EP0457905B1 - Ausdehnbares, nicht gewebtes gewebe und verfahren zur herstellung - Google Patents

Ausdehnbares, nicht gewebtes gewebe und verfahren zur herstellung Download PDF

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Publication number
EP0457905B1
EP0457905B1 EP90900366A EP90900366A EP0457905B1 EP 0457905 B1 EP0457905 B1 EP 0457905B1 EP 90900366 A EP90900366 A EP 90900366A EP 90900366 A EP90900366 A EP 90900366A EP 0457905 B1 EP0457905 B1 EP 0457905B1
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Prior art keywords
nonwoven fabric
stretchable nonwoven
fabric according
block copolymer
polymer
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French (fr)
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EP0457905A4 (en
EP0457905B2 (de
EP0457905A1 (de
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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    • 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 and a method of manufacturing the same. 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, and a method of manufacturing the same.
  • 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 blob 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 malt 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 "KRATONO 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/butylene- styrene 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/butylene- styrene 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).
  • a first 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.
  • a second object of the present invention is to provide a method of manufacturing a superior stretchable nonwoven fabric composed of a hydrogenated block copolymer.
  • a third object of the present invention is to provide a stretchable nonwoven fabric having a soft and non-sticky handling and a superior strength, extendable characteristics, weathering resistance, light resistance, and heat resistance.
  • 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 malt blown method, and the characteristics of the stretchable nonwoven fabric, and thus accomplished the present invention.
  • the first object of the present invention can be attained by a stretchable nonwoven fabric composed of a thermal plastic fiber manufactured from a hydrogenated block copolymer obtained by hydrogenating a block copolymer including 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 compound, at least one polymer block B being arranged on an end of a polymer chain thereof, a number-average molecular weight of the block copolymer being between 30,000 and 65,000 and a content of the vinyl aromatic compound in the block copolymer being between 15 wt% and 40 wt%.
  • the second object of the present invention can be attained by a method of manufacturing a stretchable nonwoven fabric, wherein a block copolymer including at least two polymer blocks A of a vinyl aromatic compound and at least two polymer blocks B of a conjugated diene, and in which a content of the vinyl aromatic compound is between 15 wt% and 40 wt% and at least one polymer block B is arranged on an end of a polymer chain, a number average molecular weight of which is between 30,000 and 65,000, is manufactured by a sequential block copolymerization, said block copolymer is hydrogenerated, the obtained hydrogenerated block copolymer is spun; and a fiber group obtained by a spinning process is accumulated on a collecting face to form a fiber web.
  • a block copolymer including at least two polymer blocks A of a vinyl aromatic compound and at least two polymer blocks B of a conjugated diene, and in which a content of the vinyl aromatic compound is between 15 wt% and 40 wt% and
  • the third object of the present invention can be attained by a stretchable nonwoven fabric composed of a fiber comprising a hydrogenated block copolymer C obtained by hydrogenating a block copolymer including 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 compound and on an end of a polymer chain of which at least one polymer block B is arranged, and a polyolefin D, wherein a polymerization ratio (C/D) of the hydrogenated block copolymer and the polyolefin D is between 40/60 and 99/1.
  • a polymerization ratio (C/D) of the hydrogenated block copolymer and the polyolefin D is between 40/60 and 99/1.
  • a pre-polymer for example, styrene, a-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, organonickle 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 hydrogenating 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 should be within 10 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. (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 an adhesion parameter defined from the following equation, and found that the value of T has a clear relationship to the peel strength, i.e., the adhesion of the nonwoven fabric.
  • 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.
  • 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.
  • a 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 When the polyolefin is less than 1 %, there is little lowering of the melt viscosity and no improvement of the spinning property. In contrast, when 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 a-olefin such as ethylene or 1-butane. 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.
  • Three blending states of two polymer exist, i.e., that wherein two polymers are blended in a single fiber, that wherein fibers constituted by a specific polymer, respectivity, are mixed in a nonwoven fabric, and that wherein the two above states are present in the nonwoven fabric. Most preferably, the first state wherein the two polymers are blended in the single fiber is used.
  • 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 hydrogonated 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. Further, another fiber may be blended with the nonwoven fabric of the present invention, within a range which do not adversely affect the object of the present invention.
  • the stretchable nonwoven fabric of the present invention can be manufactured by a melt blown method, but when the nonwoven fabric is manufactured only from the hydrogenated block copolymer, i.e., without the polyolefin, the use of a heated gas having a high speed and high pressure, i.e., 1.2 kg/cM 2 G or more produces a poor blowability, and thus the manufacturing of the fiber becomes difficult. Accordingly, an optimum pressure of the heated and high speed gas must be between 0.1 and 1.2 kg/cm 2 G, and accordingly, a fiber in the nonwoven fabric obtained must have a relatively thick diameter, e.g., about 10 ⁇ m or more.
  • 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 less than 50 /1.m, preferably 0.5 to 30 /1.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 , more preferably 10 to 200 g/m 2.
  • 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@).
  • An a method of manufacturing the stretchable nonwoven fabric of the present invention, a melt blown method, a spun bond method, and a method in which a fiber obtained by the melt spinning method is sheeted out by an ordinary dry process or wet process, can be used, but in view of the spinning properties, the melt blown method is most preferable.
  • 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 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.
  • Example 2 Tests are performed under the same conditions as in 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 Example 1.
  • Stretchable nonwoven fabrics are manufactured under the same conditions as in 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.
  • 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 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.
  • 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 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.
  • 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 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 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.
  • the nonwoven fabric in Comparative Example 9 became a film-like form, and accordingly, a measurement of the physical properties was not performed.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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 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
  • 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.
  • 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 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.

Claims (24)

1. Dehnbares nichtgewebtes Gewebe, bestehend aus einer thermischen Kunststoff-Faser, hergestellt aus einem hydrierten Block-Copolymer, erhalten durch Hydrieren eines Block-Copolymers, umfassend wenigstens zwei Polymerblöcke A, bestehend hauptsächlich aus einer aromatischen Vinylverbindung, und wenigstens zwei Polymerblöcke B, bestehend hauptsächlich aus einer konjugierten Dien-Verbindung, wobei wenigstens ein Polymerblock B am Ende einer Polymerkette davon angeordnet ist, das Zahlenmittel des Molekulargewichtes des Block-Copolymers zwischen 30 000 und 65 000 liegt und der Gehalt an aromatischer Vinylverbindung im Block-Copolymer zwischen 15 Gew.-% und 40 Gew.-% liegt.
2. Dehnbares nichtgewebtes Gewebe nach Anspruch 1, wobei der Gehalt an 1,2-Vinyl der konjugierten Dienstruktur in der Verbindung mit der konjugierten Dienstruktur zwischen 20 Gew.-% und 50 Gew.-% beträgt.
3. Dehnbares nichtgewebtes Gewebe nach Anspruch 1, wobei das Zahlenmittel des Molekulargewichtes des Block-Copolymers zwischen 35 000 und 60 000 liegt.
4. Dehnbares nichtgewebtes Gewebe nach Anspruch 1, wobei der Gehalt an aromatischer Vinylverbindung zwischen 20 Gew.-% und 35 Gew.-% liegt.
5. Dehnbares nichtgewebtes Gewebe nach Anspruch 1, wobei der Gehalt an 1,2-Vinyl der konjugierten Dienstruktur in der Verbindung mit der konjugierten Dienstruktur zwischen 25 Gew.-% und 45 Gew.-% beträgt.
6. Dehnbares nichtgewebtes Gewebe nach Anspruch 1, wobei eine Oberfläche des nichtgewebten Gewebes durch eine Hitzebehandlung geglättet wird.
7. Dehnbares nichtgewebtes Gewebe nach Anspruch 1, wobei durch eine Hitzebehandlung auf eine Oberfläche des nichtgewebten Gewebes ein Muster angebracht wird.
8. Dehnbares nichtgewebtes Gewebe nach Anspruch 1, wobei die thermische Kunststoff-Faser elektrisch geladen wird.
9. Nichtgewebtes Kompositgewebe, umfassend ein dehnbares nichtgewebtes Gewebe nach Anspruch 1 und ein folienartiges Material, das auf das dehnbare nichtgewebte Gewebe aufgezogen ist.
10. Verfahren zur Herstellung eines dehnbaren nichtgewebten Gewebes, wobei ein Block-Copolymer, umfassend wenigstens zwei Polymerblöcke A einer aromatischen Vinylverbindung und wenigstens zwei Polymerblöcke B eines konjugierten Diens und in dem der Gehalt der aromatischen Vinylverbindung zwischen 15 Gew.-% und 40 Gew.-% liegt und worin wenigstens ein Polymerblock B am Ende einer Polymerkette angeordnet ist und dessen Zahlenmittel des Molekulargewichtes zwischen 30 000 und 65 000 liegt, durch eine sequentielle Block-Copolymerisation hergestellt wird; wobei das Block-Copolymer hydriert ist; das erhaltene hydrierte Block-Copolymer versponnen wird und eine durch ein Spinnverfahren erhaltene Fasergruppe auf einer Sammelfläche gesammelt wird, wodurch ein Faservlies gebildet wird.
11. Verfahren zur Herstellung eines dehnbaren nichtgewebten Gewebes nach Anspruch 10, wobei eine Kopplungsreaktion nach Durchführung der sequentiellen Block-Copolymerisation eingesetzt wird.
12. Verfahren zur Herstellung eines dehnbaren nichtgewebten Gewebes nach Anspruch 10, wobei ein Schmelzblasverfahren als das Spinnverfahren verwendet wird, um ein Fasergewebe zu erhalten.
13. Verfahren zur Herstellung eines dehnbaren nichtgewebten Gewebes nach Anspruch 10, wobei das Verfahren weiterhin eine Hitzebehandlung umfaßt.
14. Verfahren zur Herstellung eines dehnbaren nichtgewebten Gewebes nach Anspruch 10, wobei das Verfahren weiterhin eine elektrische Behandlung umfaßt.
15. Verfahren zur Herstellung eines dehnbaren nichtgewebten Gewebes nach Anspruch 10, wobei das Verfahren weiterhin ein Verfahren zum Ansammeln eines anderen folienartigen Materials am dehnbaren nichtgewebten Gewebe umfaßt.
16. Dehnbares nichtgewebtes Gewebe, bestehend aus einer Faser, umfassend ein hydriertes Block-Copolymer C, erhalten durch das Hydrieren eines Block-Copolymers, enthaltend wenigstens zwei Polymerblöcke A, bestehend im wesentlichen aus einer aromatischen Vinylverbindung, und wenigstens zwei Polymerblöcke B, bestehend im wesentlichen aus einer konjugierten Dien-Verbindung, an einem Ende einer Polymerkette, an der wenigstens ein Polymerblock B angeordnet ist, und eines Polyolefins D, wobei ein Polymerisations-Verhältnis (C/D) des hydrierten Block-Copolymers und des Polyolefins D zwischen 40/60 und 99/1 liegt.
17. Dehnbares nichtgewebtes Gewebe nach Anspruch 16, wobei das Polymerisations-Verhältnis (C/D) zwischen 50/50 und 95/5 liegt.
18. Dehnbares nichtgewebtes Gewebe nach Anspruch 16, wobei das Polyolefin ein Polyethylen ist.
19. Dehnbares nichtgewebtes Gewebe nach Anspruch 16, wobei das Polyolefin ein Polypropylen ist.
20. Dehnbares nichtgewebtes Gewebe nach Anspruch 16, wobei der mittlere Durchmesser der Fasern, aus denen das nichtgewebte Gewebe besteht, 10 um oder weniger beträgt.
21. Dehnbares nichtgewebtes Gewebe nach Anspruch 16, wobei eine Oberfläche des nichtgewebten Gewebes durch eine Hitze-Behandlung geglättet wird.
22. Dehnbares nichtgewebtes Gewebe nach Anspruch 16, wobei auf eine Oberfläche des nichtgewebten Gewebes durch eine Hitze-Behandlung ein Muster aufgebracht wird.
23. Dehnbares nichtgewebtes Gewebe nach Anspruch 16, wobei die thermoplastische Faser elektrifiziert wird.
24. Nichtgewebte Komposit-Faser, bestehend aus einem dehnbaren nichtgewebten Gewebe nach Anspruch 16, und folienartiges Material, aufgezogen auf das dehnbare nichtgewebte Gewebe.
EP90900366A 1988-12-27 1989-12-25 Ausdehnbares, nicht gewebtes gewebe und verfahren zur herstellung Expired - Lifetime EP0457905B2 (de)

Applications Claiming Priority (4)

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JP327935/88 1988-12-27
JP32793588 1988-12-27
JP32793588 1988-12-27
PCT/JP1989/001294 WO1990007602A1 (en) 1988-12-27 1989-12-25 Extensible non-woven fabric and its production method

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

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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
NZ331962A (en) 1996-03-29 1999-05-28 Kimberly Clark Co Absorbent article comprising a vapour permeable material with a specified water vapour transmission rate
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 (en) * 1986-07-07 1992-10-27 Glenn Roy Himes Styrene-ethylene/butylene block copolymer blends with improved oil absorption resistance

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EP0457905A4 (en) 1992-07-08
EP0457905B2 (de) 2001-10-24
DE68921645T3 (de) 2002-09-12
DE68921645D1 (de) 1995-04-13
EP0457905A1 (de) 1991-11-27
DE68921645T2 (de) 1995-08-17
KR920007989B1 (ko) 1992-09-21
KR910700373A (ko) 1991-03-15
WO1990007602A1 (en) 1990-07-12

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