WO2023181789A1 - Corps stratifié - Google Patents

Corps stratifié Download PDF

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Publication number
WO2023181789A1
WO2023181789A1 PCT/JP2023/006976 JP2023006976W WO2023181789A1 WO 2023181789 A1 WO2023181789 A1 WO 2023181789A1 JP 2023006976 W JP2023006976 W JP 2023006976W WO 2023181789 A1 WO2023181789 A1 WO 2023181789A1
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WIPO (PCT)
Prior art keywords
laminate
resin
skin layer
less
layer
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Ceased
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PCT/JP2023/006976
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English (en)
Japanese (ja)
Inventor
孝樹 石井
貴大 土本
幸司 北村
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Toray Industries Inc
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Toray Industries Inc
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Priority to JP2023514403A priority Critical patent/JPWO2023181789A1/ja
Publication of WO2023181789A1 publication Critical patent/WO2023181789A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof

Definitions

  • the present invention relates to a laminate consisting of a skin layer and a lining layer, which are artificial leathers containing a fiber entangled body made of ultrafine fibers and a polymeric elastic body.
  • Artificial leather with raised naps has superior characteristics compared to natural leather, such as high durability and uniform quality, and is used in various fields such as vehicle interior materials, furniture, miscellaneous goods, and clothing.
  • artificial leather is used as the outer skin of vehicle interior materials, furniture, miscellaneous goods, etc., fabrics etc. are pasted on the back side of the artificial leather for reinforcement or cushioning purposes. (lined) to form a laminate.
  • laminates lined with artificial leather have problems such as the fibers of the laminate being strongly restricted by the resin used for adhesion, resulting in a hard texture, and the adhesive strength decreasing at high temperatures due to lack of heat resistance. .
  • the adhesive strength at high temperatures is strongly restricted by the resin used for adhesion, resulting in a hard texture, and the adhesive strength decreasing at high temperatures due to lack of heat resistance.
  • Patent Document 1 a method is disclosed in which a thermoplastic elastomer is injection molded on the back side of artificial leather to form a laminate. Further, in a technique as disclosed in Patent Document 2, a method is disclosed in which a foamed resin layer and a fiber aggregate layer are overlapped and a laminate is formed by needle punching. In the technique disclosed in Patent Document 3, a method is disclosed in which a reactive hot melt adhesive is spray coated and a polyurethane foam and a skin layer are laminated.
  • JP2017-61051A Japanese Patent Application Publication No. 2002-103496 Japanese Patent Application Publication No. 2017-136735
  • thermoplastic elastomer is injection molded on the back side of the artificial leather at high pressure, so the thermoplastic elastomer penetrates into the inside of the artificial leather, resulting in a decrease in flexibility. is the issue.
  • the laminate can be made flexible to some extent, but the problem is that the adhesive strength is weak at room temperature and at high temperature.
  • Patent Document 3 it is possible to improve the adhesive force while maintaining flexibility to some extent, but the adhesive strength is still not sufficient and it easily peels off at high temperatures. The issue is that this occurs.
  • the present invention has been made in view of the above circumstances, and its purpose is to improve adhesive strength, flexibility, and surface quality at high temperatures in a laminate consisting of a skin material and a lining material. Our goal is to provide an excellent laminate.
  • a laminate in which a layer of skin material (skin layer) and a layer of lining material (backing layer) are laminated with an adhesive resin interposed therebetween It has been found that a laminate with excellent adhesive strength at high temperatures can be obtained by forming a specific structure between the adhesive resin and the skin layer in a cross section parallel to the thickness direction of the body.
  • the resin constituting the lining layer and the skin layer are identified. It has been found that a laminate with excellent adhesive strength at high temperatures can also be obtained by forming a structure of Furthermore, it has been found that these laminates have excellent flexibility and surface quality.
  • the present invention refers to the embodiment according to [1] below (hereinafter sometimes referred to as the "first embodiment”), and [2] ] (hereinafter sometimes referred to as the "second embodiment").
  • the skin layer is an artificial leather containing a fiber entangled body containing as a component a nonwoven fabric made of ultrafine fibers with an average single fiber diameter of 0.1 ⁇ m or more and 10.0 ⁇ m or less, and a polymeric elastic body
  • the lining layer is at least one selected from the group consisting of woven fabric, knitted fabric, nonwoven fabric, felt, and foamed resin sheet, In a 500 ⁇ m x 500 ⁇ m area including at least the adhesive resin and 500 or more ultrafine fibers of the skin layer in a cross section parallel to the thickness direction of the laminate, 15 or more and 240 or less of the A laminate in which the entire outer periphery of the ultrafine fibers of the skin layer is covered with the adhesive resin.
  • a laminate in which a skin layer and a lining layer made of resin A are laminated The skin layer is an artificial leather containing a fiber entangled body containing as a component a nonwoven fabric made of ultrafine fibers with an average single fiber diameter of 0.1 ⁇ m or more and 10.0 ⁇ m or less, and a polymeric elastic body,
  • the lining layer is at least one selected from the group consisting of woven fabric, knitted fabric, nonwoven fabric, felt, and foamed resin sheet, In a 500 ⁇ m x 500 ⁇ m area including at least the resin A and 500 or more microfibers in the skin layer in a cross section parallel to the thickness direction of the laminate, 15 or more and 240 or less of the A laminate in which the entire outer periphery of the ultrafine fibers of the skin layer is covered with the resin A.
  • the adhesive resin includes an intermediate layer having a thickness of 1 ⁇ m or more and 400 ⁇ m or less, The laminate according to [1] above, wherein the intermediate layer is at least one selected from the group consisting of a woven fabric, a knitted fabric, a nonwoven fabric, a felt, a film, a foamed sheet, and a metal film.
  • the present invention it is possible to obtain a laminate that has excellent adhesive strength, flexibility, and surface quality at high temperatures in a laminate in which artificial leather as a skin layer and a backing layer are laminated. can.
  • FIG. 1 is a cross-sectional view (electron micrograph) of artificial leather, illustrating and explaining the ultrafine fiber bundle according to the present invention.
  • FIG. 2 is a conceptual cross-sectional view illustrating and explaining a state in which a skin layer and a lining layer are adhered to each other in an embodiment of the laminate according to the present invention.
  • FIG. 3 is a conceptual cross-sectional view illustrating and explaining a state in which a skin layer and a lining layer are adhered to each other in another embodiment of the laminate according to the present invention.
  • FIG. 4 is a conceptual cross-sectional view illustrating and explaining a state in which the skin layer and the lining layer are adhered to each other in still another embodiment of the laminate according to the present invention.
  • FIG. 1 is a cross-sectional view (electron micrograph) of artificial leather, illustrating and explaining the ultrafine fiber bundle according to the present invention.
  • FIG. 2 is a conceptual cross-sectional view illustrating and explaining a state in which a skin
  • FIG. 5 is a conceptual perspective view illustrating and explaining a method for evaluating the surface quality of a laminate according to the present invention.
  • FIG. 6 is a cross-sectional conceptual diagram illustrating and explaining a method for evaluating vacuum formability of a laminate according to the present invention.
  • a first aspect of the laminate of the present invention is a laminate in which a skin layer and a backing layer made of resin A are laminated via an adhesive resin.
  • a second aspect of the laminate of the present invention is a laminate in which a skin layer and a backing layer made of resin A are (directly) laminated.
  • the skin layer in the laminate of the present invention is artificial leather. This skin layer is then used as the outermost layer of the laminate.
  • the artificial leather includes a fiber entangled body containing as a component a nonwoven fabric made of ultrafine fibers with an average single fiber diameter of 0.1 ⁇ m or more and 10.0 ⁇ m or less, and a polymeric elastic body.
  • the ultrafine fibers are preferably made of polyester resin from the viewpoint of durability, particularly mechanical strength, heat resistance, etc.
  • the polyester resin refers to each polyester resin exemplified below, as well as copolymers and mixtures thereof.
  • polyester resin examples include polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, and polyethylene-1,2- Examples include bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate.
  • polyethylene terephthalate which is most commonly used, or a polyester copolymer mainly containing ethylene terephthalate units is preferably used.
  • the polyester resin a single polyester or two or more different polyesters may be used, but when two or more different polyesters are used, a phase difference between the two or more components may be used.
  • the difference in intrinsic viscosity (IV value) of the polyesters used is preferably 0.50 or less, more preferably 0.30 or less.
  • the intrinsic viscosity is calculated by the following method. (1) Dissolve 0.8 g of sample polymer in 10 mL of orthochlorophenol. (2) The relative viscosity ⁇ r is calculated using the following formula using an Ostwald viscometer at a temperature of 25° C., and rounded to the second decimal place.
  • IV value 0.0242 ⁇ r +0.2634
  • ⁇ is the viscosity of the polymer solution
  • ⁇ 0 is the viscosity of orthochlorophenol
  • t is the falling time of the solution (seconds)
  • d is the density of the solution (g/cm 3 )
  • t0 is the falling time of orthochlorophenol ( seconds)
  • d 0 represent the density (g/cm 3 ) of orthochlorophenol, respectively.
  • the cross-sectional shape of the ultrafine fibers is preferably round from the viewpoint of processing operability, but polygons such as ellipse, flat and triangular shapes, sector shapes, cross shapes, hollow shapes, Y-shape, T-shape, and U-shape are also suitable. It is also possible to adopt a cross-sectional shape with an irregular cross-section such as a mold. In this case, the average single fiber diameter of the ultrafine fibers is determined by first measuring the cross-sectional area of the single fibers and calculating the diameter when the cross section is assumed to be circular.
  • the average single fiber diameter of the ultrafine fibers is 0.1 ⁇ m or more and 10.0 ⁇ m or less.
  • the average single fiber diameter of the ultrafine fibers is 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, excellent effects are achieved in color development after dyeing, light fastness and abrasion fastness, and stability during spinning.
  • the average single fiber diameter of the ultrafine fibers is 10.0 ⁇ m or less, preferably 6.0 ⁇ m or less, more preferably 4.5 ⁇ m or less, artificial leather with excellent surface quality that is dense and soft to the touch can be obtained.
  • the average single fiber diameter of ultrafine fibers refers to the scanning electron microscope (SEM) of a cross section of the artificial leather, which is the skin layer of the laminate, such as the "VE-7800" model manufactured by Keyence Corporation. Unless otherwise specified, this measuring device is exemplified as a preferred one.) Take a photograph, measure the diameter of a circular or nearly circular single fiber, and find that the diameter is 0.05 ⁇ m or more. It shall be calculated by randomly selecting 10 fibers with a diameter of .00 ⁇ m or less, calculating the arithmetic mean value of the 10 fibers, and rounding the value to the second decimal place. However, when ultrafine fibers with an irregular cross section are adopted, the diameter of the single fibers shall be determined by first measuring the cross-sectional area of the single fibers and calculating the diameter when the cross section is assumed to be circular.
  • SEM scanning electron microscope
  • the means for obtaining the ultrafine fibers used in the present invention is characterized by the use of ultrafine fiber expression type fibers.
  • the ultra-fine fiber development type fiber is a sea-island type fiber in which two thermoplastic resin components with different solubility in solvents are used as a sea component and an island component, and the island component is made into ultra-fine fiber by dissolving and removing only the sea component using a solvent, etc.
  • Adopt peelable composite fibers or multilayer composite fibers, etc. in which composite fibers or two-component thermoplastic resins are arranged alternately in a radial or layered fiber cross section, and each component is separated and split into ultra-fine fibers.
  • sea-island composite fibers are preferably used because they can easily make the surface quality of the sheet-like article uniform.
  • the fiber entangled body of the skin layer preferably comprises an ultrafine fiber bundle consisting of 3 or more and 40 or less ultrafine fibers.
  • the number of ultrafine fibers constituting the ultrafine fiber bundle is preferably 3 or more, more preferably 8 or more, the ultrafine fibers tend to have sufficient density, and mechanical properties such as abrasion tend to improve, for example.
  • the number of ultrafine fibers constituting the ultrafine fiber bundle is preferably 40 or less, more preferably 36 or less, the flexibility after adhesion to the backing layer will be good.
  • an "ultrafine fiber bundle” is an aggregate of a plurality of ultrafine fibers that can be considered to be oriented in the same direction, and when a cross section of artificial leather is observed with an SEM at an arbitrary magnification, the fiber bundle is Refers to an aggregate of ultrafine fibers surrounded by a circle with a degree of irregularity of 1.5 or less.
  • the "fiber bundle irregularity” is defined by drawing a line (1) encircling the outer periphery of an aggregate of ultrafine fibers on a SEM image, as shown in Figure 1. It refers to the value obtained by dividing the diameter of the circumscribed circle of the line (1) surrounding the periphery by the diameter of the inscribed circle of the line surrounding the outer periphery.
  • a black pigment or pigment having an average particle size of 0.05 ⁇ m or more and 0.20 ⁇ m or less is added to the polyester resin constituting the ultrafine fibers.
  • it contains a colored fine particle oxide pigment.
  • the particle size here refers to the particle size when the black pigment or chromatic fine particle oxide pigment is present in the ultrafine fibers, and is generally referred to as the secondary particle size.
  • chromatic colors refer to colors with tints such as red, blue, green, and yellow.
  • chroma C * ) Refers to colors with a number of 10 or more.
  • the average particle diameter of the black pigment or the chromatic fine particle oxide pigment is 0.05 ⁇ m or more, preferably 0.07 ⁇ m or more, the black pigment or the chromatic fine particle oxide pigment is held inside the ultrafine fibers. Falling off from ultrafine fibers is suppressed.
  • the average particle diameter is 0.20 ⁇ m or less, preferably 0.18 ⁇ m or less, and more preferably 0.16 ⁇ m or less, the yarn has excellent stability and yarn strength during spinning.
  • the content (A) of black pigment or chromatic fine particle oxide pigment contained in the polyester resin forming the ultrafine fibers shall be 0.5% by mass or more and 2.0% by mass or less based on the mass of the ultrafine fibers. is preferred.
  • the content of the black pigment or chromatic fine particle oxide pigment is 0.5% by mass or more, preferably 0.7% by mass or more, more preferably 0.9% by mass or more, so that it has excellent deep color development. becomes.
  • the proportion of black pigment or chromatic fine particle oxide pigment to 2.0% by mass or less, preferably 1.8% by mass or less, more preferably 1.6% by mass or less, strength, elongation, etc. It can be made into artificial leather with high physical properties.
  • the black pigment in the present invention carbon-based black pigments such as carbon black and graphite, and oxide-based black pigments such as triiron tetroxide and composite oxides of copper and chromium can be used. It is preferable that the black pigment is carbon black because it is easy to obtain particles with a fine particle size and has excellent dispersibility in polymers.
  • chromatic fine particle oxide pigment known pigments close to the target color can be used, such as iron oxyhydroxide (e.g. "TM Yellow 8170” manufactured by Dainichiseika Kaisha, Ltd.), iron oxide ( Examples include “TM Red 8270” manufactured by Dainichiseika Chemical Co., Ltd.), cobalt aluminate (eg "TM Blue 3490E” manufactured by Dainichiseika Chemical Co., Ltd.), and the like. Further, the above-mentioned white oxide pigments that are not "chromatic", such as zinc oxide and titanium oxide, are not included in the chromatic fine particle oxide pigments referred to in the present invention.
  • iron oxyhydroxide e.g. "TM Yellow 8170” manufactured by Dainichiseika Kaisha, Ltd.
  • iron oxide examples include “TM Red 8270” manufactured by Dainichiseika Chemical Co., Ltd.
  • cobalt aluminate eg "TM Blue 3490E” manufactured by Dainichiseika
  • thermoplastic resin forming the ultrafine fibers may include inorganic particles such as titanium oxide particles, lubricants, heat stabilizers, ultraviolet absorbers, conductive agents, heat storage agents, etc., as necessary and within the range that does not impede the purpose of the present invention. agents, antibacterial agents, etc. can be added.
  • the fiber entangled body according to the present invention includes the nonwoven fabric made of the above-mentioned ultrafine fibers as a constituent element.
  • the nonwoven fabric By including the nonwoven fabric as a component, a uniform and elegant appearance and texture can be obtained when the surface is raised.
  • the forms of nonwoven fabrics include long fiber nonwoven fabrics mainly composed of filaments and short fiber nonwoven fabrics mainly composed of fibers of 100 mm or less.
  • the nonwoven fabric is a long fiber nonwoven fabric, it is preferable because a skin layer with excellent strength can be obtained.
  • more fibers can be oriented in the thickness direction of the epidermis layer than in the case of a long fiber nonwoven fabric, giving a high density feeling to the surface of the epidermis layer when raised. can be made to have
  • the average fiber length of the ultrafine fibers is preferably 25 mm or more and 90 mm or less.
  • the average fiber length is 90 mm or less, more preferably 80 mm or less, and even more preferably 70 mm or less, good quality and texture are achieved.
  • the average fiber length is 25 mm or more, more preferably 35 mm or more, and still more preferably 40 mm or more, the skin layer can have excellent abrasion resistance.
  • the basis weight of the nonwoven fabric constituting the artificial leather that is the skin layer according to the present invention is measured according to "6.2 Mass per unit area (ISO method)" of JIS L1913:2010 "General nonwoven fabric testing method", and is 50 g/m It is preferably in the range of 2 or more and 400 g/m 2 or less.
  • the basis weight of the nonwoven fabric is 50 g/m 2 or more, more preferably 80 g/m 2 or more, it is possible to obtain artificial leather with a full feeling and excellent texture.
  • the basis weight of the nonwoven fabric is 400 g/m 2 or less, more preferably 300 g/m 2 or less, a flexible skin layer (artificial leather) with excellent moldability can be obtained, and the laminate can be made into a flexible skin layer (artificial leather) with excellent moldability. can also be made more flexible.
  • the laminate of the present invention for the purpose of improving its strength and morphological stability, it is also preferable to laminate a woven fabric between the above-mentioned nonwoven fabrics and entangle and integrate them.
  • filament yarns As for the types of fibers constituting the above-mentioned fabrics, filament yarns, spun yarns, mixed composite yarns of filament yarns and spun yarns, etc. can be used, but spun yarns have a large amount of fuzz on their surface due to their structure, making them difficult to match with non-woven fabrics.
  • spun yarns When the woven fabric is entangled, if the fuzz falls off and is exposed on the surface, it may be a drawback with ordinary artificial leather, so it is more preferable to use filaments, and it is preferable to use multifilaments as the filaments.
  • the fiber diameter of the single fibers constituting the fabric is preferably 1 ⁇ m or more and 50 ⁇ m or less.
  • the fiber diameter of the single fiber is 50 ⁇ m or less, artificial leather with excellent flexibility can be obtained, and when the fiber diameter of the single fiber is 1 ⁇ m or more, the morphological stability of the product as an artificial leather is improved.
  • the total fineness of the yarns constituting the above-mentioned fabric is determined by method B (simplified method) of "8.3 Fineness” in “8.3 Fineness” of JIS L1013:2010 “Chemical Fiber Filament Yarn Test Method” (8.3.1 Positive Fineness b) ”, and preferably 30 dtex or more and 170 dtex or less.
  • the fineness is 170 dtex or less, artificial leather with excellent flexibility can be obtained, and when the total fineness is 30 dtex or more, the shape stability of the product as an artificial leather is improved.
  • it is preferable that the warp and weft multifilaments have the same total fineness.
  • the number of twists of the threads constituting the fabric is preferably 1000 T/m or more and 4000 T/m or less.
  • the number of twists is 4000 T/m or less, more preferably 3500 T/m or less, and even more preferably 3000 T/m or less, artificial leather with excellent flexibility can be obtained, and the number of twists is 1000 T/m or more, more preferably By being 1500 T/m or more, more preferably 2000 T/m or more, it is possible to prevent damage to the fibers constituting the woven fabric when the nonwoven fabric and the woven fabric are intertwined and integrated with a needle punch, etc., and can be used in artificial leather machines. This is preferable because it provides excellent mechanical strength.
  • the skin layer according to the laminate of the present invention is an artificial leather containing the aforementioned fiber entangled body and an elastic polymer. Since this polymeric elastic body is a binder that holds the ultrafine fibers that make up the artificial leather, in consideration of the soft texture of the laminate of the present invention, the polymeric elastic body to be used should be a polyurethane resin. is preferred.
  • polyurethane-based resin examples include organic solvent-based polyurethane, which is used in a state dissolved in an organic solvent, and water-dispersed polyurethane, which is used in a state dispersed in water, both of which can be employed.
  • a polyurethane resin obtained by reacting a polymer diol, an organic diisocyanate, and a chain extender is preferably used.
  • polycarbonate diol for example, a polycarbonate diol, a polyester diol, a polyether diol, a silicone diol, and a fluorine diol can be used, and a copolymer of a combination of these can also be used.
  • polycarbonate diols from the viewpoint of hydrolysis resistance and abrasion resistance, it is preferable to use polycarbonate diols.
  • the polycarbonate diol mentioned above is a diol having a carbonate structure, and can be produced, for example, by transesterification of alkylene glycol and carbonate ester, or reaction of phosgene or chloroformate with alkylene glycol.
  • alkylene glycol examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, etc.
  • linear alkylene glycols and branched alkylene glycols such as neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, and 2-methyl-1,8-octanediol.
  • alicyclic diols such as 1,4-cyclohexanediol
  • aromatic diols such as bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.
  • polycarbonate diols obtained from a single alkylene glycol and copolymerized polycarbonate diols obtained from two or more types of alkylene glycols can be employed.
  • polyester diols refer to diols having ester bonds, and specific examples include polyester diols obtained by condensing various low molecular weight polyols and polybasic acids.
  • low molecular weight polyols examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propane. diol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, and One or more selected from cyclohexane-1,4-dimethanol can be used.
  • adducts obtained by adding various alkylene oxides to bisphenol A can also be used.
  • polybasic acids examples include succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydrocarbonic acid.
  • succinic acid maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydrocarbonic acid.
  • isophthalic acid can be mentioned.
  • polyether diol examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymer diols that are a combination thereof.
  • the number average molecular weight of the polymer diol is preferably in the range of 500 or more and 4000 or less when the molecular weight of the polyurethane resin is constant.
  • the number average molecular weight of preferably 500 or more, more preferably 1500 or more it is possible to prevent the artificial leather from becoming hard.
  • a number average molecular weight of 4000 or less, more preferably 3000 or less the strength as a polyurethane resin can be maintained.
  • organic diisocyanate used in the present invention examples include aliphatic diisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, and aromatic diisocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate. Moreover, these can also be used in combination.
  • chain extender preferably amine chain extenders such as ethylenediamine and methylenebisaniline, and diol chain extenders such as ethylene glycol can be used.
  • amine chain extenders such as ethylenediamine and methylenebisaniline
  • diol chain extenders such as ethylene glycol
  • a polyamine obtained by reacting polyisocyanate and water can also be used as a chain extender.
  • the above-mentioned polyurethane resin can be used in combination with a crosslinking agent for the purpose of improving water resistance, abrasion resistance, hydrolysis resistance, etc.
  • the crosslinking agent may be an external crosslinking agent that is added as a third component to the polyurethane resin, or an internal crosslinking agent that introduces reactive points that form a crosslinked structure into the polyurethane molecular structure in advance. It is preferable to use an internal crosslinking agent from the viewpoint that crosslinking points can be formed more uniformly within the polyurethane molecular structure and reduction in flexibility can be alleviated.
  • crosslinking agent compounds having isocyanate groups, oxazoline groups, carbodiimide groups, epoxy groups, melamine resins, silanol groups, etc. can be used.
  • additives may be added to the polymer elastomer, such as Phosphorus-based, halogen-based and inorganic flame retardants, Antioxidants such as phenol, sulfur and phosphorus, UV absorbers such as benzotriazole type, benzophenone type, salicylate type, cyanoacrylate type and oxalic acid anilide type, Light stabilizers such as hindered amines and benzoates, Hydrolysis stabilizers such as polycarbodiimide, Plasticizers, antistatic agents, surfactants, coagulation regulators, dyes, and the like can be included.
  • Phosphorus-based, halogen-based and inorganic flame retardants such as phenol, sulfur and phosphorus
  • UV absorbers such as benzotriazole type, benzophenone type, salicylate type, cyanoacrylate type and oxalic acid anilide type
  • Light stabilizers such as hindered amines and benzoates
  • Hydrolysis stabilizers such as polycarbod
  • the content of the elastic polymer in artificial leather can be adjusted as appropriate, taking into account the type of elastic polymer used, the method of manufacturing the elastic polymer, and the texture and physical properties.
  • the content of the polymeric elastic body is preferably 10% by mass or more and 60% by mass or less based on the mass of the fiber entangled body.
  • the content of the elastic polymer is 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, the bond between the fibers by the elastic polymer can be strengthened, The wear resistance of artificial leather can be improved.
  • the content of the polymeric elastomer is 60% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less, the artificial leather can be made more flexible. can.
  • At least one surface of the artificial leather has, from the viewpoint of a design effect, a nape length and directional flexibility to the extent that so-called finger marks are left when traced with a finger due to changes in the direction of the nape. It is preferable to have a raised part.
  • the length of the raised hair in the raised portion is preferably 200 ⁇ m or more and 1000 ⁇ m or less, and more preferably 250 ⁇ m or more and 800 ⁇ m or less.
  • the nap on the surface covers the polymeric elastic material and suppresses exposure of the polymeric elastic material to the surface of the artificial leather, thereby obtaining a laminate with uniform color development. be able to.
  • the length of the raised portion of the raised portion on the surface is set within the above range, so that the fibers of the woven fabric near the surface of the artificial leather are This is preferable because it can sufficiently cover the area.
  • the nap length is 800 ⁇ m or less, a laminate having excellent design effects and wear resistance can be obtained.
  • the length of the nap of the nap on the surface of the artificial leather is calculated by the following method. (1) Using a lint brush or the like, prepare a thin section with a thickness of 1 mm in the cross-sectional direction of a plane perpendicular to the longitudinal direction of the artificial leather, with the napped portions on the surface of the artificial leather standing on end. (2) Observe the cross section of the raised portion on the surface of the artificial leather at 90x magnification using SEM. (3) In the photographed SEM image, the height of the layer consisting only of ultrafine fibers is measured at 10 points at 200 ⁇ m intervals in the width direction of the cross section of the raised portion on the surface of the artificial leather. (4) Calculate the average value (arithmetic mean) of the height of the layer consisting only of ultrafine fibers at the 10 measured points.
  • the thickness of the skin layer is preferably 0.3 mm or more and 1.5 mm or less.
  • the thickness of the skin layer is preferably 0.3 mm or more, more preferably 0.4 mm or more, and even more preferably 0.5 mm or more, the adhesive resin becomes difficult to see from the surface, resulting in good quality.
  • the thickness of the skin layer shall be measured and calculated by the following method.
  • the backing layer is at least one selected from the group consisting of woven fabrics, knitted fabrics, nonwoven fabrics, felts, and foamed resin sheets.
  • Resin A is appropriately selected depending on the aspect of the above-mentioned backing layer.
  • thermoplastic resin either a thermoplastic resin or a thermosetting resin can be preferably employed.
  • thermoplastic resin it is preferable to employ thermoplastic resin.
  • the resin A is Polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, and polyethylene-1,2-bis(2-chlorophenoxy)ethane-4 , 4'-dicarboxylate, etc., as well as copolymers and mixtures thereof, polyester resins; Polyamides such as polyamide 6, polyamide 11, polyamide 12, polyamide 6,6, polyamide 6,10, polyamide 6,T, polyamide 6,I, polyamide 9,T, polyamide 5M,T, and copolymers thereof , a polyamide resin, which is a mixture; Polyolefins such as polyethylene, polypropylene, polystyrene, and polyvinyl chloride, as well as copoly
  • Examples of the knitted fabrics include warp knitting, weft knitting typified by tricot knitting, lace knitting, and various knitted fabrics based on these knitting structures.
  • Examples of resin A in this case include resins such as polyester, polyamide, and polyolefin, various copolymers containing these components, mixtures thereof, and resins that form natural fibers such as cotton and wool. The fibers constituting this knitted fabric are made of this resin A.
  • the nonwoven fabric examples include dry nonwoven fabric, wet nonwoven fabric, spunbond nonwoven fabric, burst fiber nonwoven fabric, and the like.
  • the resin A may be a resin such as the above-mentioned polyester resin, polyamide resin, or polyolefin resin, or various copolymers thereof, or a mixture thereof, or a natural fiber such as cotton or wool.
  • the fibers constituting this nonwoven fabric are made of this resin A.
  • the felt examples include resin cotton and needle-punched nonwoven fabric.
  • the resin A may be resins such as the above-mentioned polyester resins, polyamide resins, or polyolefin resins, various copolymers containing these components, or mixtures thereof, or resins such as cotton and wool.
  • examples include resins that form natural fibers, and the fibers that make up this felt are made of resin A.
  • the resin A of the woven fabric, knitted fabric, nonwoven fabric, and felt may be the aforementioned polyester resin, polyamide resin, polyolefin resin, or various copolymers containing these components, or , and mixtures thereof.
  • the above-mentioned foamed resin sheets include those formed by molding a resin with air bubbles inside into a sheet shape, and those formed by encapsulating a foaming agent in a resin sheet and foaming them.
  • the resin A includes the above-mentioned polyolefin resins, polyester-based resins, polyurethane-based resins described in the above [polymer elastomer], polyphenylene sulfide, polycarbonate, polyether ketone, polyether imide, etc. Examples include resins, various copolymers containing these components, and mixtures thereof, and the resin constituting this foamed resin sheet is resin A.
  • the backing layer is a foamed resin sheet.
  • the main component of the foamed resin sheet is a polyolefin resin.
  • the foaming ratio of the foamed resin sheet is preferably 2 times or more and 40 times or less.
  • the expansion ratio is preferably 2 times or more, more preferably 5 times or more, a flexible laminate can be obtained.
  • the expansion ratio is preferably 40 times or less, more preferably 30 times or less, a laminate with high adhesive strength and material strength can be obtained.
  • the thickness of the backing layer is preferably 0.1 mm or more and 5.0 mm or less.
  • the thickness of the skin layer is preferably 0.1 mm or more, more preferably 0.3 mm or more, and still more preferably 0.5 mm or more, the adhesive strength and material strength are excellent, and the shape retention after molding is excellent.
  • the thickness of the lining layer is preferably 5.0 mm or less, more preferably 4.5 mm or less, and even more preferably 4.0 mm or less, it is possible to obtain a flexible artificial leather with excellent moldability. .
  • the thickness of the backing layer shall be measured and calculated by the following method. (1) A thin section with a thickness of 1 mm is prepared in the cross-sectional direction of a plane perpendicular to the longitudinal direction of the laminate. (2) Observe the cross section of the backing layer of the laminate using SEM at 50x magnification. (3) In the photographed SEM image, the length is measured at 10 points from the adhesive resin to the back surface at 200 ⁇ m intervals in the width direction of the cross section of the backing layer. (4) Calculate the average value (arithmetic mean) of the lengths of the 10 measured points.
  • the adhesive resin in the first aspect is selected depending on the material and form of the backing layer, for example, Polyacrylics such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, poly 2-ethylhexyl methacrylate, poly 2-dimethylaminoethyl methacrylate, poly 2-hydroxyethyl methacrylate, and Acrylic resin, which is a copolymer or mixture of these,
  • the material can be appropriately selected from polyurethane resins, polyester resins, polyolefin resins, polyamide resins, silicones, epoxy resins, and the like. Among these, in consideration of flexibility and adhesive strength at high temperatures, polyurethane resins or acrylic resins are preferred. In particular, it is more preferable to use a polyurethane resin that provides high adhesive strength and high flexibility.
  • polyurethane resin examples include moisture-curable reactive hot melt adhesives and two-component adhesives containing isocyanates and chain extenders, but two-component adhesives are more preferred from the viewpoint of operability. .
  • the thickness of the adhesive resin is preferably 5 ⁇ m or more and 500 ⁇ m or less.
  • the thickness of the adhesive resin is preferably 5 ⁇ m or more, more preferably 75 ⁇ m or more, and still more preferably 125 ⁇ m or more, it is possible to suppress wrinkles during vacuum forming, improve sealing performance during vacuum forming, and follow the mold. can improve sex.
  • the thickness of the adhesive resin is preferably 500 ⁇ m or less, more preferably 400 ⁇ m or less, and even more preferably 300 ⁇ m or less, a more flexible laminate can be obtained.
  • the thickness of the adhesive resin shall be measured and calculated by the following method.
  • Three 3 cm square test pieces are taken from any location on the laminate at equal intervals of 4 cm in the longitudinal direction.
  • the area containing 500 or more ultrafine fibers in the cross section is an area where the number of ultrafine fibers whose cut cross section can be observed in the cross section observed in (3) above is 500 or more. represents.
  • the thickness of the adhesive resin here refers to the length of the perpendicular line 16 to the boundary between the backing layer and the adhesive resin and the interface of the adhesive resin on the skin layer side (area with a gap of 1 ⁇ m or more). means the maximum value of
  • the first aspect includes an intermediate layer in which the adhesive resin has a thickness of 1 ⁇ m or more and 400 ⁇ m or less, and the intermediate layer is made of at least one material selected from the group consisting of woven fabric, knitted fabric, nonwoven fabric, felt, film, foam sheet, and metal film. Preferably it is a seed.
  • 3 and 4 are cross-sectional conceptual diagrams of a laminate when the adhesive resin includes an intermediate layer, and FIG. 3 shows a case where a woven fabric (the fibers constituting the woven fabric are (19a)) is used as the intermediate layer (19).
  • FIG. 4 is a cross-sectional conceptual diagram when a film (19b) is used as the intermediate layer (19).
  • the laminate has a high sealing property, so that the conformability to the mold can be greatly improved, and a molded product with high dimensional accuracy can be obtained.
  • a non-porous intermediate layer can be used when particularly sealing performance is required, but an intermediate layer with holes can also be used depending on the required use and purpose.
  • further functions can be imparted to the laminate of the present invention by, for example, using one provided with an electronic circuit or a sensor.
  • the thickness of the intermediate layer is preferably 1 ⁇ m or more and 400 ⁇ m or less.
  • the lower limit of the above range is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, and still more preferably 20 ⁇ m or more, resulting in a laminate with higher sealing properties, so it has better conformability to the mold. can be greatly improved.
  • the upper limit of the above range is preferably 400 ⁇ m or less, more preferably 350 ⁇ m or less, and even more preferably 300 ⁇ m or less, the laminate becomes more flexible, which also greatly improves the conformability to the mold. can be improved.
  • the intermediate layer is preferably at least one selected from the group consisting of woven fabrics, knitted fabrics, nonwoven fabrics, felts, films, foam sheets, and metal films.
  • these materials are Polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, and polyethylene-1,2-bis(2-chlorophenoxy)ethane-4 , 4'-dicarboxylate and other polyester resins, as well as copolymers and mixtures thereof;
  • Polyamides such as polyamide 6, polyamide 11, polyamide 12, polyamide 6,6, polyamide 6,10, polyamide 6,T, polyamide 6,I, polyamide 9,T, polyamide 5M,T, and copolymers thereof, polyamide resin, which is a mixture
  • Polyolefins such as polyethylene, polypropylene, polystyrene, and polyvinyl chloride, as well as copolymers and mixtures thereof, such as polyolefin resins;
  • the material is preferably polyurethane resin, acrylic resin, polyester resin, polyamide resin, polyolefin resin, more preferably silicone, epoxy resin, etc. .
  • the materials include the polyolefin resins, polyurethane resins, and polyester resins, as well as resins such as polyphenylene sulfide, polycarbonate, polyether ketone, and polyetherimide. Alternatively, various copolymers containing these components or a mixture thereof are more preferable.
  • the material is a metal such as platinum, gold, palladium, silver, chromium, copper, iron, tungsten, titanium, tantalum, niobium, manganese, molybdenum, aluminum, or hafnium.
  • a metal such as platinum, gold, palladium, silver, chromium, copper, iron, tungsten, titanium, tantalum, niobium, manganese, molybdenum, aluminum, or hafnium.
  • the skin layer and the backing layer are laminated (directly) without using an adhesive resin.
  • a structure can be formed, for example, by a method called a flame lamination method, in which one surface of the backing layer is heated to melt the resin A and fused to the skin layer, as will be described later.
  • the adhesive resin or the resin A in the laminate of the present invention, at least the adhesive resin or the resin A (hereinafter referred to as “the adhesive resin or the resin A”) in a cross section parallel to the thickness direction. 15 to 240 ultrafine fibers in the skin layer in an area of 500 ⁇ m x 500 ⁇ m including 500 or more microfine fibers in the skin layer (sometimes abbreviated as "resin, etc.") The entire outer periphery of the fibers is covered with the above-mentioned adhesive resin or the like.
  • the number of ultrafine fibers covered with the adhesive resin etc. is 15 or more, preferably 30 or more, more preferably 45 or more, so that the adhesive strength at high temperatures is good. can do.
  • the number of the ultrafine fibers is 240 or less, preferably 220 or less, more preferably 200 or less, the laminate can have good flexibility.
  • the number of ultrafine fibers whose entire outer periphery is covered with the adhesive resin or the like described above shall be measured and calculated by the following method.
  • 500 or more ultrafine fibers in cross section means that the number of ultrafine fibers whose cut cross section can be observed in the above cross section is 500 or more.
  • the number of microfibers whose entire periphery is covered with the adhesive resin, etc. means that the entire periphery of the microfiber is surrounded by the adhesive resin, etc., and the microfiber and its adhesive resin, etc. It means the number of ultrafine fibers that do not have a gap of 1 ⁇ m or more between them.
  • the number of ultrafine fibers whose entire outer periphery is covered with the adhesive resin, etc. depends on the viscosity of the adhesive resin before hardening, the pressure and temperature when bonding the skin layer and the lining layer, etc. It can be adjusted by adjusting.
  • the ultrafine fiber bundles made of the ultrafine fibers in the fiber entanglement of the skin layer
  • the ultrafine fiber bundles of 1 to 15 bundles in the area Preferably, the entire outer periphery of the fiber bundle is covered with the adhesive resin, etc., and the inside of the ultrafine fiber bundle is also filled with the adhesive resin, etc.
  • the number of the ultrafine fiber bundles is preferably one or more, more preferably three or more, and still more preferably five or more, so that a laminate with excellent adhesive strength at high temperatures can be obtained. Furthermore, by setting the number of bundles to preferably 15 or less, more preferably 13 or less, and even more preferably 10 or less, a laminate with excellent flexibility can be obtained.
  • the ultrafine fiber bundle whose entire outer periphery is covered with the adhesive resin, etc. means that in all of the outermost ultrafine fibers in the ultrafine fiber bundle, the outer periphery of the ultrafine fibers is entirely covered with the adhesive resin, etc. , etc., and there are no voids of 1 ⁇ m or more between the ultrafine fibers and their adhesive resin, etc.
  • the number of ultrafine fiber bundles whose entire outer periphery is covered with the above adhesive resin etc. shall be measured and calculated by the following method.
  • 500 or more ultrafine fibers in cross section means that the number of ultrafine fibers whose cut cross section can be observed in the above cross section is 500 or more.
  • the ultrafine fiber bundles are densely packed, making it difficult to confirm the boundaries of the ultrafine fiber bundles and making it difficult to calculate the number
  • the filling depth of the adhesive resin or the like into the skin layer is 5 ⁇ m or more and less than 95 ⁇ m.
  • the filling depth is preferably 5 ⁇ m or more, more preferably 15 ⁇ m or more, and even more preferably 25 ⁇ m or more, a laminate with excellent adhesive strength at high temperatures can be obtained.
  • the thickness is preferably less than 95 ⁇ m, more preferably 85 ⁇ m or less, and even more preferably 75 ⁇ m or less, a laminate with excellent flexibility can be obtained.
  • This filling depth shall be measured and calculated by the following method.
  • Three 3 cm square test pieces are taken from any location on the laminate at equal intervals of 4 cm in the longitudinal direction.
  • the area containing 500 or more ultrafine fibers in the cross section is an area where the number of ultrafine fibers whose cut cross section can be observed in the cross section observed in (3) above is 500 or more. represents.
  • the filling depth here means, as illustrated in FIG. It means the maximum value of the distance 18 along the direction perpendicular to the layer side surface to the point where there is a void of 1 ⁇ m or more.
  • the laminate of the present invention can be used as a surface material for furniture, chairs, wall materials, seats, ceilings, and interior interiors of vehicles such as automobiles, trains, and airplanes, interior materials having a very elegant appearance, shirts, jackets, and casual wear.
  • the laminate of the present invention which is suitable for use in such applications, preferably has a peel strength between the skin layer and the backing layer of 10 N/25 mm or more, more preferably 20 N/25 mm or more. By doing so, it is possible to prevent delamination between the skin layer and the lining layer over time during actual use.
  • the peel strength between the skin layer and the backing layer was measured according to JIS K6854-2:1999 "Adhesives - Peeling adhesive strength test method", and the peel strength between the skin layer and the backing layer was measured when peeled at 180°. Refers to the peel strength between
  • the thermal creep resistance between the skin layer and the lining layer is preferably 15 mm/24 h or less, more preferably 10 mm/24 h or less. By doing so, it is possible to prevent delamination between the skin layer and the lining layer over time at high temperatures such as inside an automobile.
  • the heat creep resistance of the skin layer and the backing layer is the creep resistance at high temperatures measured according to JIS K6859:1994 "Creep rupture test method for adhesives", and when peeled at 180° This refers to the length of peeling between the skin layer and the lining layer per unit time.
  • the skin layer of the laminate has a bending strength after peeling in the longitudinal direction of 40 mm or more and 300 mm or less.
  • the longitudinal stiffness of the skin layer after peeling is preferably 40 mm or more, more preferably 50 mm or more, and still more preferably 55 mm or more, the skin layer of the laminate can have higher strength.
  • the longitudinal bending resistance of the skin layer after peeling is preferably 300 mm or less, more preferably 250 mm or less, and even more preferably 200 mm or less, a more flexible laminate can be obtained.
  • the bending strength after peeling in the vertical direction of the skin layer of the laminate is measured and calculated by the following method.
  • the "longitudinal direction" in the skin layer of the present invention refers to the direction in which the napping treatment is performed on the skin layer in the manufacturing process of the skin layer.
  • the vertical direction is the direction in which the napped fibers can be laid down or stood up when traced with a finger.
  • the direction in which the lying napped fibers are most oriented is determined to be the longitudinal direction.
  • the skin layer of the present invention is the above-mentioned artificial leather, and it is preferable to form this artificial leather so as to include the following steps.
  • Step (1-4) of forming ultrafine fibers Step (1-5) of applying a polymeric elastic body: Step (1-6) of cutting the sheet-like material in half and polishing it: Step (1-6) of dyeing the gray fabric.
  • This step is to produce ultrafine fiber-expressing fibers having a sea-island composite structure in which island portions are formed from a thermoplastic resin and sea portions are formed from an easily soluble polymer.
  • the ultra-fine fiber-expressing fiber is made by using thermoplastic resins with different solvent solubility as a sea part (easily soluble polymer) and an island part (slightly soluble polymer), and by dissolving and removing the sea part using a solvent or the like.
  • a sea-island type composite fiber is used in which the island portions are ultrafine fibers.
  • a method for spinning ultrafine fiber-generating fibers having a sea-island composite structure a method using a polymer mutual array in which a sea-island composite spinneret is used and spun by arranging sea parts and island parts mutually is a method that produces uniform fibers. This is preferable from the viewpoint that ultrafine fibers with a fineness of fibers can be obtained.
  • polyethylene, polypropylene, polystyrene, copolymerized polyester copolymerized with sodium sulfoisophthalic acid, polyethylene glycol, etc., and polylactic acid can be used. From this point of view, polystyrene and copolymerized polyester are preferably used.
  • a sea-island composite fiber when using a sea-island composite fiber, it is preferable to use a sea-island composite fiber whose island portion has a strength of 2.5 cN/dtex or more.
  • the strength of the island portion By setting the strength of the island portion to 2.5 cN/dtex or more, more preferably 2.8 cN/dtex or more, and still more preferably 3.0 cN/dtex or more, the wear resistance of the laminate is improved and fibers are prevented from falling off. It is possible to suppress the accompanying decrease in fastness to friction.
  • the strength of the island portion of the sea-island composite fiber is calculated by the following method.
  • (iii) JIS L1013:2010 "Chemical Fiber Filament Yarn Test Methods”"8.5 Tensile Strength and Elongation”"8.5.1 Standard Time Test” with a grip length of 5 cm and a tensile speed of 5 cm/min. , the test is carried out 10 times under the condition of a load of 2N (N 10).
  • (iv) The value obtained by rounding off the arithmetic mean value (cN/dtex) of the test results obtained in (iii) to the second decimal place is the strength of the island portion of the sea-island composite fiber.
  • the fibers are made into a fiber web using a cross wrapper or the like, and the fibers are entangled to obtain a nonwoven fabric.
  • a method of entangling fiber webs to obtain a nonwoven fabric needle punching, water jet punching, or the like can be used.
  • short fiber nonwoven fabric As mentioned above, either short fiber nonwoven fabric or long fiber nonwoven fabric can be used, but short fiber nonwoven fabric has more fibers oriented in the thickness direction of the laminate than long fiber nonwoven fabric. A highly dense feeling can be obtained on the surface of the skin layer of the laminate when raised.
  • the obtained microfiber-expressing fiber is preferably crimped and cut into a predetermined length to obtain raw cotton, which is then spread, laminated, and entangled. By doing this, a short fiber nonwoven fabric is obtained.
  • a known method can be used for crimping and cutting.
  • the obtained nonwoven fabric and woven fabric are laminated and entangled to be integrated.
  • the woven fabric is laminated on one or both sides of the nonwoven fabric, or the woven fabric is sandwiched between multiple nonwoven fabric webs, and then the nonwoven fabric is separated by a needle punching process, a water jet punching process, etc. It can entangle the fibers of textiles.
  • the apparent density of the nonwoven fabric made of microfiber-developed fibers after needle punching or water jet punching is 0.15 g/cm 3 or more and 0.45 g/cm 3 or less.
  • the apparent density is 0.15 g/cm 3 or more and 0.45 g/cm 3 or less.
  • the artificial leather can have sufficient morphological stability and dimensional stability.
  • the apparent density is set to preferably 0.45 g/cm 3 or less, sufficient space for providing the polymer elastic body can be maintained.
  • nonwoven fabric it is also a preferable embodiment to subject the nonwoven fabric to a heat shrinkage treatment using hot water or steam in order to improve the dense feel of the fibers.
  • the water-soluble resin can be applied by impregnating the nonwoven fabric with an aqueous solution of the water-soluble resin and drying it.
  • a water-soluble resin By adding a water-soluble resin to the nonwoven fabric, fibers are fixed and dimensional stability is improved.
  • the obtained fibrous base material is treated with a solvent to develop ultrafine fibers having an average single fiber diameter of 1 ⁇ m or more and 10 ⁇ m or less.
  • the ultrafine fiber development treatment can be performed by immersing a nonwoven fabric made of sea-island composite fibers in a solvent and dissolving and removing the sea portion of the sea-island composite fibers.
  • the solvent for dissolving and removing the sea portion can be an organic solvent such as toluene or trichloroethylene when the sea portion is polyethylene, polypropylene, or polystyrene.
  • an alkaline aqueous solution such as sodium hydroxide can be used.
  • the sea part is a water-soluble thermoplastic polyvinyl alcohol resin, hot water can be used.
  • a fibrous base material containing ultrafine fibers or ultrafine fiber-expressing fibers as a main component is impregnated with a solution of an elastomer polymer and solidified to provide an elastomer polymer.
  • Methods for fixing an elastic polymer to a nonwoven fabric include a method of impregnating a solution of the elastic polymer into a nonwoven fabric (fiber entangled body) and then wet coagulation or dry coagulation. These methods can be selected as appropriate.
  • N,N'-dimethylformamide, dimethyl sulfoxide, etc. are preferably used.
  • a water-dispersed polyurethane liquid in which polyurethane is dispersed in water as an emulsion may be used.
  • the polymer elastic material may be applied to the fibrous base material before generating ultrafine fibers from ultrafine fiber generation type fibers, or after generating ultrafine fibers from ultrafine fiber generation type fibers. It's okay.
  • the surface of the sheet-like article or the sheet-like article cut in half to which the above-described polymeric elastic body is applied can be subjected to a napping treatment.
  • the raising treatment can be performed by grinding using sandpaper, a roll sander, etc. to obtain a gray fabric.
  • the napping treatment can be applied to only one surface of this sheet-like material or to both surfaces.
  • a lubricant such as a silicone emulsion can be applied to the surface of the sheet-like article before the napping treatment. Further, by applying an antistatic agent before the napping treatment, grinding powder generated from the sheet material during grinding becomes difficult to accumulate on the sandpaper.
  • ⁇ Process of dyeing gray fabric> In the method for producing artificial leather of the present invention, it is more preferable to dye the gray fabric.
  • this dyeing process include jet dyeing using a jigger dyeing machine or jet dyeing machine, thermosol dyeing using a continuous dyeing machine, roller printing, screen printing, inkjet printing, and sublimation. Printing treatment on the raised surface by printing, vacuum sublimation printing, etc. can be used.
  • a jet dyeing machine from the viewpoint of quality and elegance, since a soft texture can be obtained.
  • various resin finishing treatments such as coating can be applied as necessary.
  • the skin layer in the present invention preferably has a bending resistance in the longitudinal direction of 40 mm or more and 300 mm or less.
  • a bending resistance in the longitudinal direction of 40 mm or more and 300 mm or less.
  • the longitudinal bending resistance of the epidermis layer shall be measured and calculated by the following method.
  • the skin layer was measured based on method A (45° cantilever method) described in 8.21.1 of 8.21 “Bending resistance” of JIS L1096: 2010 "Testing methods for woven and knitted fabrics", Calculate the average value of 5 sheets.
  • the method of laminating the skin layer and the backing layer is preferably such that the backing layer is coated with a liquid adhesive or pressure-sensitive adhesive that serves as an adhesive resin, and the skin layer and the backing layer are bonded together.
  • a liquid adhesive or pressure-sensitive adhesive that serves as an adhesive resin
  • the adhesive strength at high temperatures is improved.
  • a method may be adopted in which a sheet-like adhesive material serving as an adhesive resin is placed on the backing layer and pressed against the skin layer. In this case, the thickness of the adhesive resin can be made more uniform, and a laminate that does not undergo deformation in a specific direction during molding, that is, has less anisotropy, can be obtained.
  • the adhesive resin includes the above-mentioned intermediate layer
  • the intermediate layer is laminated, and the adhesive is applied again to form the skin layer.
  • a laminate can be obtained by laminating these and pressing them together.
  • Methods for applying liquid adhesives or adhesives that serve as adhesive resin include gravure coating, knife coating, screen methods such as flat screen and rotary screen, spray coating, and release paper.
  • a method may be used in which a pressure-sensitive adhesive sheet is formed by applying an adhesive or a pressure-sensitive adhesive to a material, and then the pressure-sensitive adhesive sheet is transferred to a backing layer.
  • the gravure coating method it is possible to improve the adhesive strength at high temperatures between the skin layer and the backing layer while maintaining good operability and good quality.
  • the viscosity of the liquid adhesive or pressure-sensitive adhesive when applied to the backing layer is preferably 1.5 Pa ⁇ s or more, more preferably 3.0 Pa ⁇ s or more, so that it can penetrate into the inside of the skin layer.
  • the filling depth can be controlled.
  • the pressure to preferably 20.0 Pa ⁇ s or less, more preferably 15.0 Pa ⁇ s or less, the adhesive resin can easily penetrate into the inside of the ultrafine fiber bundle, and at high temperatures between the skin layer and the lining layer. Improves adhesive strength.
  • the coating amount of the liquid adhesive or pressure-sensitive adhesive when coating the backing layer, or the basis weight of the adhesive when placing a sheet-like adhesive is preferably 15 g/m 2 or more, More preferably, by setting it as 20 g/m 2 or more, the adhesive strength at high temperature becomes good. On the other hand, the flexibility of the laminate is improved by preferably setting it to 500 g/m 2 or less, more preferably 400 g/m 2 or less.
  • a laminate can be obtained by overlapping the adhesive-coated side of the backing layer and the back side of the skin material and pressing them together.
  • crimping with a press dry heat crimping with a calendar roll, or wet heat crimping is preferable, as it allows continuous production of a laminate, loosens the structure of the microfibers, and allows the adhesive resin to penetrate into the microfiber bundles.
  • wet heat pressure bonding using a calendar roll is more preferable because it facilitates bonding.
  • the temperature of the mold surface is preferably 40°C or more and 200°C or less.
  • the temperature is preferably 40°C, more preferably 60°C or higher, the adhesive resin can easily penetrate into the inside of the microfiber bundle, and the adhesive strength at high temperatures can be improved.
  • the temperature is preferably 200°C or lower, more preferably 140°C or lower, a laminate of good quality can be obtained.
  • the pressure of the press at this time is preferably 0.1 MPa or more and 10 MPa or less.
  • the pressure is preferably 0.2 MPa or more, more preferably 0.3 MPa or more, the adhesive resin can easily penetrate into the inside of the ultrafine fiber bundle, and the adhesive strength at high temperatures can be improved.
  • the pressure is preferably 9 MPa or less, more preferably 8 MPa or less, a flexible and high-quality laminate can be obtained.
  • the temperature of the calender roll when performing dry heat compression bonding is preferably 40°C or more and 200°C or less.
  • the temperature is preferably 40°C, more preferably 60°C or higher, the adhesive resin can easily penetrate into the inside of the microfiber bundle, and the adhesive strength at high temperatures can be improved.
  • the temperature is preferably 200°C or lower, more preferably 140°C or lower, a laminate of good quality can be obtained.
  • the pressure of the calender roll at this time is preferably 10 N/cm or more and 1000 N/cm or less.
  • the pressure is preferably 20 N/cm or more, more preferably 30 N/cm or more, the adhesive resin can easily penetrate into the inside of the ultrafine fiber bundle, and the adhesive strength at high temperatures can be improved.
  • the pressure is preferably 900 N/cm or less, more preferably 800 N/cm or less, a flexible and high-quality laminate can be obtained.
  • the steam temperature is preferably 40°C or higher, more preferably 60°C or higher, so that the adhesive resin can easily penetrate into the inside of the microfiber bundle, improving adhesive strength at high temperatures.
  • the steam temperature is preferably 100°C or lower, more preferably 90°C or lower, a laminate of good quality can be obtained.
  • the pressure of the calender roll at this time is the same as that for dry heat compression bonding.
  • Step 2 of forming a laminate when manufacturing the laminate of the second invention of the present application, the method of laminating the skin layer and the lining layer is to heat one surface of the lining layer to melt the resin A, A method called flame lamination, which fuses it with the skin layer, can be used.
  • one surface of the lining layer is melted by burning it with the flame of a gas burner using city gas, propane gas, etc., and the molten lining layer and skin layer are pressed and laminated using a calendar roll.
  • the flame of the gas burner can easily melt the backing layer by setting it to 600°C or higher, and can prevent carbonization of the backing layer by setting the flame to 4000°C or lower.
  • dry heat pressure bonding using a calendar roll or wet heat pressure bonding is preferable, since the structure of the ultrafine fibers becomes loose and the adhesive resin easily penetrates into the inside of the ultrafine fiber bundle. From this point of view, wet heat compression bonding is more preferable.
  • the preferable temperature and pressure conditions when performing dry heat compression bonding and wet heat compression bonding using a calendar roll are preferably the same as those in ⁇ Step 1 of forming a laminate>.
  • Average single fiber diameter of ultrafine fibers ( ⁇ m) The average single fiber diameter of the ultrafine fibers was measured and calculated by the method described above using a scanning electron microscope ("VE-7800" manufactured by Keyence Corporation).
  • Coating amount of adhesive resin (g/m 2 )
  • the amount of adhesive resin applied was determined by measuring the mass of the backing layer before and after applying the adhesive resin when manufacturing the laminate. Specifically, the following are (3-1) to (3-3). (3-1) Take a total of three test pieces of 10 cm x 10 cm from the center of the width direction and 10 cm from the right and left ends of the backing layer before applying the adhesive resin at any position in the longitudinal direction. The basis weight (g/m 2 ) of the backing layer before coating with the adhesive resin was calculated from the number average value of the mass. (3-2) Next, after coating the lining layer with adhesive resin, apply the adhesive resin to the lining layer before adhering it to the skin layer.
  • Viscosity of adhesive resin (Pa ⁇ s)
  • the adhesive resin before coating was measured using a "B-type viscosity tester manufactured by Tokyo Keiki Co., Ltd.” according to "Plastics - Liquid, emulsion or dispersion resin - Measuring method of apparent viscosity using a Brookfield rotational viscometer” in JIS K7117:1999. The viscosity was measured while the temperature was maintained at 25°C.
  • composition of backing layer and adhesive resin was analyzed by infrared spectroscopy using a Fourier transform infrared spectrophotometer (“FT/IR 4000 series” manufactured by JASCO Corporation). The composition was identified by
  • grades 4 to 5 were considered good.
  • Grade 5 Uniform fiber napping, good fiber dispersion, and good appearance.
  • Grade 4 Rated between grade 5 and grade 3.
  • Grade 3 Although there were some parts where the nap of the fibers was not good, the fibers were dispersed and the appearance was reasonably good.
  • 2nd grade An evaluation between 3rd grade and 1st grade.
  • Grade 1 Overall, the fibers were in a very poor state of napping and dispersion, and the appearance was poor.
  • Thickness of adhesive resin ( ⁇ m) The thickness of the adhesive resin was measured and calculated by the method described above using a scanning electron microscope ("VE-7800" manufactured by Keyence Corporation).
  • FIG. 6 is a conceptual cross-sectional diagram of a mold used for evaluating vacuum formability.
  • the mold (32) has a top (32a) width (horizontal length in FIG. 6) of 25 mm, a corner (32b) of the top (32a), a radius (corner R) of 1 mm, and a bottom (32c) corner.
  • the recess (32d) has a roundness (corner R) of 6 mm and is approximately cylindrical in shape, the width of the recess (approximate diameter of the cylinder, 32e) is 50 mm, and the depth (32f) is 14 mm.
  • a laminate (31) cut into a square of 10 mm x 10 mm is placed on the mold (32) with the skin layer side facing the mold (32), and the surface temperature of the laminate is 160°C.
  • Grade 5 The gap between the laminate and the mold during vacuum forming was less than 2 mm, and no wrinkles were observed in the obtained molded product.
  • Grade 4 The gap between the laminate and the mold during vacuum forming was 2 mm or more and less than 5 mm, and no wrinkles were observed in the obtained molded product.
  • Grade 3 The gap between the laminate and the mold during vacuum forming was 5 mm or more and less than 10 mm, or the resulting molded product had slight wrinkles.
  • Grade 2 The gap between the laminate and the mold during vacuum forming was 10 mm or more, or obvious wrinkles were observed in the obtained molded product.
  • Grade 1 The laminate did not have a top hat shape.
  • Example 1 Formation of skin layer (process of manufacturing fibrous base material) Using polystyrene as the sea component and polyethylene terephthalate with an intrinsic viscosity (IV value) of 0.72 as the island component, the composite ratio is 20% by mass for the sea component and 80% by mass for the island component, and the number of islands is 16.
  • a sea-island type conjugate fiber having a /1 filament and an average single fiber diameter of 20 ⁇ m was obtained.
  • the obtained sea-island composite fibers were cut into staples with a fiber length of 51 mm, passed through a card and a cross wrapper to form a fiber web, and needle punched to produce a fiber structure.
  • a sheet made of ultrafine fibers obtained as described above was prepared using N,N-dimethylformamide (DMF), a polyurethane whose main component is organic solvent-based polyurethane and whose solid content was adjusted to a solid content of 13% by mass. ) solution, and then the polyurethane resin was coagulated in an aqueous solution with a DMF concentration of 30% by mass. Thereafter, a polyurethane resin-applied sheet was obtained by drying with hot air at a temperature of 110° C. for 10 minutes.
  • DMF N,N-dimethylformamide
  • Adhesive resin A two-component polyurethane adhesive (abbreviated as "PU-2" in Tables 1 to 4) with a viscosity adjusted to 5 Pa s was used as the adhesive resin, and a coating amount of 60 g/m 2 was obtained using a gravure roll. It was coated on top of the above-mentioned backing layer.
  • PU-2 polyurethane adhesive
  • Step of forming a laminate After the half-cut surface of the skin layer and the surface coated with the adhesive resin of the backing layer were overlapped, moist heat compression bonding was performed using a calendar roll. Specifically, it was nipped using calender rolls at 80° C. while being subjected to moist heat treatment with 80° C. steam. Thereafter, it was dried in a dryer at 90°C to obtain a laminate. The results are shown in Table 1.
  • Example 2 A laminate was obtained in the same manner as in Example 1, except that a polyurethane foam (thickness: 2.0 mm, basis weight: 40 g/m 2 , foaming ratio: 15 times) was used as the backing layer. The results are shown in Table 1.
  • Example 3 A laminate was obtained in the same manner as in Example 1 except that tricot knitted from polyester fibers was used as the backing layer. The results are shown in Table 1.
  • Example 4 A laminate was obtained in the same manner as in Example 1, except that an acrylic pressure-sensitive adhesive (abbreviated as "AC” in Table 1) having a viscosity of 5 Pa ⁇ s was used as the adhesive resin. The results are shown in Table 1.
  • AC acrylic pressure-sensitive adhesive
  • Example 5 A laminate was obtained in the same manner as in Example 1 except that the viscosity of the adhesive resin was adjusted to 16 Pa ⁇ s. The results are shown in Table 2.
  • Example 6 A laminate was obtained in the same manner as in Example 1 except that the viscosity of the adhesive resin was adjusted to 2 Pa ⁇ s. The results are shown in Table 2.
  • Example 7 A laminate was obtained in the same manner as in Example 1 except that the coating amount of the adhesive resin was 100 g/m 2 . The results are shown in Table 2.
  • Example 8 A laminate was obtained in the same manner as in Example 1 except that the coating amount of the adhesive resin was 20 g/m 2 . The results are shown in Table 2.
  • Example 9 A laminate was obtained in the same manner as in Example 1, except that in the step of forming the laminate, it was subjected to wet heat treatment with 100°C steam and nipped with calender rolls at 150°C. The results are shown in Table 3.
  • Example 10 A laminate was obtained in the same manner as in Example 1, except that in the step of forming the laminate, it was subjected to wet heat treatment with 50°C steam and nipped with calender rolls at 50°C. The results are shown in Table 3.
  • Example 11 Formation of skin layer Artificial leather was obtained in the same manner as in Example 1 to form a skin layer.
  • Adhesive resin No adhesive resin was used.
  • Step of forming a laminate A flame lamination method was performed in which the backing layer was melted with a gas burner at 1800° C., and the half-cut surface of the skin layer and the melted surface of the backing layer were superimposed. Subsequently, it was subjected to moist heat compression bonding using a calendar roll (in Table 3, it was described as "moist heat compression bonding after flerami"). Specifically, a laminate was obtained by nipping with calender rolls at 80° C. while performing a wet heat treatment with steam at 80° C. The results are shown in Table 3.
  • Example 12 Formation of skin layer Artificial leather was obtained in the same manner as in Example 1 to form a skin layer.
  • Adhesive resin An acrylic adhesive (abbreviated as “AC” in Table 1) with a viscosity adjusted to 5 Pa s was applied onto the above backing layer using a gravure roll to a coating amount of 50 g/ m2 . Coated. Thereafter, a film made of polyurethane resin having a thickness of 50 ⁇ m (abbreviated as “50 ⁇ m PU-F” in Table 1) was laminated. Then, an acrylic adhesive (abbreviated as “AC” in Table 1) whose viscosity was adjusted to 5 Pa ⁇ s was applied onto the above film using a gravure roll in a coating amount of 50 g/ m2 . I worked on it.
  • AC acrylic adhesive
  • Example 1 A laminate was obtained in the same manner as in Example 1 except that the coating amount of the adhesive resin was adjusted to 10 g/m 2 . The results are shown in Table 4.
  • Example 4 A laminate was obtained in the same manner as in Example 1 except that the coating amount of the adhesive resin was adjusted to 100 g/m 2 . The results are shown in Table 4.
  • the entire outer periphery is covered with the adhesive resin, etc. by adjusting the viscosity of the adhesive resin etc. before curing, the temperature when bonding the skin layer and the lining layer, etc.
  • the number of ultrafine fibers By setting the number of ultrafine fibers to 15 or more and 240 or less, it was possible to obtain a laminate that has both adhesive strength at high temperatures and a flexible texture.
  • the laminate of Example 1 further includes a case in which the entire outer periphery is covered with adhesive resin, etc., the number of ultrafine fiber bundles is 1 bundle or more and 15 bundles or less, and the filling depth of the adhesive resin into the skin layer is 5 ⁇ m. Since the thickness is less than 95 ⁇ m, it was possible to obtain a laminate that exhibits both adhesive strength and soft texture especially at high temperatures.
  • the temperature of the calender roll during the process of forming the laminate was high, and the adhesive resin penetrated into the inside of the skin layer, resulting in a large number of ultrafine fibers whose entire outer periphery was covered with adhesive resin, etc.
  • the laminate had a hard texture and a deteriorated appearance quality.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

Le but de la présente invention est de fournir un corps stratifié comprenant un matériau de pellicule avant et un matériau de revêtement arrière, le corps stratifié ayant d'excellentes force adhésive à haute température, flexibilité, et qualité de surface.　L'invention concerne un corps stratifié formé par la stratification d'une couche de pellicule avant et d'une couche de revêtement arrière constituée d'une résine A, avec une résine adhésive entre elles. La couche de pellicule avant est un cuir artificiel comprenant : un corps entrelacé avec des fibres comprenant, comme élément constitutif, un textile non-tissé constitué de fibres ultrafines ayant un diamètre moyen de fibre unique de 0,1 à 10,0 µm ; et un élastomère polymère. La couche de revêtement arrière est au moins d'un type sélectionné dans le groupe constitué d'un textile tissé, d'un textile tricoté, d'un textile non tissé, d'un feutre, et d'une feuille de résine expansée. Dans une région de 500 µm x 500 µm comprenant, dans une coupe transversale parallèle au sens de l'épaisseur du corps stratifié, au moins la résine adhésive et 500 coupes transversales ou plus des fibres ultrafines de la couche de pellicule avant, la circonférence externe entière de 15 à 240 fibres ultrafines de la couche de pellicule avant est recouverte de la résine adhésive.
PCT/JP2023/006976 2022-03-22 2023-02-27 Corps stratifié Ceased WO2023181789A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59116477A (ja) * 1982-12-20 1984-07-05 東レ株式会社 裏張りされた人工皮革
JPS63159049A (ja) * 1986-12-24 1988-07-01 株式会社クラレ 皮革様シ−ト状物の裏打ち法
US5277969A (en) * 1992-10-06 1994-01-11 Alcantara S.P.A. Laminate material having a microfibrous polyurethanic base sheet and process for its preparation
JP2019108619A (ja) * 2017-12-15 2019-07-04 株式会社クラレ 刺繍付人工皮革、加飾成形体及びそれらの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59116477A (ja) * 1982-12-20 1984-07-05 東レ株式会社 裏張りされた人工皮革
JPS63159049A (ja) * 1986-12-24 1988-07-01 株式会社クラレ 皮革様シ−ト状物の裏打ち法
US5277969A (en) * 1992-10-06 1994-01-11 Alcantara S.P.A. Laminate material having a microfibrous polyurethanic base sheet and process for its preparation
JP2019108619A (ja) * 2017-12-15 2019-07-04 株式会社クラレ 刺繍付人工皮革、加飾成形体及びそれらの製造方法

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