degree of attenuation, microfibers, of a small diameter which is usually less than the diameter of the orifices 20. The gas-borne fibers or microfibers 24 are blown, by the action of the attenuating gas, onto a collecting arrangement which, in the embodiment illustrated in FIG. 1, is a foraminous endless belt 52 conventionally driven by rollers 54. Other foraminous arrangements such as a rotating drum could be utilized. One or more vacuum boxes (not illustrated) may be located below the surface of the foraminous belt 52 and between the rollers 54. The fibers or microfibers 24 are collected as a coherent matrix of fibers on the surface of the endless belt 52 which is rotating as indicated by the arrow 58 in FIG. 1. The vacuum boxes assist in retention of the matrix on the surface of the belt 52. Typically the tip 22 of the die 16 is from about 6 inches to about 14 inches from the surface of the foraminous belt 52 upon which the fibers are collected. The thus-collected, entangled fibers or microfibers 24 are coherent and may be removed from the belt 52 as a self-supporting nonwoven web 56 by a pair of pinch rollers 60 and 62 which may be designed to press the fibers of the web 56 together to improve the integrity of the web 56.
The above-described meltblowing techniques, and apparatus are discussed fully in U.S. Patent No. 4,663,220.
For example, a blend containing, by weight, 57.7, percent styrene-poly(ethylene-propylene)styrene block copolymer (molecular weight 62,000) available from the Shell Chemical Company; 18.3 percent Petrothene NA.601 polyethylene; 18.2 percent REGALREZ~1126;
and 5.8 percent Drakeol 34 was meltblown with the blend 4~~~a~~~>' ' heated to a temperature of 480° F. Generally, and intended to be illustrative and not limiting, the following described parameters can be used for meltblowing the polymer blends to form the elastic nonwoven webs of the present invention. Thus, the brands can be meltblown while at a temperature of 450° to 550°F, preferably 475° to 500°
F, during. the meltblowing. The' primary air temperature, during the meltblowing, can be .475° to 525° F, preferably 500° to 520° F; and the primary air pressure can be 1.5-8 pounds per square inch (psi) gauge, preferably 2-4 psi gauge.
In some situations, nonwoven webs of elastic fibers formed from blends that contain the previously described mixtures of a styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer and another elastomeric block copolymer such as, for example, styrene-poly(ethylene-butylene)-styrene elastomeric block copolymers may have a measured stress relaxation which is greater than 30 percent. This has been observed for relatively low basis weight webs (e. g., basis weights less than about 55 grams per 1"x 6" area) formed from certain formulations containing a mixture of styrene-polyethylene-propylene)-styrene and styrene-polyethylene-butylene)-styrene elastomeric block copolymers (See Example 6 and Table 6).
Although the invention should not be held to a particular theory of operation, it is believed that the high level of stress relaxation results from the movement of individual fibers in the loosely coherent fibrous structure of the nonwoven web. Such fiber movement may be reduced by using higher basis weight nonwoven webs which .typically have a more coherent fibrous structure. Fiber entangling may also be used to decrease the fiber movement. Fiber entangling is inherent in nonwoven web formation processe:~ (e. g., meltblowing processes) but may be generated or increased by processes such as, for example, hydraulic entangling or needlepunching. Alternatively and/or additionally, thermal bonding or a bonding agent can be utilized to decrease the fiber movement and increase the structural coherency of the web. For example, powdered bonding agents and chemical solvent bonding may be used. Additionally, it is believed formulations containing a mixture of styrene-poly(ethylene-propylene)-styrene and styrene-polyethylene-butylene)-styrene elastomeric block copolymers may be modified to reduce the level of stress relaxation by reducing the amount of certain processing aids that are believed to contribute to stress relaxation. For example, it is believed that the stress relaxation of the nonwoven webs prepared according to Example 6 may be reduced to less than 30 percent by reducing or eliminating the extending oil in the formulation in order to improve the structural coherence of the nonwoven web.
FIG. 7 illustrates another embodiment of the present invention where one or more types of nonelastic fibers 64 are distributed within or upon the stream of thermoplastic fibers or microfibers 24. Distribution of the nonelastic fibers 64 within the stream of fibers 24 may be such that the nonelastic fibers 64 are generally uniformly distributed throughout the stream of elastic block copolymer fibers 24. This may be accomplished by merging a secondary gas stream (not shown) containing the nonelastic fibers 64 with the stream of fibers 24.
Apparatus for accomplishing this merger may include a conventional picker roll 66 arrangement which has a plurality of teeth 68 that are adapted to separate a mat or batt 70 of nonelastic fibers into the individual nonelastic fibers 64. The mat or bait of fibers 70 which is fed to the picker roll 66 may be a sheet of pulp fibers (if a two component mixture of elastomeric block copolymer fibers and pulp fibers is desired), a mat of staple fibers (if a two component mixture of elastomeric block copolymer fibers and staple fibers :is desired) ar both a sheet of pulp fibers and a mat of staple fibers (if a three component mixture of elastomeric block copolymer fibers, staple fibers and pulp fibers is desired). In embodiments where, for example, an absorbent material is desired, the nonelastic fibers 64 are absorbent fibers. The nonelastic fibers 64 may generally be selected from the group including one or more polyester fibers, polyamide fibers, polyo:Lefin fibers such as, for example, polyethylene fibers and polypropylene fibers, cellulosic derived fibers such as, for example, rayon fibers and, wood pulp fibers, mufti-component fibers such as, for example, sheath-core a~ulti-component fibers or side-by-side mufti-component fibers, natural fibers such as silk fibers, wool fibers or cotton fibers or electrically conductive fibers or blends of two or more of such fibers.
Other types of nonelastic fibers 64 as well as blends of two or more of other types of fibers 64 may be utilized.
The nonelastic fibers 64 may be microfibers or the nonelastic fibers 64 may be macrofibers having an average diameter of from about 300 microns to about 1,000 microns.
The sheets or mats 70 of nonelastic fibers 64 are fed to the picker roll 66 by a roller arrangement 72. After the teeth 68 of the picker roll 66 have separated the mat of nonelastic fibers 70 into separate nonelastic fibers 64 the individual nonelastic fibers 64 are conveyed toward the stream of elastic block copolymer fibers or microfibers 24 through a nozzle 74. A housing 76 encloses the picker roll 66 and provides a passageway or gap 78 between the housing 76 and the surface of the teeth 68 of the picker roll 66.
A gas (not shown), for example air, is supplied to the passageway or gap 78 between the surface of the picker roll 66 and the housing 76 by way of a gas duct 80. The gas duct 80 may enter the passageway or gap 78 generally at the 3G junction 82 of the nozzle 74 and the gap 78. The gas is supplied in sufficient quantity to serve as a medium for conveying the nonelastic fibers 64 through the nozzle 74.
The gas supplied from the duct 80 also serves as an aid in removing the nonelastic fibers 64 from the teeth 68 of the picker roll 66. However, gas supplied through the duct 84 generally provides for the removal of the nonelastic fibers 64 from the teeth of the picker roll 66. The gas may be supplied by any conventional arrangement such as, for example, an air blower (not shown).
Generally speaking, the individual nonelastic fibers 64 are conveyed through the nozzle 74 at generally the 5 velocity at which the nonelastic fibers 64 leave the teeth 68 of the picker roll 66. In other words, the nonelastic fibers 64, upon leaving the teeth 68 of the picker roll 66 and entering the nozzle 74, generally maintain their velocity in both magnitude and direction from the point 10 where they left the teeth 68 of the picker roll 66. Such an arrangement, which is discussed in more detail in U.S.
patent 4,100,324 to Anderson et al., aids in substantially reducing fiber floccing.
As an aid in maintaining satisfactory nonelastic fiber 15 64 velocity, the nozzle 74 may be positioned so that its longitudinal axis is substantially parallel to a plane which is tangent to the picker roll 66 at the junction 82 of the nozzle 74 with the passageway 78. As a result of this configuration, the velocity of the nonelastic fibers 20 64 is not substantially changed by contact of the nonelastic fibers 64 with the walls of the nozzle 74. If the nonelastic fibers 64 temporarily remain in contact with the teeth 68 of the picker roll 66 after they have been separated from the mat or batt 70, the axis of the nozzle 25 74 may be adjusted appropriately to be aligned with the direction of nonelastic fiber 64 velocity at the point where the nonelastic fibers 64 disengage from the teeth 68 of the picker roll 66. The disengagement of the nonelastic fibers 64 from the teeth 68 of the picker roll 66 may be assisted by application of a pressurized gas, i.e., air through duct 84.
The vertical distance 86 that the nozzle 74 is below the die tip 22 may be adjusted to vary the properties of the composite web 88. Variation of the horizontal distance 90 of the tip 92 of the nozzle 74 from the die tip 22 will also achieve-variations in the final elastic nonwoven web 88. The vertical distance 86 and the horizontal distance 90 values will also vary with the material being added to the elastomeric block copolymer fibers 24. The width of the nozzle 74 along the picker roll 66 and the length that the nozzle 74 extends from the picker roll 66 are also important in obtaining optintum distribution of the nonelastic fibers 64 throughout the stream of fibers 24.
It is usually desirable far the length of the nozzle 74 to be as short as equipment design will allow. The length is usually limited to a minimum :length which is generally equal to the radius of the pick:er roll 66. Usually, the width of the nozzle 74 should not exceed the width of the sheets or mats 70 that are being fed to the picker roll 66.
The picker roll 66 may be replaced by a conventional particulate injection system to form a composite nonwoven web 88 containing various particulates. A combination of both particulates and nonelastic fibers could be added to the elastic block copolymer fibers prior to formation of the composite nonwoven web 88 if a conventional particulate injection system was added to the system illustrated in FIG. 4. FIG. 4 further illustrates that the gas stream carrying the nonelastic fibers 64 is moving in a direction which is generally perpendicular to the direction of movement of the stream of elastic block copolymer fibers 24 at the point of merger of the two streams. Other angles of merger of the two streams may be utilized. The velocity of the gas stream of nonelastic fibers 64 is usually adjusted so that it is less than the velocity of the stream of elastomeric block copolymer fibers 24. This allows the streams, upon merger and integration thereof to flow in substantially the same direction as that of the stream of elastomeric block copolymer fibers 24. Indeed, the merger of the t~ao streams may be accomplished in a manner which is somewhat like an aspirating effect where the stream of nonelastic fibers 64 is drawn into the stream of elastomeric block copolymer fibers 24. If desired the velocity difference between the two gas streams may be such that the nonelastic fibers 64 are integrated into the ~/ Y~ 1~
elastomeric block copolymer fibers 24 in a turbulent manner so that the nonelastic fibers 64 become substantially thoroughly and uniformly mixed throughout the elastomeric block copolymer fibers 24. Generally, far increased production rates the gas stream which entrains and attenuates the stream of elastomeric block copolymer fibers 24 should have a comparatively ;high initial velocity, for example from about 200 feet to aver 1,000 feet per second, and the stream of gas which carries the nonelastic fibers 64 should have a comparatively low initial velocity, for example from about 50 to about 200 feet per second. After the stream of gas that entrains and attenuates the elastomeric block copolymer fibers 24 exits the gaps 42 and 44 of the die 16, it immediately expands and decreases in velocity.
Upon merger and integration of the stream of nonelastic fibers 64 into the stream of elastomeric black copolymer fibers 24 to generally uniformly distribute the nonelastic fibers 64 throughout the stream of elastomeric block copolymer fibers 24, a composite stream 96 of thermoplastic fibers 22 and nonelastic fibers 64 is formed. Due to the fact that the elastomeric block copolymer fibers 24 are usually still semi-molten and tacky at the time of incorporation of the nonelastic fibers 64 into the elastomeric block copolymer fibers 24, the nonelastic fibers 64 are usually not only mechanically entangled within the matrix farmed by the elastomeric block copolymer fibers 24 but are also thermally bonded or joined to the elastomeric black copolymer fibers 24. In order to convert the composite stream 96 of elastomeric block copolymer fibers 24 and nonelastic fibers 64 into a composite elastic nonwoven web or mat 88 composed of a coherent matrix of the elastomeric block copolymer fibers 24 having the nonelastic fibers 64 generally uniformly distributed therein, a collecting device is located in the path of the composite stream 96. The collecting device may be the endless belt 52 of FIG. 4 upon which the composite stream 96 impacts to f.~~~~~ ~~
form the composite nonwoven web 56. The belt 52 is usually porous and a conventional vacuum arrangement (not shown) which assists in retaining the composite stream 96 on the external surface of the belt 52 is usually present. Other collecting devices are well known to those of skill in the art and may be utilized in place of the endless belt 52.
For example, a porous rotating drum arrangement could be utilized. Thereafter, the composite elastic nonwoven web 88 is removed from the screen by i:he action of rollers such as roller 60 and 62 shown in FIG. 1.
EXAMPLE I
A fibrous nonwoven elastic web was formed by meltblowing a blend of approximately 57.7 percent, by weight, styrene poly(ethylene-propylene)-styrene elastic block copolymer (molecular weight 62,000) obtained from the Shell Chemical Company, 18.3 percent, by weight, Petrothene NA 601 (polyethylene), 18.2 percent, by weight, REGALREZ~1126 tackifying resin, and 5.8 percent, by weight, Drakeol 34 mineral oil. The blend had a melt flow rate of 11.5 grams per 10 minutes. The melt flow rate of the blend was determined in accordance with ASTM D1238 at 190°C under a 2160 gram load over a 10 minute period.
Meltblowing of the blend was accomplished by extruding the blend through a meltblowing die having 30 extrusion capillaries per lineal inch of die tip. The capillaries each had a diameter of about (0.0145 inches) and a length of about (0.113 inches). The elastic blend was passed through the capillaries at a rate of about 0.1513 grams per capillary per minute at a temperature of about 480 degrees Fahrenheit. The extrusion pressure exerted upon the molten blend in the die tip was measured as 254 pounds per square inch, gauge. The die tip configuration was adjusted so that it had a positive die tip stickout of about (0.010) inches from the plane of the external surface of the lips of the air plates which form the air passageways on either side of the capillaries. The air plates were adjusted so that the two air passageways, one on each side of the extrusion capillaries, formed air passageways of a width or gap of about (0.067 inches). Forming air far meltblowing the blend was supplied to the air passageways at a temperature of about 503 degrees Fahrenheit and at a pressure of about 1.9 pounds per square inch, gauge. The meltblown fibers thus formed were blown onto a forming screen which was approximately 7.4 inches from the die tip.
The meltblown fibers were collected on the forming screen into coherent nonwoven webs having basis weights of approximately 80 grams per square meter (gsm), 65 gsm, and 50 gsm.
Examples 2 - 6 were conducted in accordance with Example 1. Extrudable blends for those examples were prepared by blending varying amounts of a styrene-poly(ethylene propylene)-styrene elastomeric block copolymer (molecular weight 62,000) available from the Shell Chemical Company, a polyolefin (Petrothane NA 601 polyethylene), a tackifying resin (REGALREZ~ 1126 hydrocarbon resin), and an extending oil (Drakeol 34 white mineral oil). Tn Example 3, the styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer is the same as that described above except that the average molecular weight ratio of polystyrene endblocks to polyethylene-propylene) midblocks is about 25:75. In Example 6, the styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer was combined with a styrene-poly(ethylene-butylene)-styrene elastomeric block copolymer available from the Shell Chemical Company under the trade designation HI2ATON~ G-1652 to form an elastomeric block copolymer mixture. The amount of each component is expressed in weight percent in Table 4 for each extrudable elastomeric composition. Additives which are present only in small amounts such as, for example, antioxidant are not shown in the formulations of Table 4.
Example Z ~ ~t 5 6 Styrene-poly 61.9 61.9 61.9 57.7 23.3 (ethylene-propylene) -styrene block copolymer KRATON~ G-1652 0 0 0 0 35.0 polyoiefin 8.7 8.7 8.7 18.3 14.0 tackifying resin 19.5 19.5 19.5 18.2 18.4 extending oil 9.9 9.9 9.9 5.8 9.3 'Average molecular weight ratio of polystyrene endblocks to polyethylene-propylene) midblocks for this SEPS elastomeric block copolymer is about 25:75.
All of the meltblown webs wexe prepared using a meltblowing die which had 30 extrusion capillaries per lineal inch of die tip. The capillaries of the meltblowing die each had a diameter of about (0.0145 inches) and a length of about (0.113 inches). The various process parameters of Examples 2 - 6 are detailed in Table 5.

>~~~~~'~
TABLE

Example 2 3 4 5 6 Melt 21 75 18.0 12.0 11.4 Flow Rate' Extrusion 0.756 0.756 0.378 0.353 0.504 Ratez Extrusion Die Temperature3 481 481 476 476 477 Extrusion Die Pressure4 357 210 295 254 300 Die p Ti Stick-Outs 0.010 0.010 0.010 -0.148 -0.148 Air Passageway 0.067 0.067 0.067 0.067 0.067 Gap6 Air 512 511 527 503 498 Temperature' Air 1.9 1.9 1.9 1.9 1.9 Pressure8 Distance Die-Tip to Forming 10 10 10 14 14 Screen9 1 es =
in grams per minut 2 y per e = minut in grams per capillar =
in degrees Fahrenheit 4 inch, in die cavity = gauge the tip in pounds per square 5 alues ate ssed tip arrangement) = indic rece die in inches (negative v =
in inches =
in degrees Fahrenheit 8 inch, = gauge in pounds per square =
in inches TENSILE TEST AND CYCLING DATA
The meltblown webs produced in Examples 1-5 were tested to determine the tensile. properties of those materials.
The results of the tests are reported in Table 6. The 5 meltblown webs were tested on a Constant Rate of Extension Tester, Instron Model 1122 Universal Testing Instrument.

~a~~;~' Samples were cut to 1" width by 6" length, with 'the 6"
dimension in the direction of stretch measurement. Three (3) samples were cut for each fabric direction (i.e., machine direction and cross machine direction). Each sample was placed lengthwise in jaw faces, 3" wide x 1"
length, with a jaw span or separation of 4 inches. The Instron crosshead speed was set at 20 inches per minute.
Measurements were taken of the load at 100% elongation (i.e., 200% of the material's initial length) and 250%
elongation (i.e., 350% of the material's initial length) during the load portion of the first cycle and the load at 100% elongation during the unload portion of the cycle.
The measurements were repeated at 100% elongation and 250%
elongation during the load portion of 'the second cycle and at 100% elongation during the unload portion of the second cycle. The sample was then extended to 300% elongation (i.e., 400% of the material's initial length) at 20 inches per minute and the load was measured (a) upon reaching 300%
elongation, (b) after being held at 300% elongation for 1 minute and (c) after being held at 300% elongation for 20 minutes. The difference between the initial load measured after 300% elongation and the load measured at 300%
elongation for 20 minutes was determined.
b O .
.. a C X 7.
7 uJ .D
N
M ~ 31 N M ~ O V O 0 ~ N
O m CO P 1~ G ~ I~ P. ~ V ~O
a o v m N V ~ ~j ~ O O O O O O O O O O
D
C
w Y.
~ O
O N N c- O. O P I~. f~ a7 N M
O N N N N N N N N V M
C
~ O X OI ~ ~ V WT O N U~ ~Y t~
O M !L N p. ~ ~ ~ O N N O
J C~ II r r ~ 'O
1~
C .1M M ~T vt t1~t(1 t P In o ' ' ..
~ O M t!

x. 1 N O vp O M X ~ N N I~ N
~

J (3 N

f-W

m ro O a N ~ ~t O i~ N f0 M ~ .O
O

O M X N p. V

p. J ~ N N O ~ N
Cd 41 H

N N r M S-I

O O m W ~tc0M a-V d V v1 ZT

~ ~ ~ N ~ U1 t!1v1 M M
C O ~
U

7 Cd M ~!1n.O N M
U

M N N N V
~

f0 1f1 M f~ I~O N ~ON ~O t(1O.
U 'O
J
N ~

Cd r N c0 O N O O

B O v O O c0V Wt InM N O.f~ ~'1 ~

to o ~ O.InM tnIWn P
~ M P
N

J Cd O O ~t t!1O ~ N ~t U

...
O O ~

O O C . . . O P ~ N CO

S ~ P ~ V

X V M V V .O N M Z,31 c ~ ,o W N C n c0O O 1~f~ ~ON -rI

J ~ ~ ~ O
a N' C a1~ ~ ~ P
d X

fU
W N N r O .w$

, O

m O P P M O N U P N V N
C

_ [v y t n!1V1V1 M
J (a Y

X r ~ ~ O. tnn N

N t ~fu1 ~ M .O '-I~O. O e-~ ~ ~ d P

r m 3 a0m O a V

% N N M ~t y~ 1I~ V1 1!Y ~O .O
W
RELATED APPLICATIONS
This application is one of a group of patent applications which are being filed on the same date. The group includes the present application and application Serial No. 2, C29, 618 in the name of L.W. Collier, IV, et al. , and entitled "Low Stress Relaxation Composite Elastic Material"
While the present invention has been described in connection with certain preferred embodiments, it is to be understood that the subject matter encompassed by way of the present invention is not to be limited to those specific embodiments. On the contrary, it is intended for the subject matter of the invention to include all alternatives, modifications and equivalents as can be included within the spirit and scope of the following claims.

Claims (47)

WHAT IS CLAIMED IS
1. An elastic nonwoven web comprising a coherent matrix of fibers formed from a blend comprising:
an elastomeric polymer selected from the group consisting of styrene-polyethylene-propylene)-styrene elastomeric block copolymer and a mixture of styrene-poly(ethylene-propylene)-styrene and styrene-polyethylene-butylene)-styrene elastomeric block copolymers; and a tackifying resin, wherein said web has a stress relaxation of less than about 30 percent.
2. The elastic nonwoven web of claim 1, wherein said styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer has the formula:
wherein m is an integer from about 38 to 337; and n is an integer from about 500 to 1860; and R is a benzyl group.
3. The elastic nonwoven web of claim 1 or 2, wherein the styrene-poly(ethylene-propylene)-styrene block copolymer has an average molecular weight ratio of polystyrene endblocks to polyethylene-propylene) midblocks ranging from about 10:90 to about 25:75.
4. The elastic nonwoven web of claim 1, 2 or 3 wherein the mixture of styrene-poly(ethylene-propylene)-styrene and styrene-polyethylene-butylene)-styrene elastomeric block copolymers contain at least about 40 parts by weight styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer per 100 parts of elastomeric block copolymer.
5. The elastic nonwoven web of any one of claims 1 to 5, wherein said tackifying resin is selected from the group consisting of hydrogenated hydrocarbon resins and terpene hydrocarbon resins.
6. The elastic nonwoven web of any one of claims 1 to 5, wherein the blend further comprises a polyolefin.
7. The elastic nonwoven web of claim 6, wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, polybutylene, polyethylene copolymers, polypropylene copolymers, polybutylene copolymers and mixtures thereof.
8. The elastic nonwoven web of any one of claims 1 to 7, wherein the blend further comprises an extending oil.
9. The elastic nonwoven web of claim 8, wherein the extending oil is a mineral oil.
10. The elastic nonwoven web of claim 8 or 9, wherein said blend comprises from about 50 to about 80 percent, by weight, of an elastomeric polymer, from about 15 to about 28 percent, by weight, of a tackifying resin, from about 3 to about 23 percent, by weight, of a polyolefin, and up to about 15 percent, by weight, of an extending oil.
11. The elastic nonwoven web of any one of claims 1 to 10, wherein said fibers are meltblown fibers.
12. The elastic nonwoven web of claim 11, wherein said meltblown fibers include microfibers.
13. An elastic nonwoven web consisting essentially of:
a coherent matrix of fibers formed from a blend comprising:
an elastomeric polymer selected from the group consisting of styrene-polyethylene-propylene)-styrene elastomeric block copolymer and a mixture of styrene-poly(ethylene-propylene)-styrene and styrene-poly(ethylene-butylene)-styrene elastomeric block copolymers:
a polyolefin;
a tackifying resin; and an extending oil, wherein said web has a stress relaxation of less than about 30 percent.
14. A elastic nonwoven web comprising:
a coherent matrix of elastic fibers formed from a blend comprising:
an elastomeric polymer selected from the group consisting of styrene-polyethylene-propylene)-styrene elastomeric block copolymer and a mixture of a styrene-poly(ethylene-propylene)-styrene and a styrene-poly(ethylene-butylene)-styrene elastomeric block copolymer; and a tackifying resin, and at least one other material selected from the group consisting of nonelastic fibers and particulates; and wherein said web has a stress relaxation of less than about 30 percent.
15. The elastic nonwoven web of claim 13 or 14, wherein said styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer has the formula:
wherein m is an integer from about 38 to 337; and n is an integer from about 500 to 1860; and R is a benzyl group.
16. The elastic nonwoven web of claim 13, 14 or 15, wherein the styrene-poly(ethylene-propylene)-styrene block copolymer has an average molecular weight ratio of polystyrene endblocks to polyethylene-propylene) midblocks ranging from about 10:90 to about 25:75.
17. The elastic nonwoven web of any one of claims 13 to 16, wherein the mixture of styrene-poly(ethylene-propylene)-styrene and styrene-polyethylene-butylene)-styrene elastomeric block copolymers contain at least about 40 parts by weight styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer per 100 parts of elastomeric block copolymer.
18. The elastic nonwoven web of any one of claims 13 to 17, wherein said tackifying resin is selected from the group consisting of hydrogenated hydrocarbon resins and terpene hydrocarbon resins.
19. The elastic nonwoven web of claim 14, wherein the blend further comprises a polyolefin.
20. The elastic nonwoven web of claim 13 or 19, wherein the polyolefin is selected from the group including polyethylene, polypropylene, polybutylene, polyethylene copolymers, polypropylene copolymers, polybutylene copolymers and mixtures thereof.
21. The elastic nonwoven web of claim 14 or 19, wherein the blend further comprises an extending oil.
22. The elastic nonwoven web of claim 13 or 21, wherein the extending oil is a mineral oil.
23. The elastic nonwoven web of claim 13, 21, or 22, wherein said blend comprises from about 50 to about 80 percent, by weight, of the elastomeric polymer, from about 15 to about 28 percent, by weight, of a tackifying resin, from about 3 to about 23 percent, by weight, of a polyolefin, and up to about 15 percent, by weight, of an extending oil.
24. The elastic nonwoven web of any one of claims 13 to 23, wherein the elastic fibers are meltblown fibers.
25. The elastic nonwoven web of claim 24, wherein the meltblown fibers include microfibers.
26. The elastic nonwoven web of claim 14 comprising from about 20 percent, by weight, to about 99 percent, by weight, of the elastic fibers formed from a blend comprising a styrene-poly(ethylene-propylene)-styrene thermoplastic elastomeric block copolymer and from about 1 percent, by weight, to about 80 percent, by weight, of the other materials.
27. The elastic nonwoven web of claim 14 comprising from about 50 percent to about 99 percent, by weight, of the elastic fibers formed from a blend comprising a styrene-poly(ethylene-propylene)-styrene thermoplastic elastomeric block copolymer and from about 1 percent, by weight, to about 49 percent, by weight, of said nonelastic fibers and from about 1 percent, by weight, to about 49 percent, by weight, of said particulates.
28. The elastic nonwoven web of claim 14, 19, 21, 22, 26 or 27, wherein said nonelastic fibers are selected from the group consisting of polyester fibers, polyamide fibers, glass fibers, polyolefin fibers, cellulosic derived fibers, multi-component fibers, natural fibers, absorbent fibers, electrically conductive fibers and blends of two or more of said nonelastic fibers.
29. The elastic nonwoven web of any one of claims 14, 19, 21, 22, and 26 to 28, wherein said particulates are selected from the group consisting of activated charcoal and superabsorbents.
30. An elastic nonwoven web consisting essentially of:
a coherent matrix of elastic fibers formed from a blend comprising:
an elaszomeric polymer selected from the group consisting of styrene-polyethylene-propylene)-styrene elastomeric block copolymer and a mixture of styrene-poly(ethylene-propylene)-styrene and styrene-polyethylene-butylene)-styrene elastomeric block copolymers;
a polyolefin;
a tackifying resin; and an extending oil, and at least one other material selected from the group consisting of nonelastic fibers and particulates; and wherein said web has a stress relaxation of less than about 30 percent.
31. Elastic fibers formed from a blend comprising:
an elastomeric polymer selected from the group consisting of styrene-polyethylene-propylene)-styrene elastomeric block copolymer and a mixture of styrene-poly(ethylene-propylene)-styrene and styrene-poly(ethylene-butylene)-styrene elastomeric block copolymers; and a tackifying resin, wherein the fibers are adapted to form a nonwoven elastic web having a stress relaxation of less than about 30 percent.
32. The elastic fibers of claim 30 or 31, wherein said styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer has the formula:
wherein m is an integer from about 38 to 337; and n is an integer from about 500 to 1860; and R is a benzyl group.
33. The elastic fibers of claim 30, 31, or 32, wherein the styrene-poly(ethylene-propylene)-styrene block copolymer has an average molecular weight ratio of polystyrene endblocks to polyethylene-propylene) midblocks ranging from about 10:90 to about 25:75.
34. The elastic nonwoven web of any one of claims 30 to 33, wherein the mixture of styrene-poly(ethylene-propylene)-styrene and styrene-polyethylene-butylene)-styrene elastomeric block copolymers contain at least about 40 parts by weight styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer per 100 parts of elastomeric block copolymer.
35. The elastic fibers of any one of claims 30 to 34, wherein the tackifying resin is selected from the group consisting of hydrogenated hydrocarbon resins and terpene hydrocarbon resins.
36. The elastic fibers of claim 31, wherein the blend further comprises a polyolefin.
37. The elastic fibers of claim 30 or 36, wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, polybutylene, polyethylene copolymers, polypropylene copolymers, polybutylene copolymers and mixtures thereof.
38. The elastic fibers of claim 31 or 36, wherein the blend further comprises an extending oil.
39. The elastic fibers of claim 30 or 38, wherein the extending oil is a mineral oil.
40. The elastic fibers of claim 30, wherein said blend comprises from about 50 to about 80 percent, by weight, of an elastomeric polymer, from about 15 to about 28 percent, by weight, of a tackifying resin, from about 3 to about 23 percent, by weight, of a polyolefin, and up to about 15 percent, by weight, of an extending oil.
41. The elastic fibers of any one of claims 30 to 40, wherein the fibers are meltblown fibers.
42. The elastic fibers of claim 41, wherein the meltblown fibers include microfibers.
43. Elastic fibers formed from a blend consisting essentially of:
an elastomeric polymer selected from the group consisting of styrene-polyethylene-propylene)-styrene elastomeric block copolymer and a mixture of styrene-poly(ethylene-propylene)-styrene and styrene-polyethylene-butylene)-styrene elastomeric block copolymers;
a polyolefin;
a tackifying resin; and an extending oil, and wherein said fibers are adapted to form a nonwoven elastic web having a stress relaxation of less than about 30 percent.
44. Elastic fibers formed from an extrudable blend, the blend comprising:
(A) from about 50 to about 80 percent, by weight, of an elastomeric polymer selected from the group consisting of styrene-poly(ethylene-propylene)-styrene elastomeric block copolymer and a mixture of styrene-poly(ethylene-propylene)-styrene and styrene-polyethylene-butylene)-styrene elastomeric block copolymers;
(B) from about 3 to about 23 percent, by weight, of a polyolefin;
(C) from about 15 to about 28 percent, by weight, of a tackifying resin; and (D) up to about 15 percent, by weight, of an extending oil, and wherein said fibers are adapted to form a nonwoven elastic web having a stress relaxation of less than about 30 percent.
45. The elastic fibers of claim 44, wherein the tackifying resin is selected from the group consisting of hydrogenated hydrocarbon resins and terpene hydrocarbon resins.
46. The elastic fibers of claim 44 or 45, wherein the polyolefin is selected from the group consisting of polyethylene, polypropylene, polybutylene, polyethylene co-polymers, polypropylene copolymers, polybutylene copolymers and mixtures thereof.
47. The elastic fibers of claim 44, 45 or 46, wherein the extending oil is a mineral oil.
CA002029617A 1990-01-10 1990-11-08 Low stress relaxation elastomeric nonwoven webs and fibers Expired - Fee Related CA2029617C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US463,079 1990-01-10
US07/463,079 US5260126A (en) 1990-01-10 1990-01-10 Low stress relaxation elastomeric nonwoven webs and fibers

Publications (2)

Publication Number Publication Date
CA2029617A1 CA2029617A1 (en) 1991-07-11
CA2029617C true CA2029617C (en) 2002-07-02

Family

ID=23838778

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002029617A Expired - Fee Related CA2029617C (en) 1990-01-10 1990-11-08 Low stress relaxation elastomeric nonwoven webs and fibers

Country Status (2)

Country Link
US (2) US5260126A (en)
CA (1) CA2029617C (en)

Families Citing this family (101)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6059764A (en) * 1990-06-18 2000-05-09 The Procter & Gamble Company Stretchable absorbent articles
US5702382A (en) * 1990-06-18 1997-12-30 The Procter & Gamble Company Extensible absorbent articles
US5824004A (en) * 1990-06-18 1998-10-20 The Procter & Gamble Company Stretchable absorbent articles
US5674212A (en) * 1990-10-29 1997-10-07 The Procter & Gamble Company Extensible absorbent articles
US5658269A (en) * 1990-10-29 1997-08-19 The Procter & Gamble Company Extensible absorbent articles
US5997989A (en) * 1992-02-03 1999-12-07 Bba Nonwovens Simpsonville, Inc. Elastic nonwoven webs and method of making same
US5470639A (en) * 1992-02-03 1995-11-28 Fiberweb North America, Inc. Elastic nonwoven webs and method of making same
US5332613A (en) * 1993-06-09 1994-07-26 Kimberly-Clark Corporation High performance elastomeric nonwoven fibrous webs
CA2191470C (en) * 1994-06-01 2002-12-17 Stephen R. Betso Thermoelastic blend compositions
US5635290A (en) * 1994-07-18 1997-06-03 Kimberly-Clark Corporation Knit like nonwoven fabric composite
US5869591A (en) * 1994-09-02 1999-02-09 The Dow Chemical Company Thermoset interpolymers and foams
US5977271A (en) * 1994-09-02 1999-11-02 The Dow Chemical Company Process for preparing thermoset interpolymers and foams
USH1808H (en) * 1994-11-17 1999-10-05 Shell Oil Company Extrudable styrenic block copolymer compositions containing a metallocene polyolefin
USH1798H (en) * 1994-12-22 1999-07-06 Shell Oil Company Soft compounds containing elastomeric metallocene polyolefins and styrenic block copolymers
US5773375A (en) * 1996-05-29 1998-06-30 Swan; Michael D. Thermally stable acoustical insulation
US6191197B1 (en) 1996-09-23 2001-02-20 Bridgestone Corporation Extended polymer compostion derived from blends of elastomers and syndiotactic polystyrene
US6329459B1 (en) 1996-09-23 2001-12-11 Bridgestone Corporation Extended syndiotactic polystyrene-elastomeric block copolymers
US6187425B1 (en) 1996-12-30 2001-02-13 Kimberly-Clark Worldwide, Inc. Elastic materials with improved performance at body temperature
ZA985672B (en) * 1997-06-30 1999-11-25 Procter & Gamble Multi-directionally extensible sanitary napkin.
US6238767B1 (en) 1997-09-15 2001-05-29 Kimberly-Clark Worldwide, Inc. Laminate having improved barrier properties
US6045900A (en) 1997-09-15 2000-04-04 Kimberly-Clark Worldwide, Inc. Breathable filled film laminate
AU9601298A (en) 1997-10-03 1999-04-27 Kimberly-Clark Worldwide, Inc. High performance elastic composite materials made from high molecular weight thermoplastic triblock elastomers
US6086984A (en) * 1998-05-22 2000-07-11 Delaware Valley Corporation Elastic nonwoven fabric
US6362389B1 (en) * 1998-11-20 2002-03-26 Kimberly-Clark Worldwide, Inc. Elastic absorbent structures
US6277916B1 (en) 1999-02-25 2001-08-21 The Dow Chemical Company Process for preparing thermoplastic vulcanizates
US6387471B1 (en) 1999-03-31 2002-05-14 Kimberly-Clark Worldwide, Inc. Creep resistant composite elastic material with improved aesthetics, dimensional stability and inherent latency and method of producing same
US6547915B2 (en) 1999-04-15 2003-04-15 Kimberly-Clark Worldwide, Inc. Creep resistant composite elastic material with improved aesthetics, dimensional stability and inherent latency and method of producing same
US6777082B2 (en) 1999-07-28 2004-08-17 The Dow Chemical Company Hydrogenated block copolymers having elasticity and articles made therefrom
WO2001019920A1 (en) 1999-09-17 2001-03-22 The Procter & Gamble Company Low stress relaxation elastomeric materials
US6794024B1 (en) 1999-11-01 2004-09-21 Kimberly-Clark Worldwide, Inc. Styrenic block copolymer breathable elastomeric films
US6479154B1 (en) 1999-11-01 2002-11-12 Kimberly-Clark Worldwide, Inc. Coextruded, elastomeric breathable films, process for making same and articles made therefrom
US20030045844A1 (en) * 2000-04-14 2003-03-06 Taylor Jack Draper Dimensionally stable, breathable, stretch-thinned, elastic films
US20050106971A1 (en) * 2000-05-15 2005-05-19 Thomas Oomman P. Elastomeric laminate with film and strands suitable for a nonwoven garment
US6969441B2 (en) * 2000-05-15 2005-11-29 Kimberly-Clark Worldwide, Inc. Method and apparatus for producing laminated articles
US6833179B2 (en) 2000-05-15 2004-12-21 Kimberly-Clark Worldwide, Inc. Targeted elastic laminate having zones of different basis weights
US8182457B2 (en) 2000-05-15 2012-05-22 Kimberly-Clark Worldwide, Inc. Garment having an apparent elastic band
JP2002030581A (en) * 2000-07-19 2002-01-31 Kuraray Co Ltd Laminated sheet for house wrap or roof ground cover
US20020099107A1 (en) * 2000-10-27 2002-07-25 Tucker John David Textile fibers made from strengthened polypropylene
JP4155042B2 (en) * 2002-02-20 2008-09-24 チッソ株式会社 Elastic long fiber nonwoven fabric and fiber product using the same
US20030207639A1 (en) * 2002-05-02 2003-11-06 Tingdong Lin Nonwoven web with improved adhesion and reduced dust formation
JP3790496B2 (en) * 2002-05-20 2006-06-28 株式会社クラレ Composite nonwoven fabric for protective clothing and method for producing the same
US7316842B2 (en) 2002-07-02 2008-01-08 Kimberly-Clark Worldwide, Inc. High-viscosity elastomeric adhesive composition
US7335273B2 (en) * 2002-12-26 2008-02-26 Kimberly-Clark Worldwide, Inc. Method of making strand-reinforced elastomeric composites
US7316840B2 (en) * 2002-07-02 2008-01-08 Kimberly-Clark Worldwide, Inc. Strand-reinforced composite material
US7405171B2 (en) * 2002-08-08 2008-07-29 Chisso Corporation Elastic nonwoven fabric and fiber products manufactured therefrom
US20040110442A1 (en) * 2002-08-30 2004-06-10 Hannong Rhim Stretchable nonwoven materials with controlled retraction force and methods of making same
US20040043214A1 (en) * 2002-08-30 2004-03-04 Kimberly-Clark Worldwide, Inc. Method of forming a 3-dimensional fiber and a web formed from such fibers
WO2004020174A1 (en) * 2002-08-30 2004-03-11 Kimberly-Clark Worldwide, Inc. Device and process for treating flexible web by stretching between intermeshing forming surfaces
US8043273B2 (en) * 2002-12-19 2011-10-25 Kimberly-Clark Worldwide, Inc. Disposable undergarment with a stretchable absorbent insert and method for the use thereof
US7837665B2 (en) 2002-10-01 2010-11-23 Kimberly-Clark Worldwide, Inc. Three-piece disposable undergarment with folded crotch member
US6979380B2 (en) 2002-10-01 2005-12-27 Kimberly-Clark Worldwide, Inc. Three-piece disposable undergarment and method for the manufacture thereof
US7220335B2 (en) * 2002-10-01 2007-05-22 Kimberly-Clark Worldwide, Inc. Three-piece disposable undergarment with stretchable crotch member and method for the manufacture thereof
US8389634B2 (en) * 2002-10-02 2013-03-05 Dow Global Technologies Llc Polymer compositions comprising a low-viscosity, homogeneously branched ethylene α-olefin extender
US7749211B2 (en) * 2002-10-18 2010-07-06 Kimberly-Clark Worldwide, Inc. Body conforming absorbent garment and methods for the use and manufacture thereof
JP4489346B2 (en) * 2002-12-17 2010-06-23 シャープ株式会社 Liquid crystal display
US7476447B2 (en) 2002-12-31 2009-01-13 Kimberly-Clark Worldwide, Inc. Elastomeric materials
US6916750B2 (en) 2003-03-24 2005-07-12 Kimberly-Clark Worldwide, Inc. High performance elastic laminates made from high molecular weight styrenic tetrablock copolymer
US20040210205A1 (en) * 2003-04-15 2004-10-21 Kimberly-Clark Worldwide, Inc. Disposable pant-like undergarment
US7604624B2 (en) 2003-05-30 2009-10-20 Kimberly-Clark Worldwide, Inc. Disposable absorbent article with overlapping absorbent assembly secured to front and back panels
US7018369B2 (en) * 2003-05-30 2006-03-28 Kimberly-Clark Worldwide, Inc. Disposable pant-like undergarment having an elastic band adjacent the waist opening
US20040243085A1 (en) * 2003-05-30 2004-12-02 Kimberly-Clark Worldwide, Inc. Disposable absorbent article having an integral waistband
US20050004549A1 (en) * 2003-07-01 2005-01-06 Kimberly-Clark Worldwide, Inc. Disposable pant-like undergarment
US7220478B2 (en) * 2003-08-22 2007-05-22 Kimberly-Clark Worldwide, Inc. Microporous breathable elastic films, methods of making same, and limited use or disposable product applications
US7932196B2 (en) 2003-08-22 2011-04-26 Kimberly-Clark Worldwide, Inc. Microporous stretch thinned film/nonwoven laminates and limited use or disposable product applications
US20050118435A1 (en) * 2003-12-01 2005-06-02 Kimberly-Clark Worldwide, Inc. Films and methods of forming films having polyorganosiloxane enriched surface layers
US7326751B2 (en) * 2003-12-01 2008-02-05 Kimberly-Clark Worlwide, Inc. Method of thermally processing elastomeric compositions and elastomeric compositions with improved processability
US7662745B2 (en) 2003-12-18 2010-02-16 Kimberly-Clark Corporation Stretchable absorbent composites having high permeability
US20050142339A1 (en) * 2003-12-30 2005-06-30 Price Cindy L. Reinforced elastic laminate
US7601657B2 (en) * 2003-12-31 2009-10-13 Kimberly-Clark Worldwide, Inc. Single sided stretch bonded laminates, and methods of making same
JP5080967B2 (en) * 2004-03-03 2012-11-21 クレイトン・ポリマーズ・リサーチ・ベー・ベー Block copolymer with high flow and high elasticity
US7717893B2 (en) * 2004-06-04 2010-05-18 The Procter & Gamble Company Absorbent articles comprising a slow recovery elastomer
US7247215B2 (en) 2004-06-30 2007-07-24 Kimberly-Clark Worldwide, Inc. Method of making absorbent articles having shaped absorbent cores on a substrate
US7772456B2 (en) 2004-06-30 2010-08-10 Kimberly-Clark Worldwide, Inc. Stretchable absorbent composite with low superaborbent shake-out
US7938813B2 (en) 2004-06-30 2011-05-10 Kimberly-Clark Worldwide, Inc. Absorbent article having shaped absorbent core formed on a substrate
US20060069365A1 (en) * 2004-09-30 2006-03-30 Sperl Michael D Absorbent composite having selective regions for improved attachment
US20060135923A1 (en) * 2004-12-20 2006-06-22 Boggs Lavada C Nonwoven fabrics for use in personal care products
US20060135932A1 (en) * 2004-12-21 2006-06-22 Abuto Frank P Stretchable absorbent core and wrap
US20060147685A1 (en) 2004-12-30 2006-07-06 Kimberly-Clark Worldwide, Inc. Multilayer film structure with higher processability
US7612134B2 (en) * 2005-02-23 2009-11-03 Callaway Golf Company Golf ball and thermoplastic material
US7910658B2 (en) 2005-03-17 2011-03-22 Dow Global Technologies Llc Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates
US20070048497A1 (en) * 2005-08-31 2007-03-01 Peiguang Zhou Single-faced neck bonded laminates and methods of making same
US20070135785A1 (en) * 2005-12-12 2007-06-14 Jian Qin Absorbent articles comprising thermoplastic coated superabsorbent polymer materials
US20070141937A1 (en) * 2005-12-15 2007-06-21 Joerg Hendrix Filament-meltblown composite materials, and methods of making same
US20070141352A1 (en) * 2005-12-15 2007-06-21 Calhoun Patricia H Cross-directional elastic films with machine direction stiffness
US7612135B2 (en) * 2006-02-17 2009-11-03 Callaway Golf Company Golf ball and thermoplastic material
US20070255243A1 (en) * 2006-04-28 2007-11-01 Kaun James M Dimensionally stable stretchable absorbent composite
US7985802B2 (en) 2008-04-18 2011-07-26 Exxonmobil Chemical Patents Inc. Synthetic fabrics, components thereof, and methods for making the same
US7968479B2 (en) * 2008-06-30 2011-06-28 Kimberly-Clark Worldwide, Inc. Elastic multilayer composite including pattern unbonded elastic materials, articles containing same, and methods of making same
US9168718B2 (en) 2009-04-21 2015-10-27 Exxonmobil Chemical Patents Inc. Method for producing temperature resistant nonwovens
US9498932B2 (en) 2008-09-30 2016-11-22 Exxonmobil Chemical Patents Inc. Multi-layered meltblown composite and methods for making same
US10161063B2 (en) 2008-09-30 2018-12-25 Exxonmobil Chemical Patents Inc. Polyolefin-based elastic meltblown fabrics
US20100266824A1 (en) * 2009-04-21 2010-10-21 Alistair Duncan Westwood Elastic Meltblown Laminate Constructions and Methods for Making Same
US20100266818A1 (en) * 2009-04-21 2010-10-21 Alistair Duncan Westwood Multilayer Composites And Apparatuses And Methods For Their Making
US8664129B2 (en) 2008-11-14 2014-03-04 Exxonmobil Chemical Patents Inc. Extensible nonwoven facing layer for elastic multilayer fabrics
US8554350B2 (en) 2008-10-15 2013-10-08 Personics Holdings Inc. Device and method to reduce ear wax clogging of acoustic ports, hearing aid sealing system, and feedback reduction system
MX2011009060A (en) 2009-02-27 2011-11-18 Exxonmobil Chem Patents Inc Multi-layer nonwoven in situ laminates and method of producing the same.
US8668975B2 (en) 2009-11-24 2014-03-11 Exxonmobil Chemical Patents Inc. Fabric with discrete elastic and plastic regions and method for making same
US8895126B2 (en) 2010-12-31 2014-11-25 Kimberly-Clark Worldwide, Inc. Segmented films with high strength seams
US8945324B2 (en) 2011-04-04 2015-02-03 Kimberly-Clark Worldwide, Inc. Process for making elastomeric absorbent garments to reduce absorbent bunching
KR102384286B1 (en) * 2018-06-22 2022-04-06 주식회사 엘지화학 An assessment method for polypropylene resin, a method for preparing polypropylene non-woven fabric, a polypropylene non-woven fabric
ES2948399T3 (en) * 2019-11-08 2023-09-11 Tsrc Corp Polymeric composition and fiber or non-woven fabric made from it

Family Cites Families (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3507934A (en) * 1965-12-20 1970-04-21 Shell Oil Co Block copolymer compositions having improved processability
NL6601741A (en) * 1966-02-11 1967-08-14
US3614836A (en) * 1968-07-08 1971-10-26 Shell Oil Co Block copolymer foxing and soling composition
US3880976A (en) * 1968-12-04 1975-04-29 Toyo Boseki Production of elastic yarn
US3595942A (en) * 1968-12-24 1971-07-27 Shell Oil Co Partially hydrogenated block copolymers
US4340704A (en) * 1974-02-15 1982-07-20 Montedison S.P.A. Thermoplastic rubbers and process for preparing same
US4209563A (en) * 1975-06-06 1980-06-24 The Procter & Gamble Company Method for making random laid bonded continuous filament cloth
FR2322883A1 (en) * 1975-09-02 1977-04-01 Michelin & Cie ELASTOMERS OF THE E P T TYPE, AND ARTICLES CONTAINING SUCH ELASTOMERS
US4166464A (en) * 1976-06-23 1979-09-04 Johnson & Johnson Absorbent dressing
US4369284A (en) * 1977-03-17 1983-01-18 Applied Elastomerics, Incorporated Thermoplastic elastomer gelatinous compositions
US4250273A (en) * 1977-06-13 1981-02-10 The Firestone Tire & Rubber Company Thermoplastic elastomer blends
US4197377A (en) * 1977-06-13 1980-04-08 The Firestone Tire & Rubber Company Thermoplastic elastomer compositions
US4340684A (en) * 1977-06-13 1982-07-20 The Firestone Tire & Rubber Company Thermoplastic elastomer blends
US4350795A (en) * 1977-06-13 1982-09-21 The Firestone Tire & Rubber Company Thermoplastic elastomer blends
US4305990A (en) * 1977-11-03 1981-12-15 Chicopee Thermoplastic rubber film
US4324245A (en) * 1977-12-20 1982-04-13 Johnson & Johnson Comformable disposable diapers having absorbent panel with bulged side members
US4259540A (en) * 1978-05-30 1981-03-31 Bell Telephone Laboratories, Incorporated Filled cables
US4418123A (en) * 1978-12-06 1983-11-29 H. B. Fuller Company Extrudable self-adhering elastic and method of employing same
US4267096A (en) * 1979-11-09 1981-05-12 General Electric Company Composition of a selectively hydrogenated block copolymer of a vinyl aromatic compound and a diolefin, a polycarbonate and an amorphous polyester
US4361507A (en) * 1980-10-20 1982-11-30 Arco Polymers, Inc. Cable filler composition containing (a) crystalline polypropylene homopolymer, (b) styrene block copolymer and (c) mineral oil
US4446189A (en) * 1983-05-12 1984-05-01 Phillips Petroleum Company Textured nonwoven textile fabric laminate and process of making said
JPS6020977A (en) * 1983-07-13 1985-02-02 Arakawa Chem Ind Co Ltd Pressure-sensitive adhesive composition
USRE32634E (en) * 1983-12-27 1988-03-29 Uniroyal Plastics Company, Inc. Adhesive for bonding cured EPDM rubber
US4692371A (en) * 1985-07-30 1987-09-08 Kimberly-Clark Corporation High temperature method of making elastomeric materials and materials obtained thereby
US4720415A (en) * 1985-07-30 1988-01-19 Kimberly-Clark Corporation Composite elastomeric material and process for making the same
GB8519379D0 (en) * 1985-08-01 1985-09-04 Shell Int Research Processing by melt-spinning/blowing
DE3532357A1 (en) * 1985-09-11 1987-03-19 Bayer Ag THERMOPLASTIC ELASTOMERS
US4716183A (en) * 1985-11-22 1987-12-29 Raychem Corp. Styrene-diene block copolymer compositions
US4728461A (en) * 1985-11-26 1988-03-01 General Electric Company Thermoplastic composition of polyphenylene ether, ethylenemethacrylic acid copolymer, and styrene-glycidyl methacrylate copolymer
US4892903A (en) * 1986-07-07 1990-01-09 Shell Oil Company Elastomeric fibers, structures fashioned therefrom and elastomeric films
US4789699A (en) * 1986-10-15 1988-12-06 Kimberly-Clark Corporation Ambient temperature bondable elastomeric nonwoven web
US4777080A (en) * 1986-10-15 1988-10-11 Kimberly-Clark Corporation Elastic abrasion resistant laminate
US4781966A (en) * 1986-10-15 1988-11-01 Kimberly-Clark Corporation Spunlaced polyester-meltblown polyetherester laminate
US4745139A (en) * 1987-02-09 1988-05-17 Pdi, Inc. Elastomeric coatings containing glass bubbles
JPH0699605B2 (en) * 1987-04-15 1994-12-07 チッソ株式会社 Thermoplastic resin composition
US4822653A (en) * 1987-08-05 1989-04-18 National Starch And Chemical Corporation Recyclable hot melt adhesive compositions
EP0304124A3 (en) * 1987-08-20 1991-06-12 Shell Internationale Researchmaatschappij B.V. Elastomeric fibres, structures fashioned therefrom and elastomeric films
US4847134A (en) * 1987-12-22 1989-07-11 Kimberly-Clark Corporation Stretchable absorbent undergarment
EP0460040B1 (en) * 1989-02-25 1994-09-21 Smith & Nephew P.L.C. Woven or knitted elastic bandage
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

Also Published As

Publication number Publication date
US5260126A (en) 1993-11-09
US5288791A (en) 1994-02-22
CA2029617A1 (en) 1991-07-11

Similar Documents

Publication Publication Date Title
CA2029617C (en) Low stress relaxation elastomeric nonwoven webs and fibers
EP0702733B1 (en) High performance elastomeric nonwoven fibrous webs
CA2029618C (en) Low stress relaxation composite elastic material
US4923742A (en) Elastomeric polyether block amide nonwoven web
US4820572A (en) Composite elastomeric polyether block amide nonwoven web
US4724184A (en) Elastomeric polyether block amide nonwoven web
US7476447B2 (en) Elastomeric materials
US4741949A (en) Elastic polyetherester nonwoven web
US4803117A (en) Coformed ethylene-vinyl copolymer elastomeric fibrous webs
US4663220A (en) Polyolefin-containing extrudable compositions and methods for their formation into elastomeric products including microfibers
US4707398A (en) Elastic polyetherester nonwoven web
US4777080A (en) Elastic abrasion resistant laminate
US5385775A (en) Composite elastic material including an anisotropic elastic fibrous web and process to make the same
EP0564784B1 (en) Anisotropic nonwoven fibrous web
US4883549A (en) Method of attaching a composite elastic material to an article
EP0239080A2 (en) Elastomeric fibers, fibrous webs, composite elastomeric webs and an extrudable composition on the basis of ethylene-vinyl copolymers

Legal Events

Date Code Title Description
EEER Examination request
MKLA Lapsed
MKLA Lapsed

Effective date: 20041108