WO2022044945A1 - Cuir artificiel - Google Patents

Cuir artificiel Download PDF

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Publication number
WO2022044945A1
WO2022044945A1 PCT/JP2021/030343 JP2021030343W WO2022044945A1 WO 2022044945 A1 WO2022044945 A1 WO 2022044945A1 JP 2021030343 W JP2021030343 W JP 2021030343W WO 2022044945 A1 WO2022044945 A1 WO 2022044945A1
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Prior art keywords
artificial leather
layer
density
elastic body
polymer elastic
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PCT/JP2021/030343
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English (en)
Japanese (ja)
Inventor
上野勝
橘惣之助
田口法大
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東レ株式会社
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Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to CN202180043399.XA priority Critical patent/CN115917076A/zh
Priority to US18/020,997 priority patent/US20230287625A1/en
Priority to EP21861373.5A priority patent/EP4206398A1/fr
Priority to KR1020227037843A priority patent/KR20230056624A/ko
Priority to JP2021550176A priority patent/JPWO2022044945A1/ja
Publication of WO2022044945A1 publication Critical patent/WO2022044945A1/fr

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    • 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
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/186—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials one of the layers is on one surface of the fibrous web and the other layer is on the other surface of the fibrous web
    • 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
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
    • 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
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
    • 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
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0025—Rubber threads; Elastomeric fibres; Stretchable, bulked or crimped fibres; Retractable, crimpable fibres; Shrinking or stretching of fibres during manufacture; Obliquely threaded fabrics
    • 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
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0025—Rubber threads; Elastomeric fibres; Stretchable, bulked or crimped fibres; Retractable, crimpable fibres; Shrinking or stretching of fibres during manufacture; Obliquely threaded fabrics
    • D06N3/0027—Rubber or elastomeric fibres
    • 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
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0036—Polyester fibres
    • 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
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/0052—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by leaching out of a compound, e.g. water soluble salts, fibres or fillers; obtained by freezing or sublimation; obtained by eliminating drops of sublimable fluid
    • 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
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0075—Napping, teasing, raising or abrading of the resin coating
    • 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
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/10—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with styrene-butadiene copolymerisation products or other synthetic rubbers or elastomers except polyurethanes
    • D06N3/106—Elastomers
    • 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
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • 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
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/02—Synthetic macromolecular fibres
    • D06N2201/0254—Polyolefin fibres
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1635—Elasticity
    • 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

Definitions

  • the present invention relates to a leather-like artificial leather made of a non-woven fabric made of ultrafine fibers and a polymer elastic body, and particularly preferably, it has a supple flexibility and moderate thickness while having a full thickness like natural leather. It relates to artificial leather having a feeling of repulsion.
  • Artificial leather which is mainly composed of ultrafine fibers and polymer elastic material, has excellent characteristics compared to natural leather such as high durability and uniformity of quality. It is used in various fields such as interiors, shoes, and miscellaneous goods.
  • the suede-like artificial leather has a specific density structure or is divided to achieve a certain texture and physical properties when the material is thinned. Is possible. However, when the thickness is suitable for a wide variety of products, the texture and physical properties are not sufficient.
  • Patent Document 3 it is possible to achieve a certain sense of fulfillment and flexibility by setting the density in the thickness direction to a specific ratio, but moderate repulsion in the supple flexibility of natural leather. Not enough about the feeling.
  • Patent Document 4 it is possible to achieve the feel and fluffiness of nubuck leather to some extent, but it is not sufficient to have not only the surface feeling but also the supple texture and the repulsive feeling.
  • an object of the present invention is to provide artificial leather having a supple flexibility and an appropriate repulsive feeling while having a full thickness. be.
  • the present inventors have made a layer on one surface side regarding the density of each layer when a specific artificial leather is divided into three equal parts in the thickness direction.
  • the artificial leather of the present invention is an artificial leather containing a non-woven fabric made of ultrafine fibers having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less and a polymer elastic body as components, and has the following formula (a) and. (B) is satisfied.
  • FA , FB , and FC are the density (g / cm 3 ) and thickness of the fibers in the layer on one surface side when the artificial leather is divided into three equal parts in the thickness direction, respectively.
  • the artificial leather has at least one napped layer formed by raising.
  • the artificial leather further has at least one resin layer.
  • the resin layer is intermittently formed in the surface of the artificial leather.
  • the artificial leather further satisfies the following formulas (c) and (d).
  • P A , P B , and P C each have the density (g / cm 3 ) of the polymer elastic body in the layer on one surface side when the artificial leather is divided into three equal parts in the thickness direction. ), The density of the polymer elastic body in the central layer in the thickness direction (g / cm 3 ), and the density of the polymer elastic body in the other surface side layer (g / cm 3 ).
  • the total density of the artificial leather is 0.2 g / cm 3 or more and 0.7 g / cm 3 or less.
  • the thickness of the artificial leather is 0.8 mm or more and 4.0 mm or less.
  • the present invention it is possible to obtain artificial leather having a supple flexibility and an appropriate repulsive feeling while having a full thickness.
  • the artificial leather of the present invention has a specific density in the thickness direction, creases and dubbing that occur when the artificial leather is bent are suppressed, so that clothing, vehicle interior materials, and furniture are suppressed. It can be used in various fields such as interior materials, building materials, shoes, bags, and miscellaneous goods, but is particularly suitable for shoes, bags, and miscellaneous goods that require a natural leather-like appearance and texture.
  • FIG. 1 is a schematic cross-sectional view schematically illustrating an embodiment of a cross section of the artificial leather of the present invention.
  • FIG. 2 is a schematic plan view illustrating the morphology of the surface in one embodiment of the artificial leather of the present invention.
  • FIG. 3 is a schematic cross-sectional view schematically illustrating another embodiment of the cross section of the artificial leather of the present invention.
  • the artificial leather of the present invention is an artificial leather containing a non-woven fabric made of ultrafine fibers having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less and a polymer elastic body as components, and has the following formula (a) and. (B) is satisfied.
  • FA , FB, and FC are the densities of fibers (g / cm 3 ) in the layer on one surface side when the artificial leather is divided into three equal parts in the thickness direction, respectively.
  • the artificial leather of the present invention contains a non-woven fabric made of ultrafine fibers having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less as a component.
  • synthetic fibers are preferably used in order to obtain artificial leather having excellent mechanical strength, heat resistance and light resistance.
  • Synthetic fibers include, for example, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate and polylactic acid, polyamides such as polyamide 6 and polyamide 66, acrylics, polyethylene, polypropylene and Examples thereof include various synthetic fibers made of thermoplastic cellulose and the like. In the synthetic fibers described above, polyester fibers and polyamide fibers are particularly preferably used.
  • polyester fibers made of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and the like are particularly preferably used from the viewpoint of being excellent in strength, dimensional stability, light resistance and dyeability.
  • synthetic fibers when synthetic fibers are used as the fibers constituting the non-woven fabric, fibers containing components derived from recycled raw materials or biomass resources may be used from the viewpoint of environmental consideration. Further, ultrafine fibers of different materials may be mixed.
  • the component derived from the biomass resource when the polyester fiber is used as the synthetic fiber, the component derived from the biomass resource may be used as the dicarboxylic acid which is the raw material of the polyester and / or the ester-forming derivative thereof. Further, a component derived from a biomass resource may be used as the diol. From the viewpoint of reducing the environmental load, it is preferable to use a component derived from a biomass resource for both the dicarboxylic acid and / or its ester-forming derivative and the diol.
  • polyester When polyester is used as a synthetic fiber, examples of the dicarboxylic acid that can be used as a raw material include "terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid (for example, 2,6-naphthalenedicarboxylic acid), and diphenyldicarboxylic acid (for example, diphenyl).
  • Aromatic dicarboxylic acids such as -4,4'-dicarboxylic acid) "," oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecane
  • An aliphatic dicarboxylic acid such as "diacid", an alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, "5-sulfoisophthalate (5-sulfoisophthalic acid lithium salt, 5-sulfoisophthalate potassium salt, 5)” -Aromatic dicarboxylic acid salts such as "-sulfoisophthalic acid sodium salt, etc.)” can be mentioned.
  • ester-forming derivative of the dicarboxylic acid that is the raw material of the polyester examples include lower alkyl esters of the dicarboxylic acid, acid anhydrides, and acyl chlorides. Specifically, methyl ester, ethyl ester, hydroxy ethyl ester and the like are preferably used.
  • the diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, diethylene glycol, 2-methyl-1,3.
  • Examples thereof include propanediol, polyoxyalkylene glycol having a molecular weight of 500 or more and 20000 or less (for example, polyethylene glycol), and bisphenol A-ethylene oxide adduct.
  • polyamide 6 polyamide 66
  • polyamide 56 polyamide 610
  • polyamide 11 polyamide 12, and copolymerized polyamide
  • polyamide 56, polyamide 610, and polyamide 11 that easily contain components derived from biomass resources are preferably used.
  • the polymers forming the fibers include inorganic particles such as titanium oxide particles, lubricants, pigments, heat stabilizers, and ultraviolet absorbers, depending on various purposes. , Conductive agent, heat storage agent, antibacterial agent and the like can be added.
  • the average single fiber diameter of the ultrafine fibers is 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the average single fiber diameter is 10.0 ⁇ m or less, preferably 7.0 ⁇ m or less, more preferably 4.0 ⁇ m or less.
  • artificial leather having a fine and soft touch and excellent surface quality can be obtained.
  • the average single fiber diameter is set to 0.1 ⁇ m or more, preferably 1.0 ⁇ m or more, and more preferably 1.5 ⁇ m or more, the effect of excellent color development and fastness after dyeing can be obtained.
  • the average single fiber diameter is measured by taking a scanning electron microscope (SEM) photograph of an artificial leather cross section, randomly selecting 50 circular or near-circular elliptical ultrafine fibers, and measuring the single fiber diameter.
  • the arithmetic mean value of 50 lines is calculated, and the value is calculated by rounding off to the second digit after the decimal point when expressed in ⁇ m units.
  • the ultrafine fiber has a modified cross section
  • the single fiber diameter is obtained by first measuring the cross-sectional area of the single fiber and calculating the equivalent circle diameter.
  • the cross-sectional shape of the ultrafine fibers may be a round cross-section, but polygonal shapes such as ellipses, flats, and triangles, and irregular cross-sections such as fan-shaped and cross-shaped can be adopted.
  • non-woven fabric used in the present invention both long-fiber non-woven fabrics and short-fiber non-woven fabrics are used, but short-fiber non-woven fabrics are preferable because they have a large number of naps on the product surface and an elegant appearance can be easily obtained. ..
  • the fiber length of the ultrafine fibers when the short fiber non-woven fabric is used is preferably 25 mm or more and 90 mm or less. By setting the fiber length to 90 mm or less, good quality and texture can be obtained, and by setting the fiber length to 25 mm or more, artificial leather having excellent wear resistance can be obtained.
  • the fiber length is more preferably 35 mm or more and 80 mm or less, and further preferably 40 mm or more and 70 mm or less.
  • the basis weight of the nonwoven fabric used in the present invention is preferably 50 g / m 2 or more and 1000 g / m 2 or less.
  • the basis weight of the non-woven fabric is preferably 50 g / m 2 or more and 1000 g / m 2 or less.
  • the basis weight of the non-woven fabric is 1000 g / m 2 or less, more preferably 900 g / m 2 or less, the texture of the artificial leather is less likely to become hard and becomes soft.
  • the basis weight of the non-woven fabric is measured based on "6.2 Mass per unit area" of JIS L1913: 2010 "General non-woven fabric test method”.
  • the nonwoven fabric used in the present invention may be entangled and integrated by laminating the nonwoven fabric inside or on one side of the nonwoven fabric for the purpose of improving strength and morphological stability.
  • a filament, a spun yarn, an innovative spun yarn, a mixed composite yarn of a filament and a spun yarn, or the like can be used. Due to the structure of the spun yarn, a large number of fluffs are present on the surface, and when the non-woven fabric and the woven fabric are entangled, if the fluffs fall off and are exposed on the surface, it tends to be a defect. Therefore, it is more preferable to use a filament, and it is preferable to use a multifilament as the filament.
  • the average single fiber diameter of the fibers constituting the woven fabric is preferably 1 ⁇ m or more and 50 ⁇ m or less.
  • the average single fiber diameter of the fibers constituting the woven fabric is preferably 1 ⁇ m or more and 50 ⁇ m or less.
  • the average single fiber diameter of the fibers constituting the woven fabric used in the present invention is the same as the method for measuring the average single fiber diameter of the ultrafine fibers described above.
  • the total fineness of the threads constituting the woven fabric was measured based on "8.3.1 Positive fineness b) B method (simple method)" of JIS L1013: 2010 "Chemical fiber filament yarn test method”. Therefore, 30 dtex or more and 170 dtex or less are preferable. By setting the total fineness to 170 dtex or less, artificial leather having excellent flexibility can be obtained, and by setting the total fineness to 30 dtex or more, the morphological stability of the product as artificial leather is improved. It is preferable that the total fineness of the multifilaments of the warp and weft is the same.
  • the component of the fiber constituting the woven fabric it is preferable to use the same component as the component of the non-woven fabric, and from the viewpoint of reducing the environmental load, it is preferable to contain the component derived from the biomass resource.
  • the ultrafine fibers constituting the non-woven fabric, or the above-mentioned woven fabric the biomass plastic degree defined by ISO16620 (2015) is preferably 5% or more and 100% or less. Further, the biomass plasticity of the non-woven fabric is more preferably 15% or more, because the environmental load can be further reduced, the fiber strength of the ultrafine fibers in the artificial leather, and the wear resistance of the artificial leather are improved. % Or more is more preferable.
  • biomass plastic degree of the non-woven fabric and the woven fabric integrated is defined as the "biomass plastic degree of the non-woven fabric”.
  • the degree of biomass plastic of non-woven fabric and artificial leather is measured as follows. (1) Based on ISO16620-2, the biobase carbon content in the total carbon of the components constituting the sample is measured. (2) Identify the components and component ratios that make up the sample. For identification, known methods such as GC-MS, NMR, and elemental analysis can be used. (3) From the results of (1) and (2), the components derived from the biomass resource are specified. (4) The ratio (mass ratio) of the components derived from the biomass resource among the components of the sample is calculated as the biomass plastic degree of the sample.
  • a method of extracting and isolating the components of the non-woven fabric using a solvent in which only the non-woven fabric is soluble, or conversely, a polymer elastic body and a resin layer from artificial leather can be appropriately adopted depending on the constituent components of the artificial leather, such as a method of removing these components using a soluble solvent.
  • a method for removing components other than non-woven fabric from artificial leather for example, a method of extracting components including a polymer elastic body or a resin layer using N, N-dimethylformamide heated to 60 ° C or higher and 100 ° C or lower. Can be used.
  • the artificial leather of the present invention contains the above-mentioned non-woven fabric and a polymer elastic body as constituent elements.
  • the polymer elastic body used in the present invention mainly serves as a binder for gripping the non-woven fabric which is a component of artificial leather.
  • polyurethane styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), acrylic resin and the like can be used as the polymer elastic body.
  • SBR styrene-butadiene rubber
  • NBR acrylonitrile-butadiene rubber
  • acrylic resin and the like can be used as the polymer elastic body.
  • polyurethane it is preferable to use polyurethane as a main component.
  • polyurethane By using polyurethane, it is possible to obtain artificial leather having a full feel, a leather-like appearance, and physical characteristics that can withstand actual use.
  • the main component referred to here means that the mass of polyurethane is more than 50% by mass with respect to the mass of the entire polymer elastic body.
  • both organic solvent-based polyurethane used in a state of being dissolved in an organic solvent and water-dispersible polyurethane used in a state of being dispersed in water can be used.
  • a polyurethane obtained by reacting a polymer diol with an organic diisocyanate and a chain extender is preferably used.
  • polyurethane when polyurethane is used as the polymer elastic body as the component derived from the biomass resource, it is relatively easy to procure the raw material derived from the biomass resource among the constituent components, and the polymer diol is derived from the biomass resource. It is preferable to use the ingredients.
  • preferred embodiments of each component constituting polyurethane when polyurethane is used as the polymer elastic body in the present invention will be further described.
  • the suitable polymer diol is at least one polymer diol selected from polyester diols, polyether diols, polycarbonate diols, polymer diols such as polyester diols and polyether diols, and the like. However, it is preferable to contain a polycarbonate diol having excellent hydrolysis resistance.
  • the above-mentioned polycarbonate-based diol can be produced by a transesterification reaction between an alkylene glycol and a carbonic acid ester, a reaction between a phosgen or a chloralilate ester and an alkylene glycol, or the like.
  • alkylene glycol examples include "ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol and 1,10-decanediol".
  • Etc. "neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol and 2-methyl-1,8-octanediol", etc.
  • Examples thereof include branched alkylene glycols, alicyclic diols such as 1,4-cyclohexanediol, aromatic diols such as bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.
  • alicyclic diols such as 1,4-cyclohexanediol
  • aromatic diols such as bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.
  • a polycarbonate-based diol obtained from a single alkylene glycol or a copolymerized polycarbonate-based diol obtained from two or more types of alkylene glycols may be used.
  • polyester-based diol examples include polyester diols obtained by condensing various low molecular weight polyols with polybasic acids.
  • Examples of the low molecular weight polyol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, and 2,2-dimethyl-1,3.
  • polybasic acid examples include succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecandicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexa.
  • hydroisophthalic acid One or more selected from hydroisophthalic acid can be mentioned.
  • polyether diol examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and a copolymer diol in which they are combined.
  • the number average molecular weight of the polymer diol used in the present invention is preferably 500 or more and 4000 or more.
  • the number average molecular weight is preferably 500 or more, more preferably 1500 or more, it is possible to prevent the texture of the artificial leather from becoming hard. Further, by setting the number average molecular weight to preferably 4000 or less, more preferably 3000 or less, the strength as polyurethane can be maintained.
  • the polymer diol may be composed of only the component derived from the biomass resource or a copolymer of the polymer diol derived from the biomass resource and the polymer diol derived from the petroleum resource. good. From the viewpoint of reducing the environmental load, it is preferable that the amount of the polymer diol derived from the biomass resource is larger than that of the polymer diol derived from the petroleum resource.
  • the organic diisocyanate used is an aliphatic diisocyanate such as "hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate” or "4,4'-diphenylmethane diisocyanate”.
  • aromatic diisocyanates such as "tolylene diisocyanate”, and these can also be used in combination.
  • aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate are preferable when durability and heat resistance are important, and hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate and the like are preferable when light resistance is important.
  • the aliphatic diisocyanate of the above is preferably used.
  • the organic diisocyanate one of these may be used, or two or more thereof may be used in combination.
  • suitable chain extenders include at least one having two or more active hydrogen atoms such as water, ethylene glycol, butanediol, ethylenediamine and 4,4'-diaminodiphenylmethane. Low molecular weight compounds can be mentioned. From the viewpoint of reducing the environmental load, it is preferable to use a chain extender containing a component derived from a biomass resource.
  • a cross-linking agent can be used in combination for the purpose of improving water resistance, wear resistance, hydrolysis resistance and the like, if desired.
  • the cross-linking agent may be an external cross-linking agent added to the polyurethane as a third component, or an internal cross-linking agent in which a reaction point having a cross-linked structure is introduced in advance in the polyurethane molecular structure.
  • an internal cross-linking agent it is preferable to use an internal cross-linking agent from the viewpoint that cross-linking points can be formed more uniformly in the polyurethane molecular structure and the decrease in flexibility can be reduced.
  • cross-linking agent a compound having an isocyanate group, an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, a silanol group and the like can be used.
  • a cross-linking agent having a silanol group is preferably used in terms of the balance between reactivity and flexibility.
  • an internal emulsifier in order to disperse the polyurethane in water.
  • the internal emulsifier include a cationic internal emulsifier such as a quaternary amine salt, an anionic internal emulsifier such as a sulfonate and a carboxylate, and a nonionic internal emulsifier such as polyethylene glycol, and further, a cationic internal emulsifier. Any combination of an anionic and nonionic internal emulsifiers and a combination of anionic and nonionic internal emulsifiers can be adopted. Among them, the nonionic internal emulsifier is preferably used because it has excellent light resistance as compared with the cationic internal emulsifier and is not adversely affected by the neutralizing agent as compared with the anionic internal emulsifier.
  • additives such as pigments such as carbon black, flame retardants such as phosphorus-based, halogen-based and inorganic-based, and oxidation of phenol-based, sulfur-based and phosphorus-based substances are added to the polymer elastic body depending on the purpose.
  • Inhibitors benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based and oxalic acid-anilide-based UV absorbers, hindered amine-based and benzoate-based light stabilizers, hydrolysis-resistant stabilizers such as polycarbodiimide, etc. It can contain plasticizers, antistatic agents, surfactants, coagulation modifiers, dyes and the like.
  • the polymer elastic body used in the present invention may contain elastomer resins such as polyester, polyamide and polyolefin, acrylic resins, ethylene-vinyl acetate resins and the like as long as the performance and texture as a binder are not impaired. good.
  • elastomer resins such as polyester, polyamide and polyolefin, acrylic resins, ethylene-vinyl acetate resins and the like as long as the performance and texture as a binder are not impaired. good.
  • the content of the polymer elastic body in the artificial leather can be appropriately adjusted in consideration of the type of the polymer elastic body to be used, the manufacturing method of the polymer elastic body, and the texture and physical properties.
  • the content of the polymer elastic body is preferably 10% by mass or more with respect to the mass of the non-woven fabric (in the case where the non-woven fabric is entangled and integrated with the woven fabric, it means the total mass of the non-woven fabric and the woven fabric). It is 60% by mass or less.
  • the bond by the molecular elastic body can be enhanced, and the wear resistance of the artificial leather can be improved.
  • the content of the polymer elastic body is preferably 60% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less with respect to the mass of the nonwoven fabric, the texture of the artificial leather is made flexible. Can be.
  • the biomass plastic degree defined by ISO16620 (2015) is 5% or more and 100% or less. Further, the biomass plasticity of the polymer elastic body is more preferably 15% or more, further preferably 25% or more, because the environmental load can be further reduced or the texture of the artificial leather is improved. ..
  • the components of the polymer elastic body are simply extracted using a solvent in which only the polymer elastic body is soluble.
  • examples thereof include a method of separating the components and, conversely, a method of removing these components from the artificial leather using a solvent in which the ultrafine fibers and the resin layer are soluble. It can be appropriately adopted depending on the constituent components of the artificial leather. Other than that, it is basically measured by the same method as the biomass plastic degree of the non-woven fabric described above.
  • the polymer elastic is soluble in an organic solvent
  • the polymer elastic can be extracted and isolated with an organic solvent such as N, N-dimethylformamide.
  • an organic solvent such as N, N-dimethylformamide.
  • a method of decomposing and extracting a water-dispersed polymer elastic body with N, N-dimethylformamide heated to 60 ° C. or higher and 100 ° C. or lower can be used.
  • the polymer elastic body is isolated by the above-mentioned method by slicing or peeling off the resin layer in advance and removing it. Can be done.
  • the artificial leather of the present invention is an artificial leather containing the above-mentioned nonwoven fabric and the above-mentioned polymer elastic body as constituent elements, and satisfies the following formulas (a) and (b).
  • FA , FB, and FC are the densities of fibers (g / cm 3 ) in the layer on one surface side when the artificial leather is divided into three equal parts in the thickness direction, respectively.
  • the fiber density ratio ( FA / FB or FC / FB ) is less than 1, preferably 0.95 or less, more preferably 0.9 or less, still more preferably 0.85 or less. Particularly preferably, when it is set to 0.8 or less, it is easy to raise one surface, and it is easy to obtain a fine and soft surface quality. Further, by setting the fiber density ratio to 0.5 or more, preferably 0.6 or more, and more preferably 0.65 or more, both supple flexibility and repulsive feeling can be achieved.
  • the FA , FB , and FC can be measured as follows.
  • the fiber density referred to in the present invention is a fiber structure including the ultrafine fibers constituting the non-woven fabric and the woven fabric when the woven fabric is laminated inside or on one side of the non-woven fabric and entangled and integrated. It shows the density.
  • the artificial leather 11 is divided into one surface side layer (A), a central layer (B) in the thickness direction, and the other surface side layer (C). ..
  • the nap layer When the nap layer is formed on the surface side layer (A), it is divided into three equal parts in the thickness direction including the nap layer. As shown in FIG. 3, when the resin layer is arranged on the fluff layer on one surface side layer (A), the portion including the resin layer is the one surface side layer ( As D), the layer (E) at the center in the thickness direction and the layer (F) on the other surface side are divided in the same manner below. Then, the divided sample is immersed in N, N-dimethylformamide for 8 hours to completely extract the polymer elastic body. (3) The sample was sufficiently dried, the mass of the dried sample was measured, and the density of fibers in each layer was calculated by the following formula.
  • Fiber density (g / cm 3 ) sample mass after extraction (g) / (20 (cm) x 20 (cm) x sample thickness before extraction (cm))
  • the thickness of the sample before extraction 10 images were taken at different cross sections of the sample before extraction at a magnification of 200 times using a scanning electron microscope, and the thickness of the sample was obtained from each of these photographed images.
  • the thickness excluding the thickness of the nap layer was taken as the sample thickness.
  • the fiber density ratio ( FA / FB or FC / FB ) was calculated, and the average of the values measured at 10 points was used as the result. do.
  • the artificial leather of the present invention preferably has at least one napped layer formed by raising.
  • the napped layer By having the napped layer, a surface feel similar to that of natural leather can be obtained, and the adhesiveness with the resin layer described later is excellent. Furthermore, the fluffy fibers exposed on the surface of the artificial leather having the resin layer formed intermittently can obtain a surface feel closer to that of natural leather.
  • the artificial leather of the present invention has at least one resin layer.
  • the resin layer By having the resin layer, it is possible to obtain a silver-like or nubuck-like natural leather-like surface texture.
  • the resin layer is intermittently formed in the surface of the artificial leather.
  • the resin layer is intermittently formed in the surface of the artificial leather
  • the resin layer 2 in which the layered resin is scattered in an island shape is arranged on the napped layer 1 which is continuously present even under the resin layer 2.
  • a resin layer and an exposed fluff portion are present, and for example, the case where the resin layer 2 is surrounded by the fluff layer 1 and has an independent shape is also included.
  • the cross section of the artificial leather in this case is illustrated in FIG.
  • the resin layers 2 scattered in an island shape may be present regularly, but since the shape and arrangement are random, the surface feeling closer to that of natural leather can be obtained, so that the resin layer 2 can be present. It is preferable that the shape and arrangement of the above are random.
  • the area ratio of the resin layer to the surface of the artificial leather is preferably 10 to 90%. By setting this ratio to 10% or more, preferably 20% or more, it is possible to obtain a resin layer-containing artificial leather having excellent wear resistance, a nubuck-like or grain-like surface feeling, and a tactile feeling. On the other hand, by setting the above ratio to 90% or less, preferably 80% or less, the resin layer-containing artificial leather can be imparted with breathability and a fluffy feeling like a suede-like base material.
  • the resin layer is composed of at least two layers. More preferably, it is composed of at least three layers. More preferably, the resin layer has a three-layer structure of an adhesive layer, an intermediate layer and a surface layer.
  • the adhesive layer has a function of adhering the fiber structure and the intermediate layer.
  • the adhesive layer is a resin layer having excellent adhesion to the fibers of the napped layer in which the ultrafine fibers of the fiber structure are raised and the intermediate layer, and by being present between them, the adhesiveness between the fiber structure and the resin layer is excellent. It becomes an artificial leather with excellent wear resistance.
  • the resin layer is two or more layers, it is possible to obtain artificial leather having excellent wear resistance, which requires more durability, such as an automobile seat or a sofa.
  • the wear resistance is inferior.
  • the resin used in the resin layer preferably has rubber elasticity that expands and contracts, and for example, polyurethane, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), acrylic resin, and the like can be used. Can be mentioned. Among them, a material containing polyurethane as a main component, specifically, a material containing 50% by mass or more of polyurethane is preferably used because the texture and physical properties can be balanced.
  • SBR styrene-butadiene rubber
  • NBR acrylonitrile-butadiene rubber
  • acrylic resin and the like
  • a material containing polyurethane as a main component specifically, a material containing 50% by mass or more of polyurethane is preferably used because the texture and physical properties can be balanced.
  • polyurethane includes organic solvent-based polyurethane used in a state of being dissolved in an organic solvent and water-dispersed polyurethane used in a state of being dispersed in water, both of which can be adopted in the present invention. can.
  • polyurethane used for the resin layer polyurethane obtained by reacting a polymer diol with an organic diisocyanate and a chain extender is preferably used.
  • a component derived from a biomass resource when polyurethane is used as the resin used in the resin layer, it is relatively easy to procure the raw material derived from the biomass resource among the constituent components. It is preferable to use the derived component.
  • preferred embodiments of each component constituting the polyurethane when polyurethane is used as the resin used in the resin layer in the present invention will be further described.
  • a suitable polymer diol for example, a polycarbonate diol, a polyester diol, a polyether diol, a silicone-based diol, a fluorine-based diol, or a copolymer obtained by combining these can be used.
  • polycarbonate diols and polyester diols are preferably used from the viewpoint of light resistance. Further, from the viewpoint of hydrolysis resistance and heat resistance, polycarbonate diol is preferably used.
  • a polyether diol or a polyester diol is preferably used because of its adhesiveness to the surface of artificial leather.
  • This polycarbonate-based diol can be produced by a transesterification reaction between an alkylene glycol and a carbonic acid ester, or a reaction between a phosgen or a chloralilate ester and an alkylene glycol.
  • alkylene glycol examples include direct such as "ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol".
  • Chain alkylene glycols and branched alkylene glycols such as "neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol", Examples thereof include alicyclic diols such as 1,4-cyclohexanediol, aromatic diols such as bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.
  • either a polycarbonate diol obtained from a single alkylene glycol or a copolymerized polycarbonate diol obtained from two or more types of alkylene glycol can be used.
  • organic diisocyanate to be reacted with a suitable polymer diol examples include aliphatic polyisocyanates such as "hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate and xylylene diisocyanate". And aromatic polyisocyanates such as "4,4'-diphenylmethane diisocyanate and tolylene diisocyanate”. Further, these can be used in combination.
  • aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate are preferable when durability and heat resistance are important.
  • aliphatic polyisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate are preferable.
  • the organic diisocyanate one of these may be used, or two or more thereof may be used in combination.
  • suitable chain extenders include at least one low element having two or more active hydrogen atoms such as water, ethylene glycol, butanediol, ethylenediamine and 4,4'-diaminodiphenylmethane. Molecular compounds can be mentioned.
  • the resin used in the resin layer in the present invention may contain elastomer resins such as polyester, polyamide and polyolefin, acrylic resins and ethylene-vinyl acetate resins as long as the wear resistance and texture are not impaired. can.
  • these resins include various additives such as pigments such as carbon black, flame retardants such as phosphorus, halogen and inorganic, antioxidants such as phenol, sulfur and phosphorus, and hindered amines.
  • It can contain a light stabilizer such as a benzoate or a benzoate, a hydrolysis resistant stabilizer such as polycarbodiimide, a plasticizer, an antistatic agent, a surfactant, a coagulation adjuster, and a dye.
  • the thickness of the resin layer is not particularly limited, but the total thickness is preferably 0.001 mm or more and 0.500 mm or less.
  • the total thickness is 0.001 mm or more, more preferably 0.010 mm or more, still more preferably 0.050 mm or more, a resin layer-containing artificial leather having excellent wear resistance can be obtained.
  • the total thickness is 0.500 mm or less, more preferably 0.400 mm or less, still more preferably 0.300 mm or less, a resin layer-containing artificial leather having a flexible texture can be obtained.
  • each layer of the resin layer is preferably 0.001 mm or more and 0.200 mm or less for the first layer and the second layer, respectively, and preferably 0.008 mm or more and 0.300 mm or less for the third layer. ..
  • the total thickness of the resin layer of artificial leather shall be measured as follows. (1) Cut out a cross section of the artificial leather perpendicular to the plane direction and the machine direction, and install it on the sample table so that the cross section is not distorted. (2) Using a scanning electron microscope, 10 photographs of different sections of a sample piece of artificial leather are taken at a magnification of 200 times. (3) From each of these captured images, the highest position z1 of the resin layer and the lowest of the resin layer when the direction parallel to the cross section is horizontal, the napped layer side of the cross section is up, and the other side is down. The distance between the two points at the position z2 is acquired, and the total thickness of the resin layer is calculated. (4) The average value of the 10 values obtained by calculation is taken as the total thickness of the resin layer.
  • the artificial leather of the present invention further satisfies the following formulas (c) and (d).
  • P A , P B , and P C each have the density (g / cm 3 ) of the polymer elastic body in the layer on one surface side when the artificial leather is divided into three equal parts in the thickness direction. ), The density of the polymer elastic body in the central layer in the thickness direction (g / cm 3 ), and the density of the polymer elastic body in the other surface side layer (g / cm 3 ).
  • the polymer elastic body density in the layer on one surface side and the layer on the other surface side can be lowered, and the polymer elastic body density in the central layer in the thickness direction can be increased. preferable.
  • the surface quality is easy to raise, dense and soft to the touch. Is obtained.
  • the polymer elastic body density in the layer on the other surface side with respect to the layer in the center in the thickness direction by lowering the polymer elastic body density in the layer on the other surface side with respect to the layer in the center in the thickness direction, the artificial leather is imparted with supple flexibility. be able to.
  • the polymer elastic body density in the layer on one surface side and in the layer on the other surface side is lowered with respect to the inside of the central layer in the thickness direction, thereby making it supple.
  • the polymer elastic body density ratio ( PA / P B or PC / P B ) is less than 1, preferably 0.95 or less, more preferably 0.9 or less, still more preferably 0.85.
  • the ratio of the polymer elastic body density is 0.6 or more, preferably 0.7 or more, and more preferably 0.75 or more, both supple flexibility and repulsive feeling can be achieved.
  • the above PA, P B , and PC can be measured as follows.
  • Artificial leather is divided into three equal parts in the thickness direction using a sample of 20 cm ⁇ 20 cm.
  • it is divided into one surface side layer (A), a central layer (B) in the thickness direction, and the other surface side layer (C).
  • the resin layer is arranged on the fluff layer on one surface side layer (A)
  • the portion including the resin layer is the one surface side layer ( As D)
  • the layer (E) at the center in the thickness direction and the layer (F) on the other surface side are divided in the same manner below.
  • the resin layer existing in the layer (D) on one surface side is removed.
  • the divided sample is immersed in N, N-dimethylformamide for 8 hours to completely extract the polymer elastic body.
  • the sample was sufficiently dried, the mass of the dried sample was measured, and the density of the polymer elastic body in each layer was calculated by the following formula.
  • the thickness of the sample before extraction 10 images were taken at different cross sections of the sample before extraction at a magnification of 200 times using a scanning electron microscope, and the thickness of the sample was obtained from each of these photographed images. When a nap layer was provided, the thickness excluding the thickness of the nap layer was taken as the sample thickness.
  • the polymer elastic body density ratio PA / P B or PC / P B ) is calculated , and the average of the values measured at 10 points is the result. And.
  • the density of the entire artificial leather is preferably 0.20 g / cm 3 or more and 0.70 g / cm 3 or less.
  • the density of the entire artificial leather is more preferably 0.22 g / cm 3 or more and 0.60 g / cm 3 or less, and further preferably 0.25 g / cm 3 or more and 0.50 g / cm 3 or less.
  • the density of the entire artificial leather refers to the average of the values measured at 10 points by calculating the density of the entire artificial leather by the following formula using the mass of a sample of 20 cm ⁇ 20 cm for the artificial leather. It shall be.
  • the thickness of the artificial leather of the present invention is preferably 0.8 mm or more and 4.0 mm or less, more preferably 0.9 mm or more and 3.5 mm. It is as follows.
  • the thickness of the artificial leather is measured by measuring the thickness of 10 points in the width direction of the artificial leather using a thickness measuring device (for example, a dial thickness gauge "Peacock Model H” manufactured by Ozaki Seisakusho Co., Ltd.). It shall refer to the arithmetic mean.
  • the artificial leather of the present invention contains, for example, a dye, a pigment, a softener, a texture adjusting agent, an anti-pilling agent, an antibacterial agent, a deodorant, a water repellent agent, a light resistant agent, a weather resistant agent and the like. ..
  • the method for producing artificial leather of the present invention is a method for producing artificial leather containing a non-woven fabric made of ultrafine fibers having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less and a polymer elastic body as constituent elements. It is preferable to include the steps (i) to (v) in this order.
  • the nonwoven fabric is impregnated with an aqueous solution of a water-soluble resin at 110 ° C.
  • Step of applying the water-soluble resin by drying as described above Step of compressing the nonwoven fabric to which the water-soluble resin is applied in the thickness direction to form a sheet
  • Step of compressing the nonwoven fabric to which the water-soluble resin is applied in the thickness direction to form a sheet (iv) Treating the sheet obtained in the above (iii) with a solvent.
  • the sheet After expressing ultrafine fibers having an average fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less, the sheet is impregnated with a solvent solution of a polymer elastic material and solidified to impart the polymer elastic material.
  • the sheet obtained in (iii) is impregnated with a solvent solution of a polymer elastic body and solidified to give the polymer elastic body, and then the sheet is treated with a solvent so that the average fiber diameter of the single fiber is 0.
  • Step of expressing ultrafine fibers of 1 ⁇ m or more and 10 ⁇ m or less Step of forming fluff on at least one surface without dividing the sheet obtained in (iv) into a plurality in the thickness direction Steps (i) to ( By carrying out the steps of v) in this order, artificial leather having supple flexibility and an appropriate repulsive feeling can be obtained.
  • a non-woven fabric is produced by entwining ultrafine fiber-generating fibers made of two or more types of thermoplastic resins having different solubilitys in a solvent.
  • a non-woven fabric formed by entwining the ultrafine fibers can be obtained.
  • the ultrafine fiber generation type fiber a sea-island type fiber in which two components of thermoplastic resins having different solvent solubility are used as a sea component and an island component, and the sea component is dissolved and removed using a solvent or the like to make the island component an ultrafine fiber. It is possible to adopt a peelable composite fiber in which composite fibers or two-component thermoplastic resins are alternately arranged in a radial or multi-layered manner, and each component is peeled and divided into ultrafine fibers. .. Among them, the sea-island type composite fiber is preferably used from the viewpoint of texture and surface quality because it is possible to provide appropriate voids between the island components, that is, between the ultrafine fibers inside the fiber bundle by removing the sea component. ..
  • sea-island type composite fiber For the sea-island type composite fiber, a method using a sea-island type composite base and a polymer mutual arrangement in which two components of the sea component and the island component are mutually arranged and spun, and a method of mixing the two components of the sea component and the island component are mixed.
  • a mixed spinning method or the like can be used, but a sea-island type composite fiber by a method using a polymer array is preferably used in that ultrafine fibers having a uniform fineness can be obtained.
  • the obtained ultrafine fiber-expressing fiber is preferably crimped and cut to a predetermined length to obtain raw cotton.
  • a known method can be used for the crimping process and the cutting process.
  • the obtained raw cotton is used as a fiber web with a cloth wrapper or the like and entangled to obtain a non-woven fabric.
  • a needle punch, a water jet punch, or the like can be used as a method for obtaining a nonwoven fabric by entwining fiber webs.
  • the non-woven fabric is heat-shrinked by hot water or steam treatment in order to improve the denseness of the fibers.
  • the nonwoven fabric is impregnated with an aqueous solution of a water-soluble resin and dried at 110 ° C. or higher to impart the water-soluble resin.
  • the water-soluble resin is unevenly distributed on both surface layer portions of the nonwoven fabric by migration and applied to the nonwoven fabric.
  • both surface layers have a low fiber density and the inner layer has a high fiber density. ..
  • the later step (iv) when the polymer elastic body is applied after the expression of the ultrafine fibers, the water-soluble resin is unevenly distributed on both surface portions, so that both surface layer portions having a large amount of water-soluble resin are high.
  • the number of molecular elastic bodies is small, and the adhesive area between the ultrafine fibers and the polymer elastic body is small because it is hindered by the water-soluble resin. It is possible to impart a larger amount of the polymer elastic body to the inner layer side of the nonwoven fabric having less water-soluble resin, and the adhesive area between the ultrafine fiber and the polymer elastic body becomes large.
  • the fiber density and the density of the polymer elastic body are low and the adhesive area between the two is small on both surface layer sides of the fiber sheet thus obtained, a product surface that is easy to raise, is dense and has a soft touch is formed. It is possible to give supple flexibility to artificial leather.
  • the density of the fiber and the polymer elastic body is high, and the adhesive area between the two is large, so that an appropriate repulsive feeling can be given to the artificial leather.
  • FA , FB , and FC are the density (g / cm 3 ) and thickness of the fibers in the layer on one surface side when the artificial leather is divided into three equal parts in the thickness direction, respectively.
  • polyvinyl alcohol having a saponification degree of 80% or more is preferably used as the water-soluble resin.
  • Examples of the method of applying the water-soluble resin to the non-woven fabric include a method of impregnating the non-woven fabric with an aqueous solution of the water-soluble resin and drying the non-woven fabric.
  • concentration of the aqueous solution of the water-soluble resin is preferably 1% or more and 20% or less. It is important that the drying temperature is 110 ° C. or higher for further migration.
  • the amount of the water-soluble resin applied is preferably 5% by mass or more and 60% by mass or less with respect to the nonwoven fabric (sheet) immediately before application.
  • the above-mentioned structure can be obtained by setting the imparting amount to 5% by mass or more, more preferably 10% by mass or more. Further, by setting the applied amount to 60% by mass or less, more preferably 50% by mass or less, a processed intermediate sheet and artificial leather having good workability and physical properties such as wear resistance can be obtained.
  • the water-soluble resin applied to the non-woven fabric is removed with hot water or the like after the polymer elastic body in the step (iv) is applied.
  • the nonwoven fabric to which the water-soluble resin is applied is compressed in the thickness direction to form a sheet.
  • the inner layer side of the nonwoven fabric to which the ultrafine fibers are not fixed is preferentially compressed due to the small amount of the water-soluble resin, so that the fiber density on the inner layer side is higher than that on the surface layer side.
  • the non-woven fabric As a method of compressing the non-woven fabric, it can be performed at the same time as calendar processing or when the solvent during the ultrafine fiber expression treatment is squeezed.
  • the sheet obtained in the step (iii) is treated with a solvent to express ultrafine fibers having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less, and then the sheet is made of a polymer elastic material.
  • the polymer elastic body is imparted by impregnating and solidifying the solvent solution, or by impregnating the sheet obtained in the step (iii) with the solvent solution of the polymer elastic body and solidifying the polymer elastic body. After that, the sheet is treated with a solvent to develop ultrafine fibers having an average single fiber diameter of 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the expression treatment of ultrafine fibers can be performed by immersing a non-woven fabric made of sea-island type composite fibers in a solvent to dissolve and remove sea components.
  • the ultrafine fiber-expressing fiber is a sea-island type composite fiber
  • an organic solvent such as toluene or trichlorethylene can be used as the solvent for dissolving and removing the sea component when the sea component is polyethylene, polypropylene or polystyrene.
  • an alkaline aqueous solution such as sodium hydroxide can be used.
  • the sea component is a water-soluble thermoplastic polyvinyl alcohol-based resin, hot water can be used.
  • step (v) at least one surface of the sheet obtained in the step (iv) is raised without being divided into a plurality of sheets in the thickness direction to form fluff.
  • the brushing treatment may be performed on both sides. As described above, the surface having a low ratio of the fiber to the polymer elastic body is easily raised and a soft touch can be obtained.
  • the brushing treatment can be performed by a method such as grinding using sandpaper or a roll sander.
  • a lubricant such as a silicone emulsion can be applied prior to the brushing process.
  • the fiber density and the polymer elastic body density on the fluffy surface side and the other surface side in the thickness direction are low, it is easy to raise hair, and a fine and soft surface quality can be obtained, and supple flexibility is obtained. Can be given.
  • the center in the thickness direction to have high fiber density and polymer elastic body density, it is possible to give an appropriate repulsive feeling to the artificial leather. As a result, it is possible to achieve both supple flexibility and an appropriate repulsive feeling, and to suppress the occurrence of creases and dubbing when the seat is bent.
  • the artificial leather of the present invention can be dyed.
  • the dye can be selected according to the ultrafine fibers constituting the artificial leather.
  • a disperse dye can be used
  • the ultrafine fiber is made of polyamide fiber
  • an acid dye or a gold-containing dye can be used.
  • dyed with a disperse dye it is preferable to perform reduction cleaning after dyeing.
  • a dyeing aid for the purpose of improving the uniformity and reproducibility of dyeing.
  • the artificial leather of the present invention can also be treated with a softener such as silicone or a finishing agent such as an antistatic agent.
  • a softener such as silicone
  • a finishing agent such as an antistatic agent.
  • the finishing agent treatment can be performed after dyeing or in the same bath as the dyeing.
  • the artificial leather of the present invention can be formed with a resin layer.
  • a method for forming the resin layer in the present invention a method of forming a resin layer by drying after application by a screen method such as a flat screen or a rotary screen or a gravure coating method, or continuous on a supporting base material fiber such as a release paper.
  • the artificial leather it is preferable to apply the artificial leather so that the resin layer is intermittently formed on the surface layer of the fluffy surface of the artificial leather. Further, in order to make the resin layer into two or three layers, it can be formed by repeating the above method twice or three times. Further, regarding the above method, the same method may be repeated, or two or more types may be used in combination.
  • the surface of the above artificial leather can be designed as needed.
  • post-processing such as perforation and other drilling, embossing, laser processing, pinsonic processing, and printing can be performed.
  • ⁇ Fiber density in layer> For the obtained artificial leather, using a sample of 20 cm ⁇ 20 cm, using a slicer, one surface side layer (A), the central layer (B) in the thickness direction, and the other surface side in the thickness direction. It was divided into three equal parts with the layer (C) of. The thickness of the sample divided into three equal parts was measured at a magnification of 200 times using a scanning electron microscope, and it was confirmed that the three samples had the same thickness. Then, the divided sample was immersed in N, N-dimethylformamide for 8 hours to completely extract the polymer elastic body. Then, the N, N-dimethylformamide contained in the sample was washed away with water, and the sample was sufficiently dried under the conditions of 100 ° C. ⁇ 20 minutes in a hot air dryer. The mass of the dried sample was measured, and the density of fibers in each layer was calculated by the following formula.
  • 10 images were taken at 200 times magnification for different cross-sections of the sample before extraction, and the thickness of the sample was taken from each of these captured images. Asked. When a nap layer was provided, the thickness excluding the thickness of the nap layer was taken as the sample thickness.
  • the fiber density ratio ( FA / FB or FC / FB ) was calculated, and the average of the values measured at 10 points was used as the result.
  • ⁇ Density of polymer elastic in the layer> For the obtained artificial leather, using a sample of 20 cm ⁇ 20 cm, using a slicer, one surface side layer (A), the central layer (B) in the thickness direction, and the other surface side in the thickness direction. It was divided into three equal parts with the layer (C). In addition, the thickness of the sample divided into three equal parts was measured, and it was confirmed that the three samples had the same thickness. Then, the divided sample was immersed in N, N-dimethylformamide for 8 hours to completely extract the polymer elastic body. Then, the N, N-dimethylformamide contained in the sample was washed away with water, and the sample was sufficiently dried under the conditions of 100 ° C. ⁇ 20 minutes in a hot air dryer. The mass of the dried sample was measured, and the density of the polymer elastic body in each layer was calculated by the following formula.
  • 10 images were taken at 200 times magnification for different sections of the sample before extraction, and the sample was taken from each of these captured images. The thickness of was calculated. When a nap layer was provided, the thickness excluding the thickness of the nap layer was taken as the sample thickness.
  • the polymer elastic body density ratio ( PA / P B or PC / P B ) was calculated , and the average of the values measured at 10 points was used as the result.
  • ⁇ Evaluation method> (1) Surface quality: A total of 20 people, 10 healthy adult men and 10 adult women, were evaluated as 5 to 1 below by visual and sensory evaluation, and the most common evaluation was the appearance quality. A good level in the present invention is 4 or more. 5: The dispersed state of the fibers is good, and the touch is soft. Between 4: 3 and 5 3: There is a part where the dispersed state of the fiber is not good, but the touch is soft. Between 2: 1 and 3: 1: The dispersed state of the fibers is very poor as a whole, and the touch is rough.
  • Repulsion A total of 20 people, 10 healthy adult men and 10 adult women, were evaluated by sensory evaluation as shown in 5-1 below, and the most common evaluation was the appearance quality. A good level in the present invention is 4 or more. 5: When deformed, it returns to its original state, and when you grasp it, you feel the core. Between 4: 3 and 5 3: When deformed, it tries to return to its original state, but it does not return completely, and when you grasp it, you feel a little core. Between 2: 1 and 3: 1: Does not return from the deformed state and does not feel the core when grasped.
  • PET polyethylene terephthalate-PU: polyurethane-MDI: 4,4'-diphenylmethane diisocyanate-DMF: N, N-dimethylformamide-PVA: polyvinyl alcohol.
  • ⁇ Ultrafine fiber resin Polyethylene terephthalate A (PET-A) ⁇ Ethylene glycol: derived from petroleum resources ⁇ Terephthalic acid: derived from petroleum resources ⁇ Biomass plastic degree: 0% (2) Polyethylene terephthalate B (PET-B) ⁇ Ethylene glycol: derived from biomass resources ⁇ Terephthalic acid: derived from petroleum resources ⁇ Biomass plastic degree: 31% ⁇ Polymer elastic body> (1) Polycarbonate polyurethane A (PU-A) -Polyol: Polycarbonate diol (derived from petroleum resources) -Polyisocyanate: MDI -Chain extender: EG ⁇ Biomass plastic degree: 0% (2) Polycarbonate polyurethane B (PU-B) -Polyol: Polycarbonate diol (derived from biomass resources) -Polyisocyanate: MDI -Chain extender: EG ⁇ Biomass plastic degree: 38% [Example 1]
  • the above fluffy sheet was dyed using a liquid flow dyeing machine under a temperature condition of 120 ° C. and dried using a dryer to obtain artificial leather.
  • the obtained artificial leather had good surface quality, supple flexibility, and an appropriate repulsive feeling, and was free from wrinkles and dubs during bending.
  • the results are shown in Table 1.
  • Example 2 (raw cotton) Raw cotton of sea-island type composite fiber was obtained in the same manner as in Example 1.
  • the obtained artificial leather had good surface quality, supple flexibility, and an appropriate repulsive feeling, and was free from wrinkles and dubs during bending.
  • the results are shown in Table 1.
  • Example 3 (raw cotton) Raw cotton of sea-island type composite fiber was obtained in the same manner as in Example 1.
  • the obtained artificial leather had good surface quality, supple flexibility, and an appropriate repulsive feeling, and was free from wrinkles and dubs during bending.
  • the results are shown in Table 1.
  • Example 4 (raw cotton) Using polyethylene terephthalate B (PET-B) as the island component, polystyrene as the sea component, and a sea-island type composite base with 16 islands / hole, spinning temperature 285 ° C, island / sea mass ratio 80. Melt spinning was performed at a discharge rate of 1.2 g / min / hole and a spinning speed of 1100 m / min. Next, the fibers were stretched 2.8 times in an oil bath for spinning at 90 ° C., crimped using a push-in crimping machine, and then cut to a length of 51 mm to be ultrafine, which is an island component. Raw cotton of a sea-island type composite fiber having an average straight fiber diameter of 5.0 ⁇ m was obtained.
  • PET-B polyethylene terephthalate B
  • the obtained artificial leather had good surface quality, supple flexibility, and an appropriate repulsive feeling, and was free from wrinkles and dubs during bending.
  • the results are shown in Table 1.
  • the obtained artificial leather had good surface quality, supple flexibility, and an appropriate repulsive feeling, and was free from wrinkles and dubs during bending.
  • the results are shown in Table 1.
  • the obtained artificial leather had good surface quality, supple flexibility, and an appropriate repulsive feeling, and was free from wrinkles and dubs during bending.
  • the results are shown in Table 1.
  • Example 7 (raw cotton) Using polyethylene terephthalate A (PET-A) as the island component, polystyrene as the sea component, and a sea-island type composite base with 200 islands / hole, spinning temperature 280 ° C., island / sea mass ratio 60. Melt spinning was performed at / 40, a discharge rate of 1.1 g / min, a hole, and a spinning speed of 1300 m / min. Next, the fibers were stretched 2.8 times in an oil bath for spinning at 90 ° C., crimped using a push-in crimping machine, and then cut to a length of 51 mm to be ultrafine, which is an island component. Raw cotton of a sea-island type composite fiber having an average straight fiber diameter of 0.7 ⁇ m was obtained.
  • PET-A polyethylene terephthalate A
  • the obtained artificial leather had good surface quality, supple flexibility, and an appropriate repulsive feeling, and was free from wrinkles and dubs during bending.
  • the results are shown in Table 1.
  • the obtained artificial leather had poor surface quality, inferior flexibility, and less repulsive feeling, and wrinkles and duplication during bending were conspicuous.
  • the results are shown in Table 2.
  • the obtained artificial leather had poor surface quality, inferior flexibility, and a feeling of repulsion, but wrinkles and duplication during bending were conspicuous.
  • the results are shown in Table 2.
  • the obtained artificial leather had poor surface quality, inferior flexibility, and less repulsive feeling, and wrinkles and duplication during bending were conspicuous.
  • the results are shown in Table 2.
  • Example 8 (Raw cotton-dyeing) Artificial leather was obtained in the same manner as in Example 1.
  • the obtained artificial leather had good surface quality, supple flexibility, and an appropriate repulsive feeling, and was free from wrinkles and dubs during bending.
  • the results are shown in Table 3.
  • Example 9 (Raw cotton-dyeing) Artificial leather was obtained in the same manner as in Example 4.
  • the obtained artificial leather had good surface quality, supple flexibility, and an appropriate repulsive feeling, and was free from wrinkles and dubs during bending.
  • the results are shown in Table 3.
  • the obtained artificial leather had poor surface quality, inferior flexibility, and less repulsive feeling, and wrinkles and duplication during bending were conspicuous.
  • the results are shown in Table 3.
  • Fleece layer 2 Resin layer 11: Artificial leather A, D: One surface side layer B, E: Thickness direction center layer C, F: The other surface side layer

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

La présente invention aborde le problème de la réalisation d'un cuir artificiel qui est pliable et flexible et qui présente une élasticité appropriée tout en ayant une épaisseur satisfaisante. Le principal objet de la présente invention est de fournir un cuir artificiel qui comprend, en tant que composants constitutifs, un non tissé comprenant des fibres ultrafines ayant un diamètre moyen de fibre unique de 0,1 à 10 µm, et un corps élastique polymère, ledit cuir artificiel satisfaisant les formules (a) et (b) ci-dessous.　(a) 0,5≤FA/FB<1 (b) 0,5≤FC/FB<1. Ici, FA, FB, et FC sont respectivement la densité de fibres intra-couche (g/cm3) sur un côté de la surface, la densité de fibres intra-couche (g/cm3) au centre dans le sens de l'épaisseur, et la densité des fibres intra-couche (g/cm3) sur l'autre côté de la surface lorsque le cuir artificiel a été divisé en trois dans le sens de l'épaisseur.
PCT/JP2021/030343 2020-08-28 2021-08-19 Cuir artificiel WO2022044945A1 (fr)

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CN202180043399.XA CN115917076A (zh) 2020-08-28 2021-08-19 人工皮革
US18/020,997 US20230287625A1 (en) 2020-08-28 2021-08-19 Artificial leather
EP21861373.5A EP4206398A1 (fr) 2020-08-28 2021-08-19 Cuir artificiel
KR1020227037843A KR20230056624A (ko) 2020-08-28 2021-08-19 인공피혁
JP2021550176A JPWO2022044945A1 (fr) 2020-08-28 2021-08-19

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CN (1) CN115917076A (fr)
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4746887B1 (fr) * 1969-05-14 1972-11-27
JP2004091960A (ja) 2002-08-30 2004-03-25 Kuraray Co Ltd スエード調人工皮革の製造方法
WO2011121940A1 (fr) 2010-03-31 2011-10-06 株式会社クラレ Feuille de similicuir
WO2015037528A1 (fr) 2013-09-13 2015-03-19 東レ株式会社 Objet en forme de feuille et son procédé de production
WO2017022387A1 (fr) 2015-07-31 2017-02-09 東レ株式会社 Tissu de type cuir

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4746887B1 (fr) * 1969-05-14 1972-11-27
JP2004091960A (ja) 2002-08-30 2004-03-25 Kuraray Co Ltd スエード調人工皮革の製造方法
WO2011121940A1 (fr) 2010-03-31 2011-10-06 株式会社クラレ Feuille de similicuir
WO2015037528A1 (fr) 2013-09-13 2015-03-19 東レ株式会社 Objet en forme de feuille et son procédé de production
WO2017022387A1 (fr) 2015-07-31 2017-02-09 東レ株式会社 Tissu de type cuir

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TW202208721A (zh) 2022-03-01
KR20230056624A (ko) 2023-04-27
US20230287625A1 (en) 2023-09-14
CN115917076A (zh) 2023-04-04
JPWO2022044945A1 (fr) 2022-03-03

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