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EP0457905B2 - Tissu non tisse extensible et procede de production - Google Patents
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EP0457905B2 - Tissu non tisse extensible et procede de production - Google Patents

Tissu non tisse extensible et procede de production Download PDF

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Publication number
EP0457905B2
EP0457905B2 EP90900366A EP90900366A EP0457905B2 EP 0457905 B2 EP0457905 B2 EP 0457905B2 EP 90900366 A EP90900366 A EP 90900366A EP 90900366 A EP90900366 A EP 90900366A EP 0457905 B2 EP0457905 B2 EP 0457905B2
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EP
European Patent Office
Prior art keywords
nonwoven fabric
polymer
strength
block copolymer
elongation
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 - Lifetime
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EP90900366A
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German (de)
English (en)
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EP0457905A4 (en
EP0457905A1 (fr
EP0457905B1 (fr
Inventor
Kohichi Shohji
Masataka Ikeda
Yasushi Kishimoto
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Chemical Industry Co Ltd
Asahi Kasei Kogyo KK
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Application filed by Asahi Chemical Industry Co Ltd, Asahi Kasei Kogyo KK filed Critical Asahi Chemical Industry Co Ltd
Publication of EP0457905A1 publication Critical patent/EP0457905A1/fr
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING 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
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-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
    • D04H1/42—Non-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 characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING 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
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING 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
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-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
    • D04H1/42—Non-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 characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4291—Olefin series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING 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
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-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
    • D04H1/54—Non-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 welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING 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
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005—Synthetic yarns or filaments
    • D04H3/007—Addition polymers
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING 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
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/016—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the fineness

Definitions

  • This invention relates to a stretchable nonwoven fabric. More particularly, this invention relates to a stretchable nonwoven fabric manufactured by using a hydrogenate block copolymer as a main material and having a superior strength, extension characteristics, i.e., elongation and extension recovery properties, weathering resistance, light resistance, heat resistance, chemical resistance and electrical resistance, and a soft handling.
  • Nonwoven fabrics of various synthetic fibers including a nonwoven fabric obtained by spinning a thermal plastic resin by using a melt blown method are known.
  • Japanese Unexamined Patent Publication (Kokai) No. 59-223347 discloses a melt blown nonwoven fabric composed of a polyurethane elastic filament
  • Japanese Unexamined Patent Publication (Kokai) No. 1-132858 discloses a melt blown nonwoven fabric composed of a polyurethane using a polyester diol
  • U.S. Patent No. 4,692,371 discloses a melt blob nonwoven fabric composed of an A-B-A' block polymer
  • Japanese Unexamined Patent Publication (Kokai) No. 62-84143 discloses a melt blown nonwoven fabric composed of an A-B-A' block polymer and a polyolefin.
  • a thermal plastic material Kraton® is known as a typical material having a block copolymer composition and a hydrogenate thereof, and the block copolymer composition and the hydrogenate thereof are disclosed in Japanese Unexamined Patent publications (Kokai) No. 61-42554 and No. 61-155446.
  • the thermal plastic material Kraton® is described in detail in the reference "KRATON® THERMOPLASTIC RUBBER Typical Properties 1986" issued by the Shell Chemical Company. Namely, the most common structure is the linear A-B-A block type; styrene-butadiene-styrene (S-B-S), and a styrene-isoprene-styrene (S-I-S), and Kraton D rubber series, and second generation polymer of the styrene-ethylene/butylenestyrene type (S-EB-S), the Kraton G series.
  • S-B-S styrene-butadiene-styrene
  • S-I-S styrene-isoprene-styrene
  • S-EB-S second generation polymer of the styrene-ethylene/butylenestyrene type
  • Japanese Unexamined Patent Publication (Kokai) No. 61-42554 discloses a composition composed of a hydrogenated block copolymer of 100 parts by weight including at least one polymer block A constituted mainly by a vinyl aromatic compound and at least one polymer block B constituted mainly by a hydrogenated and conjugated diene compound, and a hindered amine group compound of 0.01 part by weight to 3 parts by weight.
  • Japanese Unexamined Patent Publication (Kokai) No. 61-155446 discloses a composition composed of a hydrogenated block copolymer of 100 weight portion having a block copolymer which includes at least two polymer blocks A constituted mainly by a vinyl aromatic compound and at least two polymer blocks B constituted mainly by a conjugated diene, and having a number-average molecular weight of between 20,000 and 100,000 and a polyolefin of 5 parts by weight to 400 parts by weight.
  • the above known melt blown nonwoven fabric has the following problems.
  • the melt blown nonwoven fabrics disclosed in Japanese Unexamined Patent Publications (Kokai) No. 59-223347 and No. 1-132858 are nonwoven fabrics manufactured of polyurethane, and accordingly, those nonwoven fabric have problems of a poor weathering resistance and light resistance. Further, the polyurethane itself is very expensive, and accordingly, these nonwoven fabrics have a problem in that the price of the nonwoven fabric becomes expensive.
  • a nonwoven fabric disclosed in Japanese Unexamined Patent publication No. 62-84143 and composed of the A-B-A' hydrogenated block copolymer and the polyethylene has a problem in that a strength of the nonwoven fabric is weak (see Table 7 in a description of examples described hereafter).
  • US-A-4,663,220 discloses fibrous nonwoven elastomeric webs made from an exhudable elastomeric composition formed by blending from at least 10 percent by weight of an A-B-A' block copolymer where A and A' are each a thermosplastic end-block which includes a styrenic moiety and where B is an elastomeric poly(ethylene-butylene) mid block with up to at least 90 percent by weight of at least one polyolefin.
  • Suitable block copolymers are disclosed to be those of the Kraton G type, such as Kraton G 1650, Kraton G 1652 and Kraton G1657.
  • the sum of the molecular weight of A with the molecular weight of A' is from 14 percent to 29 percent of the molecular weight of the A-B-A' block co polymer.
  • the nonwoven web is formed of microfibers having a fiber diameter of not greater than 100 ⁇ m, preferably from 0.5 ⁇ m to 50 ⁇ m.
  • the nonwoven web has a basis weight of not more than 300 g/m 2 , preferably 5 g/m 2 to 100 g/m 2 .
  • An object of the present invention is to solve the problems of the prior art and to provide a stretchable nonwoven fabric having a superior strength, extendable characteristics, i.e., elongation and elastic recovery of elongation, weathering resistance, light resistance, heat resistance, chemical resistance and electrical resistance, and a soft handling.
  • the nonwoven fabric including a hydrogenated block copolymer of A-B-A' type and manufactured by the melt blown method is known as described before, but in the above known technique, a constitution of the hydrogenated block copolymer, i.e., a block structure, a number-average molecular weight, a content of a vinyl aromatic compound, a 1,2-vinyl content of a conjugated diene structure or the like, a spinning ability in the melt blown method, and characteristics of the stretchable nonwoven fabric obtained are synthetically studied, has not been found before.
  • the inventors in the present application synthetically studied the constitution of the hydrogenated block copolymer, the spinning ability in the melt blown method, and the characteristics of the stretchable nonwoven fabric, and thus accomplished the present invention.
  • the object of the present invention can be attained by a stretchable, meltblown nonwoven fabric having a weight per unit area of 5 to 500 g/m 2 , a mean diameter of fibers of 0.5 to 30 ⁇ m, composed of a thermoplastic fiber comprising
  • a pre-polymer for example, styrene, ⁇ -methylstyrene, vinyltoluene, p-tert-butylstyrene and the like can be used, but styrene is most preferred. These compounds can be used alone or as a combination of two or more thereof.
  • conjugated diene compound constituting the pre-polymer for example, 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, or the like can be used, but butadiene and isoprene are most preferred. These compounds can be used alone or as a combination of two or more thereof.
  • pre-polymers can be manufactured by a successive block copolymerization, with the aid of lithium alkyl catalyst, or by a coupling reaction after the successive block copolymerization, and subsequently, the thus obtained pre-polymer is selectively hydrogenated.
  • the hydrogenating reaction can be conducted by the use of known hydrogenating catalysts, for example, precious metallic support catalysts such as platinum and palladium, catalysts such as Raney nickel, organonickel compounds, and or-, ganocobalt compounds, or a complex catalyst of these compounds and other organometallic compounds.
  • a titanocene compound is preferable because it has an extremely high activity as a hydrogenat-ing catalyst for the block copolymer, a small amount of the catalyst is needed for the hydrogenating reaction, and the catalyst residue does not adversely affect a heat-resistance stability of the hydrogenated black copolymer, and thus there is no need for the removal of the catalyst residue, as disclosed in Japanese Unexamined Patent Publication (Kokai) No. 61-155446.
  • the hydrogenation is selectively conducted for a double bond of the conjugated diene compound.
  • the hydrogenation should be selectively conducted because a double bonding of the conjugated diene compound leads to a deterioration in the weathering resistance, light exposure resistance, and heat resistance, which is undesirable.
  • the hydrogenation causes a poor fluidity, which is undesirable from the viewpoint of the spinning properties.
  • a partial hydrogenation where at least 80%, preferably 90% of the conjugated diene compound is hydrogenated, and at most 20%, preferably 5%, of the vinyl aromatic compound is hydrogenated, is preferable with respect to the resistances to weather light and heat, and the spinning properties of the nonwoven fabric.
  • the number-average molecular weight of a pre-polymer in total (hereinafter abbreviated as M n ) is within the range of 30,000 to 65,000, preferably 35,000 to 60,000, more preferably 40,000 to 55,000.
  • M n The number-average molecular weight of a pre-polymer in total
  • the content of the vinyl aromatic compound in the pre-polymer is within 15 to 40 per cent by weight (hereinafter abbreviated as wt%), preferably 20 to 35 wt%.
  • the vinyl aromatic compound serves as a hard segment which contributes to the strength of the material
  • the conjugated diene compound serves as a soft segment which contributes to the stretchability.
  • a strength of the polymer increases in accordance with a content of the vinyl aromatic compound, but a strength of the nonwoven fabric has a maximum value with regard to a content of the vinyl aromatic compound. Namely, when the content of the vinyl aromatic compound is under 15 wt%, the strength of the nonwoven fabric becomes too low, and thus a nonwoven fabric having broad application cannot be obtained.
  • the strength and the elongation of the nonwoven fabric are lowered, and the nonwoven fabric becomes hard. Also the melt viscosity, and accordingly the pressure in the die part, are raised, which results in inferior spinning properties.
  • the thus-produced nonwoven fabric includes polymer balls, and has a larger average fiber diameter, poor dispersion properties of the single fiber, and an inferior feeling and appearance, and thus cannot be used as a product. Therefore, within the range of 15 to 45 wt%, the spinning properties are satisfactory, and a soft and high quality nonwoven fabric having a superior strength and elongation can be obtained.
  • a 1,2-vinyl content of the conjugated diene structure of the conjugated diene compound of the pre-polymer is preferably within the range of 20 to 50 wt%, more preferably 25 to 45 wt%.
  • the bonding amount is less than 20 wt%, a recovery of the elongation of the obtained nonwoven fabric is poor, and the thus obtained nonwoven fabric cannot be used as a product.
  • the bonding amount is more than 50%, the spinning properties are poor, and a superior web cannot be obtained.
  • At least one polymer block B must be arranged on an end of a polymer chain of the pre-polymer, because the spinning property and characteristics of the nonwoven fabric depend off a ratio of the polymer block for all ends of the polymer chain.
  • the ratio of the polymer block B for all ends of the polymer chain in the pre-polymer is preferably within 3 to 25 wt%, more preferably 5 to 20 wt%.
  • the ratio is less than 3%, a superior web cannot be obtained due to a high melt viscosity and an inferior spinning property.
  • the ratio is more than 25 wt%, the strength of the nonwoven fabric is lowered.
  • the spinning property of G-1652 is poor due to a lower flowability, the fibers cannot be continued and many polymer balls are generated, and thus a sample of the nonwoven fabric cannot be obtained. Although a sample of a nonwoven fabric can be obtained from G-1657X, the strength of the nonwoven fabric is extremely low despite a high value of a strength of the polymer.
  • a nonwoven fabric product having a superior appearance and handling, a very high strength, and superior extendable characteristics and softness can be obtained by using the block copolymer including at least two polymer blocks A constituted mainly by the vinyl aromatic compound and at least two polymer blocks B constituted mainly by a conjugated diene compound, at least one polymer block B being arranged on an end of a polymer as the pre-polymer of the hydrogenated block copolymer in the present invention. Further in the manufacture of the nonwoven fabric in the present invention, the spinning property is improved due to the lower melt viscosity and the superior flowability thereof.
  • the pre-polymer may have a linear, divergent, or radial constitution, examples of which are expressed by the following general formulae.
  • (B - A)n n ⁇ 2 (B - A)n - B n ⁇ 2 (B - A)m - X(B - A)n m,n ⁇ 1, m + n 2 ⁇ 4 (X in the expressions represents a coupling agent)
  • a hindered amine compound As a stabilizer for the hydrogenated block copolymer used in the present invention, a hindered amine compound, hindered phenol compound, phosphorus compound, benzophenone compound, benzotriazole compound, and a mixture thereof can be used.
  • An improvement of the heat resistance and weathering resistance of the hindered amino is remarkable, and accordingly, more preferably the hindered amine is used as the stabilizer. If the content of the stabilizer is more than 5 parts by weight per 100 parts by height of the hydrogenated block copolymer, coloring and other drawbacks can arise without a corresponding further improvement in the effects of the stabilizer.
  • a value of an adhesion of the stretchable nonwoven fabric can be widely changed according to the type of pre-polymer used.
  • the peel strength of the nonwoven fabric can be used to measure the adhesion, when the peel strength in nigh, the adhesion of the nonwoven fabric is also high.
  • T V/S
  • V denotes a 1,2-vinyl content of a conjugated diene structure in a conjugated diene compound and expressed by wt%
  • S denotes a content of a vinyl aromatic compound in a pre-polymer and expressed by wt%.
  • the adhesion can be divided into two portions, from a boundary having a T value of 1.25; i.e., when T is greater than 1.25, the adhesion becomes larger, and when T is lower than 1.25, the peel strength is lower than 10 g/cm and thus there is substantially no adhesion in practical use.
  • the applications of the nonwoven fabrics can be determined according to the value of the nonwoven fabric, and the nonwoven fabric having an adhesion T of more than 1.25 can be suitably used for applications such as diaper, apparel or the like, as a laminated material formed by piling the nonwoven fabric of the present invention on another nonwoven fabric, a knitted fabric, a woven fabric or the like.
  • the nonwoven fabric having an adhesion T of less than 1.25 i.e., a nonwoven fabric having no adhesion, can be used for applications wherein the nonwoven fabric is used alone, e.g., for gloves, hats, stretch tapes used for, for example, in a waist bund of a diaper, or the like.
  • the stretchable nonwoven fabric having further improved properties is obtained by adding a polyolefin to the hydrogenated block copolymer. Since the polyolefin is blended with the hydrogenated block copolymer, a melt viscosity of the blended polymer becomes lower, and thus the spinning property is improved, and a mean diameter of fibers in the nonwoven fabric becomes smaller and therefore, no adhesion appears. Nevertheless, when the blending ratio of the polyolefin is too high, an elastic recovery from an elongation of the nonwoven fabric is lowered.
  • a blending ratio of the polyolefin to a total weight of the polymer may be determined to be from 1 to 60 wt%, preferably 5 to 50 wt%, more preferably 10 to 40 wt%.
  • the polyolefin is less than 1%, there is little lowering of the melt viscosity and no improvement of the spinning property.
  • the polyolefin is more than 60 wt%, the elongation and elastic recovery from the elongation become very poor.
  • polystyrene resin examples include a polyethylene, a polypropylene, and a copolymer of propylene with ⁇ -olefin such as ethylene or 1-butene. Most preferably, a block copolymer of propylene with ethylene, the polypropylene and the polyethylene are used.
  • Mn number-average molecular weight
  • MFR melting flow rate
  • the use of the polyethylene is preferable, because this reduces the lowering of the elastic recovery from an elongation.
  • a method of blending two polymers when spinning the polymers, and a method of using a chip in which the two polymers are previously blended by melting the two polymers or the like, can be used as the method of blending the hydrogenated block copolymer with the polyolefin.
  • the method of blending the two polymers is not especially limited, the latter method is preferred.
  • a third polymer may be added to a fiber of the stretchable nonwoven fabric within a range which does not adversely affect the object of the present invention.
  • the stretchable nonwoven fabric of the present invention is manufactured by a melt blown method.
  • a polypropylene is used as the polyolefin and two polymers are blended in a chip to make a nonwoven fabric
  • a blowing operation under a high pressure e.g., 3 kg/cm 2 G
  • a fiber in the obtained nonwoven fabric becomes an extra fine fiber, and thus a nonwoven fabric having an extremely soft handling is obtained.
  • An elastic recovery from elongation which is a superior feature of the stretchable nonwoven fabric of the present invention, is maintained up to a blending ratio of 30 wt% of the polypropylene, without any substantial change.
  • the blending ratio of the polypropylene may be increased to 60 wt%, in practical use.
  • the present invention has a feature that on extra fine fiber having a mean diameter of less than 10 ⁇ m can be obtained. Further, an effect that a strength of the nonwoven fabric is further improved by blending the polypropylene, and an adhesion of the nonwoven fabric is lowered, is obtained.
  • a mean diameter of a fiber constituting the stretchable nonwoven fabric of the present invention is 0.5 to 30 ⁇ m.
  • the mean diameter is less than 0.5 ⁇ m, the obtained nonwoven fabric is soft but has a lower strength and poor air permeability and moisture permeability.
  • the mean, diameter is more than 50 ⁇ m, the nonwoven fabric has a rough feel and a hard handling, and a waterproof pressure and bacteria barrier property of the nonwoven fabric become poor.
  • the mean diameter is less than 10 ⁇ m, and further, is between 1.0 and 6.0 ⁇ m, a collective efficiency, air permeability, moisture permeability and handling of the nonwoven fabric are improved, and the nonwoven fabric has a preferable high waterproof resistance and superior bacteria barrier and dust collecting properties.
  • the nonwoven fabric in the present invention has a weight per unit area of 5 to 500 g/m 2 , preferably 10 to 200 g/m 2 . When the weight per unit area is lower than 5 g/m 2 , the strength of the stretchable nonwoven fabric is lowered.
  • a staple fiber and a filament may be used as the fiber constituting the stretchable nonwoven fabric of the present invention, but in view of a strength of the nonwoven fabric, the filament is preferable.
  • the thus-obtained stretchable nonwoven fabric of the present invention has a superior extendability (elongation, and extension recovery), a superior resistance to weather, light, heat, and chemicals, and superior electrical insulating properties, as well as a soft feel.
  • the resistance to weather thereof is superior in particular to the polyurethane stretchable nonwoven fabric now on the market (for example, ESPANSIORE®).
  • a hydrogenated block copolymer is melted by an extruder 1 to be fed into a die 2, and extruded from multiple spinning orifices arranged in a line on a nozzle.
  • the molten polymer is extruded from the orifice 12 through a polymer flow path 11, and at the same time, a heated high-speed gas, supplied through a gas inlet 13, is injected from slits 15 provided on both sides of the orifice 12 through a gas header 14, and blown onto the flow of the extruded molten polymer.
  • the gas header 14 and the injection slit 15 can be provided between the nozzle 9 and a lip 10.
  • the molten polymer extruded with the aid of the high-speed air flow is drawn, thinned, and hardened into extrafine fibers 4, and the thus-produced extrafine fibers are deposited on a screen (a collector) 7 circulating between a pair of revolving rollers 6, 6, to thus form a random web.
  • the gas steam or air or the like is preferred, and the gas conditions are a temperature of 300 to 450°C, preferably 350 to 420 ° C, and a pressure of 0.1 kg/cm 2 G or more, preferably 0.2 to 5.0 kg/cm 2 G, which differs depending on the discharge rate.
  • the temperature of the extruder is 260 to 330 ° C, preferably 260 to 330 ° C, and the temperature of the die is 260 to 330 ° C, preferably 270 to 320 ° C.
  • a strength of a raw web i.e., a web to which an after-treatment in not applied, has a high strength obtained due to an entanglement of fibers, and a self-heat bonding property without the after-treatment. Accordingly, it is important to suitably determine a distance between a die 2 and a collector 7, for an improvement of the strength of the nonwoven fabric caused by bonding the fibers having the self-heat bonding property, i.e., when the distance is shortened, the strength is increased. Further, it is preferable to shorten the distance to increase the dispersion of the fibers in the nonwoven fabric. Namely, the distance is preferably 70 cm or less, more preferably 50 cm or less, most preferably 40 cm or less.
  • a self-heat bonding method is used as a method of bonding the fibers in the stretchable nonwoven fabric of the present invention, because this self-heat bonding method can improve the quality of the nonwoven fabric product due to an improved dispersion of the fibers, and has a lower cost.
  • heat bonding methods such as a heat embossing method, a heated roll method, a heated air method, an ultrasonic bonding method or the like can be used.
  • the heat embossing method and the heated roll method using, for example, an upper metal roller and a lower rubber roll is more preferable, because a bonding between the fibers of the nonwoven fabric is thus increased and the strength, water proof bacteria barrier, dust proof properties and a surface smoothness, are improved by using this method.
  • a treatment by the heat embossing method or the heated roll method may be conducted continuously without applying a winding process to the obtained web, or may be conducted as a separate process after the web is wound.
  • the heat embossing treatment or the heated roll treatment are conducted at a temperature of 150°C or lower, preferably 50 to 130 ° C, more preferably 60 to 120 ° C and under a pressure of 0.5 to 100 kg/cm, preferably 1 to 75 kg/cm.
  • a temperature and pressure higher than the above range the fiber is melted and a nonwoven fabric having a film-like form and a lower air permeability is obtained.
  • the treatment is conducted at a temperature and pressure lower than the above range, the heat bonding effect becomes poor, and thus it is impossible to improve the strength and the surface smoothness of the nonwoven fabric.
  • Either a continuous pattern or a discontinuous pattern can be used as an embossing pattern using in the heat-embossing treatment. Further, various patterns such as a line, a dotted line, a lattice, a diagonal lattice, a circle, a diamond, or a woven fabric-like pattern, or the like, can be used.
  • An electret treatment may be applied to improve a filtering property of the stretchable nonwoven fabric of the present invention.
  • the stretchable nonwoven fabric of the present invention can be used by piling or laminating same with a sheet-like material such as another nonwoven fabric manufactured by a spun bond method, a carding method, a wet method or the like, a knitted fabric, a woven fabric, a film or the like. After these materials are piled, if necessary, the stretchable nonwoven fabric and the sheet-like material may be bonded by a heat bonding method, or an entanglement method or the like.
  • a sheet-like material such as another nonwoven fabric manufactured by a spun bond method, a carding method, a wet method or the like, a knitted fabric, a woven fabric, a film or the like.
  • a successive block copolymerization is performed by using a lithium alkyl catalyst, to synthesize a butadiene-styrene-butadiene-styrene type block copolymer having a composition ratio wt% of 10-12.5-65-12.5, as a pre-polymer, whereby a pre-polymer having an Mn of 47,000, a polystyrene content S of 25 wt%, and a 1,2-vinyl content V of a conjugated diene structure of 31 wt% is obtained. Hydrogenation is applied to this pre-polymer, and a hindered amine series stabilizer of 0.5 wt% is added to produce a hydrogenated block copolymer as a raw material a pellet.
  • the thus-obtained hydrogenated block copolymer has a melt viscosity of a pellet thereof of 520 poise, and is fed to the extruder and heat-melted at an extruder temperature of 290°C.
  • the molten copolymer then is fed into a nozzle having 200 orifices with a diameter of 0.4 mm ⁇ and aligned at a pitch of 1 mm, and extruded as a high speed fluid at an extruding rate of 0.2 g per minute.
  • a super heated steam controlled to a temperature of 380°C in used as the fluid and this super-heated steam is injected from slits of a melt blown nozzle onto a molten copolymer, at a pressure of 0.6 kg/cm 2 G, to thereby draw and thin the molten polymer.
  • thinned fibers are sequentially collected on a running net conveyor, in which a distance between a die and a collector is 15 cm, to form a web.
  • the obtained web is a nonwoven fabric having a superior stretchability and a soft handling. Tests of the physical properties of the obtained nonwoven were performed, and the results are shown in Table 1.
  • B-A-B-A (10-12.5-65-12.5) Physical properties of Nonwover Fabric Weight per unit area 101 g/m 2 Mean diameter of fiber 12.7 ⁇ m strength 424 g/cm Elongation 571% Extension recovery rate 99% Elongation stress 62 g/cm Stiffness 3.2 cm Peel strength 3 g/cm Light resistance (Fading) 4-5 grade Water resistance pressure 60 mm H 2 O Collecting efficiency 28%
  • Tests are performed under the same conditions as in Reference-Example 1, except that Kraton G-1657X and G-1652 supplied from Shell Chemical are used as a raw material. Note, when using G-1652 the yarn is not tied, and thus a nonwoven fabric cannot be obtained.
  • a constitution of a polymer, physical properties of the polymer, and physical properties of the nonwoven fabric of Comparative Example 1 are shown in Table 2, in comparison to Reference-Example 1.
  • Stretchable nonwoven fabrics are manufactured under the same conditions as in Reference-Example 1, except that a pre-polymer having a different number-average molecular weight Mn was used.
  • the physical properties of the nonwoven fabric were investigated. The results are shown in Table 3.
  • the polymer in Comparative Example 3 is not solidified when forming a chip, and accordingly, a chip cannot be obtained, and thus the test was stopped.
  • the melt viscosity in Comparative Example 4 is high, and a spinning property thereof is poor, and thus a web cannot be obtained.
  • Comparative Example 3 Reference-Example 2 Reference-Example 3 Reference-Example 4 Comparative Example 4 Mn (10000) 2.5 3.7 4.6 5.4 6.8 S (wt%) 26 28 26 24 25 V (wt%) 33 32 36 38 34 Weight per unit area (g/m 2 ) Chip cannot be obtained due to impossibility of set up 102 106 113 Spinning is impossible due to high melting viscosity strength (g/cm) 263 482 361 strangth/weigh t per unit area (g/cm/g/m 2 ) 2.6 4.5 32 Elongation action (%) 516 703 441 extension recovery rate (%) 98 100 94 Peeling strength (g/cm) 4 30 67
  • Pre-polymers having different content(s) of styrene are synthesized to obtain block copolymers, stretchable nonwoven fabrics are manufactured under the same conditions as in Reference-Example 1, and the physical properties are investigated.
  • the results are shown in Table 4.
  • the polymer in Comparative Example 5 is not solidified when forming a chip, and accordingly, the chip cannot be obtained, and thus the test was stopped.
  • the melt viscosity in Comparative Example 6 is high, a spinning property thereof is poor, and many polymer balls are generated, and thus a satisfactory web cannot be obtained.
  • Comparative Example 5 Reference-Example 5 Reference-Example 6 Reference-Example 7 Comparative Example 6 Mn (10000) 4.8 5.1 4.6 4.7 4.6 S (wt%) 11 19 25 33 42 V (wt%) 32 36 37 35 33 Weight per unit area (g/m 2 ) Chip cannot be obtained due to impossibility of set up 90 104 101 Polymer balls are generated due to high melting viscosity strength (g/cm) 281 364 272 strength/weight per unit area (g/cm/g/m 2 ) 3.1 3.5 2.7 Elongation (%) 867 649 456 extension recovery rate (%) 100 99 96 Peeling strength (g/cm) 82 74 1
  • Pre-polymers having different 1,2-vinyl contents (V) of conjugated diene structures in a conjugated diene compound are synthesized to obtain block polymers, and stretchable nonwoven nonwoven fabrics are manufactured under the same conditions as in Reference-Example 1.
  • the physical properties are investigated, and the results shown in Table 5.
  • a spinning property thereof is poor, a length of fiber obtained is short, and balls or powder-like materials exist in the web, and thus a satisfactory web cannot be obtained.
  • Comparative Example 7 Reference-Example 8 Reference-Example 9 Reference-Example 10 Comparative Example 8 Mn (10000) 4.3 4.2 4.2 4.6 4.1 S (wt%) 25 28 25 25 29 V (wt%) 15 23 33 42 53 Weight per unit area (g/m 2 ) 95 98 101 103 Short length of fiber ball or powder like materials strength (g/cm) 141 253 364 341 strength/weight per unit area (g/cm/g/m 2 ) 1.5 2.6 3.6 3.3 Elongation (%) 162 394 560 738 extension recovery rate (%) 44 87 99 100 Peeling strength (g/cm) 0 0.5 16 238
  • a raw material is prepared by hydrogenating a pre-polymer having Mn of 51000, S of 25,5 wt% and V of 36 wt%, and stretchable nonwoven fabrics are manufactured under the same conditions as in Reference-Example 1, except that the extruder temperature is 300 ° C, the gas temperature is 400°C, the gas pressure is 0.5 kg/cm 2 G and the distance between a die and a collector is 10 cm.
  • the stretchable nonwoven fabric in Reference-Example 11 is treated by a pair of heated roller an upper roller of which is a metal roller and a lower roller of which is a rubber roller, under conditions of a temperature and a pressure as shown in Table 6. The results are shown in Table 6.
  • Comparative Example 9 The nonwoven fabric in Comparative Example 9 became a film-like form, and accordingly, a measurement of the physical properties was not performed.
  • Reference-Example 11 Reference-Example 12
  • a hydrogenated block copolymer is manufactured by hydrogenating a pre-polymer having an Mn of 49,000, S of 29 wt%, and V of 36 wt%, and sequentially, a chip is made from the hydrogenated block copolymer. Further, a polyethylene having an Mn of 2880 and the density of 0.930 is added to the chip of the hydrogenated block copolymer by 30 wt%, and then a raw material is prepared by melting and blending the two materials in a double-screw extruder.
  • a stretchable nonwoven fabric of Example 14 is manufactured from the raw material under the same conditions as in Reference-Example 1, except that a gas pressure is 0.3 kg/cm 2 G and a distance between the die and the collector is 10 cm, and physical properties thereof investigated.
  • Stretchable nonwoven fabrics in Comparative Examples 10 and 11 are manufactured under the same conditions as in Example 14, except that Kraton G-1657X and G-1652 supplied from Shell Chemical Co. are used in place of the hydrogenated block copolymer of the present invention, and the physical properties thereof investigated. The results are shown in Table 7.
  • the nonwoven fabrics prepared from Kraton G-1657X and G-1652 have a lower strength and elongation than the nonwoven fabric of Example 14.
  • Example 14 Comparative example 10 Kraton G-1657X Comparative example 11 Kraton G-1652 Additional amount of Polyethylene (wt%) 30 30 30 weight per unit area (g/m 2 ) 98 90 94 strength (g/cm) 291 68 141 strength/weight per unit area (g/cm/g/m 2 ) 3.0 0.8 1.5 Elongation (%) 526 388 360 Extension recovery rate (%) 97 97 97 Elongation stress (g/cm) 102 60 69 Peeling strength (g/cm) 0 43 0 Collecting efficiency (%) 19.8 11.4 6.6
  • Stretchable nonwoven fabrics are manufactured under the same conditions as in Example 14, except that added amount of the polyethylene is 5 wt%, 15 wt%, 45 wt% and 70 wt%, the gas pressure is 0.6 kg/cm 2 G and the distance between the die and the collector is 7 cm, and physical properties thereof investigated. The results are shown in Table 8.
  • Example 15 Example 16 Example 17 Comparative Example 12 Additional amount of polyethylene (wt%) 5 15 45 70 Weight per unit area (g/m 2 ) 96 96 101 99 Strength (g/cm) 265 388 455 460 Strength/weight per unit area (g/cm/g/m 2 ) 2.8 4.0 4.5 4.6 Elongation (%) 434 563 310 142 Extension recovery rate (%) 98 99 92 67 Elongation stress (g/cm) 79 91 240 310 Peeling strength (g/cm) 0 0 0 0 0 0
  • Stretchable nonwoven fabrics are manufactured under the same conditions as in Example 16, the added amount of the polyethylene being 15 wt%, except that the Mn of the polyethylene is made 2800 (density of 0.930), 3400 (density of 0.928), 12000 (density of 0.918) and 17000 (density of 0.929) and the gas pressure is 0.7 kg/cm 2 G, and physical properties thereof investigated. The results are shown in Table 9.
  • Example 18 Example 19 Example 20
  • Example 21 Polyethylene (Mn) 2880 3400 12000 17000 Weight per unit area (g/m 2 ) 100 99 94 102 Strength (g/cm) 292 369 226 256 Strength/weight per unit area (g/cm/g/m 2 ) 2.9 3.7 2.4 2.5 Elongation (%) 566 558 320 270 Extension recovery rate (%) 99 99 97 96 Elongation stress (g/cm) 65 69 82 120 Peeling strength (g/cm) 0 0 0 0 0 0
  • Stretchable nonwoven fabrics are manufactured under the same conditions as in Example 14, except that two types of polypropylenes having an Mn of 40,000 (MFR of 240) and an Mn of 50,000 (MFR of 80) are added by 12 wt%, in place of the polyethylene, and physical properties thereof investigated. The results are shown in Table 10.
  • Example 22 polypropylene (Mn) 40,000 50,000 Mean diameter of fiber ( ⁇ m) 18.5 19.6 Weight per unit area (g/m 2 ) 99 102 Strength (g/cm) 335 300 Strength/weight per unit area (g/cm/g/m 2 ) 3.4 2.9 Elongation (%) 436 451 Extension recovery rate (%) 95 93 Elongation stress (g/cm) 109 115 Peeling strength (g/cm) 0 0 0
  • a stretchable nonwoven fabric is manufactured under the same conditions as in Example 14, except that a polypropylene having an Mn of 50,000 (MFR of 80) is added by 20 wt%, and a raw material is prepared by a chip blending operation, the gas pressure is 3.0 kg/cm 2 G and the distance between the die and the collector is 30 cm, and the physical properties thereof investigated.
  • MFR polypropylene having an Mn of 50,000
  • MFR MFR of 80
  • Example 24 Weight per unit area (g/m 2 ) 123 Mean diameter of fiber ( ⁇ m) 3 Strength (g/cm) 742 Elongation (%) 280 Extension recovery rate (%) 93 Water resistant pressure (mmH 2 O) 540 Air Permeability (cc/cm/sec) 10 Collecting efficiency (%) 55 Light resistance Retaining ratio of Strength (%) 92 Fading (grade) 4 - 5
  • the obtained nonwoven fabric is applied with the voltage of 19 KV to perform an electric treatment, and the collecting efficiency thus improved to 86%.
  • Stretchable nonwoven fabrics are manufactured under the same conditions as in Example 24, except that an amount of the polypropylene chip to be blended are changed, and the physical properties thereof investigated. The results are shown in Table 12.
  • Stretchable nonwoven fabrics are manufactured under the same conditions as in Reference-Example 1, except that a hydrogenated block copolymer is manufactured by hydrogenating a pre-polymer having an Mn of 53,000, an S of 20 wt% and a V of 36 wt%, and sequentially, a chip is made from the hydrogenated block copolymer, three types of polypropylenes having an Mn of 45,000 (MFR of 140), an Mn of 50,000 (MFR of 80) or an Mn of 53,000 (MFR of 40) are added to the chip, to blend the polypropylene with the hydrogenated block copolymer in the chip state, and the obtained chip is fed to an extruder under the conditions of a gas pressure of 2.5 kg/cm 2 G and a distance between the die and the collector of 50 cm.
  • MFR of 140 Mn of 45,000
  • MFR of 80 Mn of 50,000
  • MFR of 40 Mn of 53,000
  • Example 28 Example 29
  • Polypropylene (10,000) 4.5 5.0 5.3 Weight per unit area (g/m 2 ) 38 42 38 Strength (g/cm) 102 259 188 Strength/weight per unit area (g/cm/g/m 2 ) 2.7 6.2 5.0 Elongation (%) 158 160 124 Extension recovery rate (%) 84 92 90
  • a raw web is manufactured under the same conditions as in Example 24, except that a distance between the die and the collector is 50 cm, and sequentially, a heat bonding treatment is applied by a heat embossing roll, and the physical properties of the obtained nonwoven fabric investigated. The results are shown in Table 14.
  • An embossing pattern applied with the heat embossing roll is a pattern 20 having a compressed portion 21, an unpressed portion 22, and an area ratio of the compressed portion of 22%, as shown in Fig. 4.
  • Example 31 Example 32
  • Example 33 Condition of treatment temperature (°C) untreated 70 90 pressure (kg/cm) 15 15 weight per unit area (g/m 2 ) 116 119 125 strength (g/cm) 381 351 760 Strength/weight per unit area (g/cm/g/m 2 ) 3.3 4.6 6.1 Elongation (%) 192 253 304 Extension recovery rate (%) 98 94 93 Elongation stress (g/cm) 213 245 285 voter resistant pressure (mmAq) 420 640 800 collecting efficiency (%) 52 58 63
  • the nonwoven fabric in Example 24 is stretched to a length twice that of an original length, and then inserted between two spun-bonded nonwoven fabrics of polypropylene, and further, a heat bonding treatment is applied to the piled nonwoven fabrics by an embossing roll having a discontinuously arranged circular pattern.
  • the obtained composite nonwoven fabric is a nonwoven fabric with gathers, and an elongation thereof is 100%.
  • the hydrogenated block copolymer obtained in Reference-Example 1 is fed into an extruder, and the copolymer is melted under a superheated heated condition at 300°C, and is extruded from 100 orifices at an individual extruding amount of 0.7 g/min.
  • the fibers are drawn by an air sucker arranged below the extruder, and are piled on a net conveyor arranged below the sucker, to form a web. A dispersion property of the web just after spinning is not good.
  • This web is applied with a heat bonding treatment by a heat roll, an upper roll of which is a metal roll and a lower roll of which is a rubber roll, having a temperature of 110° C and at a pressure of 15 kg/cm, to obtain nonwoven fabric.
  • the obtained nonwoven fabric having a weight per unit area of 130 g/m 2 has a strong strength, i.e., 1.1 kg/cm, and a superior strechability.
  • the stretchable nonwoven fabric in accordance with the present invention is constituted as described above, the stretchable nonwoven fabric of the present invention has a superior strength, extension characteristics i.e., elongation and extension recovery, weathering resistance, light resistance, heat resistance, chemical resistance and electrical resistance, and a soft handling.
  • the stretchable nonwoven fabric in accordance with the present invention can be broadly used as a medical and sanitary material, for such articles as a compress, a stretchable tape, a bandage, a diaper or the like, an apparel such as surgical wear, working wear, caps or hats or the like, or as industrial goods such as gloves, a covering material for an electric wire, or the like.
  • the stretchable nonwoven fabric in accordance with the present invention and having the above described characteristics can be stably manufactured by the manufacturing method in accordance with the' present invention.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Nonwoven Fabrics (AREA)

Claims (4)

  1. Etoffe non tissée, extensible, soufflée en phase fondue, ayant un poids par aire unitaire de 5 à 500 g/m2; un diamètre moyen des fibres de 0,5 à 30 µm, composée d'une fibre thermoplatique comprenant
    un copolymère séquencé hydrogéné C obtenu par hydrogénation d'un copolymère séquencé comprenant au moins deux blocs polymères A constitués principalement d'un composé vinylique aromatique et au moins deux blocs polymères B constitués principalement d'un composé diène conjugué, au moins un bloc polymère B étant arrangé sur une extrémité de sa chaíne polymère, le poids moléculaire moyen en nombre dudit copolymère séquencé étant entre 30 000 et 65 000, la teneur S du composé vinylique aromatique dans le copolymère séquencé étant entre 15% en poids et 40% en poids, et la teneur V en 1,2-vinyle de la structure diène conjugué dans le composé diène conjugué étant entre 20% en poids et 50% en poids, avant qu'une hydrogénation soit appliquée, et
    une polyoléfine D,
    où le rapport de mélange de la polyofine D au poids total du polymère est de 1 à 60% en poids.
  2. Etoffe non tissée extensible selon la revendication 1, où ledit rapport de mélange de la polyoléfine D au poids total du polymère est de 5 à 50% en poids.
  3. Etoffe non tissée extensible selon la revendication 1, où ladite polyoléfine est un polypropylène.
  4. Etoffe non tissée extensible selon la revendication 1, où le diamètre moyen des fibres constituant ladite étoffe non tissée est entre 1,0 et 6,0 µm.
EP90900366A 1988-12-27 1989-12-25 Tissu non tisse extensible et procede de production Expired - Lifetime EP0457905B2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP32793588 1988-12-27
JP327935/88 1988-12-27
JP32793588 1988-12-27
PCT/JP1989/001294 WO1990007602A1 (fr) 1988-12-27 1989-12-25 Tissu non tisse extensible et procede de production

Publications (4)

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EP0457905A1 EP0457905A1 (fr) 1991-11-27
EP0457905A4 EP0457905A4 (en) 1992-07-08
EP0457905B1 EP0457905B1 (fr) 1995-03-08
EP0457905B2 true EP0457905B2 (fr) 2001-10-24

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KR (1) KR920007989B1 (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6659990B1 (en) 1996-03-29 2003-12-09 Kimberly-Clark Worldwide, Inc. Absorbent article having a breathability gradient

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5366793A (en) * 1992-04-07 1994-11-22 Kimberly Clark Co Anisotropic nonwoven fibrous web
US5332613A (en) * 1993-06-09 1994-07-26 Kimberly-Clark Corporation High performance elastomeric nonwoven fibrous webs
US5589542A (en) * 1993-11-03 1996-12-31 Shell Oil Company Multiblock hydrogenated polymers for adhesives
KR101896611B1 (ko) * 2017-02-03 2018-09-07 아주대학교산학협력단 설포닐기 함유 화합물의 제조 방법

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JPH0615649B2 (ja) * 1984-07-26 1994-03-02 旭化成工業株式会社 水素添加したブロツク共重合体組成物
US4692371A (en) * 1985-07-30 1987-09-08 Kimberly-Clark Corporation High temperature method of making elastomeric materials and materials obtained thereby
AU582455B2 (en) * 1985-07-30 1989-03-23 Kimberly-Clark Corporation Polyolefin containing extrudable compositions and methods for their formation into elastomeric products
JPS6242554A (ja) * 1985-08-20 1987-02-24 Fujitsu Ltd 半導体装置の製造方法
CA1309530C (fr) * 1986-07-07 1992-10-27 Glenn Roy Himes Melanges de copolymere bloque styrene-ethylene, a resistance amelioree a l'absorption d'huile

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6659990B1 (en) 1996-03-29 2003-12-09 Kimberly-Clark Worldwide, Inc. Absorbent article having a breathability gradient

Also Published As

Publication number Publication date
DE68921645D1 (de) 1995-04-13
EP0457905A4 (en) 1992-07-08
DE68921645T3 (de) 2002-09-12
DE68921645T2 (de) 1995-08-17
KR910700373A (ko) 1991-03-15
WO1990007602A1 (fr) 1990-07-12
EP0457905A1 (fr) 1991-11-27
KR920007989B1 (ko) 1992-09-21
EP0457905B1 (fr) 1995-03-08

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