WO2005106108A1 - Cuir artificiel de ton argente - Google Patents

Cuir artificiel de ton argente Download PDF

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Publication number
WO2005106108A1
WO2005106108A1 PCT/JP2005/007863 JP2005007863W WO2005106108A1 WO 2005106108 A1 WO2005106108 A1 WO 2005106108A1 JP 2005007863 W JP2005007863 W JP 2005007863W WO 2005106108 A1 WO2005106108 A1 WO 2005106108A1
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WO
WIPO (PCT)
Prior art keywords
layer
coating layer
polymer
elastic body
artificial leather
Prior art date
Application number
PCT/JP2005/007863
Other languages
English (en)
Japanese (ja)
Inventor
Masaru Makimura
Hisao Yoneda
Original Assignee
Kuraray Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Co., Ltd. filed Critical Kuraray Co., Ltd.
Priority to CN2005800166129A priority Critical patent/CN1957136B/zh
Priority to US11/587,593 priority patent/US7442429B2/en
Priority to EP05736597A priority patent/EP1749920A4/fr
Priority to KR1020067022483A priority patent/KR101166273B1/ko
Priority to JP2006512781A priority patent/JP4560511B2/ja
Publication of WO2005106108A1 publication Critical patent/WO2005106108A1/fr

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Classifications

    • 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
    • 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
    • D06N3/141—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 mixture of two or more polyurethanes in the same layer
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic System
    • D06M11/42—Oxides or hydroxides of copper, silver or gold
    • 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
    • D06N3/12—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
    • D06N3/145—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 two or more layers of polyurethanes

Definitions

  • the present invention also relates to a silver-tone artificial leather having a natural leather-like elegant appearance, excellent softness, flexibility, and high peel strength.
  • the artificial leather with a silver tone can be widely used for applications such as shoes, balls, and so on.
  • a leather-like sheet produced by coating a polyurethane solution on the surface of the substrate and wet-solidifying to form a foamed layer, and then coloring and embossing the foamed layer.
  • a leather-like sheet has the appearance of a natural leather.
  • a relatively small amount of a soft elastic body is filled in the substrate, so that sufficient peel strength cannot be obtained.
  • a relatively hard elastic body needs to be filled in a large amount, and as a result, softness and flexibility are lost.
  • An entangled nonwoven fabric made of ultrafine fiber-generating fibers is impregnated with polyurethane resin and wet-coagulated, and one component is removed from the ultrafine fiber-generating fibers to produce an ultrafine fiber bundle of 0.1 dtex or less.
  • a leather-like sheet obtained by obtaining a substrate consisting of and then subjecting the substrate to a surface finishing process (for example, see Patent Document 1). Has a natural leather appearance, but has insufficient flexibility and peel strength.
  • a leather-like sheet made of the same elastic resin as that impregnated in the surface layer of the base and having a surface porous layer provided continuously with the surface layer of the base see, for example, Patent Document 2.
  • the surface porous layer is formed directly on the substrate using a relatively hard elastic body, or the surface porous layer is formed on the substrate surface via a high-density resin layer. It is also known to form a porous film layer on the surface porous layer.
  • a leather-like sheet when a natural leather-like appearance is obtained by embossing, sufficient peel strength is obtained, but softness is reduced. Conversely, if priority is given to softness, it becomes difficult to obtain the appearance of natural leather by embossing.
  • silver-finished artificial leather that combines excellent peel strength, soft surface, flexibility, and a clear and elegant appearance comparable to that of natural leather is still available.
  • Patent Document 1 Japanese Patent Publication No. 63-5518
  • Patent Document 2 JP-A-11-140779
  • Patent Document 3 JP 2003-105679 A
  • An object of the present invention is to provide artificial leather with silver that combines an elegant appearance of natural leather with excellent softness, flexibility, and high peeling strength. More specifically, it has a soft surface and high peeling strength. And silver-like artificial leather excellent in flexibility and a method for producing the same.
  • the present invention provides a entangled nonwoven fabric X comprising a bundle of ultrafine fibers having an average single fiber fineness of 0.07 dtex or less, and a base comprising a polymer elastic body A and a polymer elastic body B impregnated therein. And a covering layer Y formed on one surface of the base layer.
  • the entangled nonwoven fabric X comprises a lower layer X and an upper layer X.
  • the coating layer Y is formed on the upper layer X with a thickness of 1 to
  • the present invention provides an artificial leather with silver, characterized in that:
  • the artificial leather with silver of the present invention is provided on a base layer comprising an entangled nonwoven fabric X and a polymer elastic body A and a polymer elastic body B impregnated therein, and on one surface of the base layer.
  • a base layer comprising an entangled nonwoven fabric X and a polymer elastic body A and a polymer elastic body B impregnated therein, and on one surface of the base layer.
  • the base layer is mainly composed of the lower layer X containing the elastic polymer A and the main layer.
  • the upper layer X including the elastic polymer B is formed.
  • the substrate layer used in the present invention comprises a bundle of ultrafine fibers having an average single fiber fineness of 0.07 dtex or less, preferably 0.0001 to 0.07 dtex, more preferably 0.0001 to 0.05 dtex.
  • This is a smooth surface layer composed of the three-dimensional entangled nonwoven fabric X and the polymer elastic bodies A and B contained therein. If the average single fiber fineness exceeds 0.07 deciters, the texture and the smoothness of the substrate layer will be poor, and it will be difficult to form a uniform grain pattern by embossing.
  • the bundle of ultrafine fibers having an average single fiber fineness of 0.07 dtex or less is produced by a conventionally known method.
  • At least two It can be obtained by dissolving or decomposing and removing at least one component from a polymer ultrafine fiber-generating fiber, or by peeling off at the interface between two components by mechanical or chemical treatment.
  • the ultrafine fiber bundle and the elastic polymer constituting the artificial leather with silver of the present invention need not be substantially bonded to each other in terms of the soft feeling of natural leather. It is necessary to form an ultrafine fiber bundle from the ultrafine fiber-generating fibers in order to make the state substantially not adhered, and it is preferable to form them from sea-island type ultrafine fiber-generating fibers.
  • Examples of the polymer constituting the ultrafine fibers in the ultrafine fiber-generating fibers include melt-spinnable polyamides such as 6 nylon and 66 nylon, polyethylene terephthalate, polyethylene terephthalate, and cationic dyeable modified polyethylene terephthalate. Examples include at least one polymer selected from the group consisting of spinnable polyesters.
  • the polymer to be dissolved or decomposed and removed is different from the polymer constituting the ultrafine fiber in solubility in a solvent or decomposability by a decomposer, and has low compatibility with the polymer constituting the ultrafine fiber and spinning conditions.
  • at least one kind of polymer such as polyethylene, polystyrene, polyethylene propylene copolymer, and modified polyester, which is also selected for its polymer power is used.
  • the ultrafine fiber generating fibers are defibrated with a card and formed on a web through a webber.
  • the obtained web is laminated so as to have a desired weight and thickness, and then entangled by a known method such as needle punching or high-speed water flow to obtain an entangled nonwoven fabric X.
  • a woven or knitted fabric having a bundle strength of ultrafine fibers having an average single fiber fineness of 0.07 dtex or less can be laminated on the web.
  • the surface of the entangled nonwoven fabric X can be uniformly smoothed by a press treatment or the like before impregnation with the elastic polymer to improve the surface smoothness of the resulting silver-finished artificial leather and form a grain pattern uniformly. It is preferred in that respect.
  • the thickness of the obtained entangled nonwoven fabric X or the pressed entangled nonwoven fabric X is selected according to the use of the artificial leather with silver, and is not particularly limited.
  • entangled nonwoven fabric X in a single layer Has a thickness of 0.2 ⁇ : preferably about LOmm, preferably about 0.4 ⁇ 5mm.
  • Density ⁇ or 0. 15 ⁇ 0. 60g / cm 3 power preferably, 0. 20 ⁇ 0. 40g / cm 3 force ⁇ good more preferable.
  • the density is within the above range, an appropriate amount of the polymer elastic body can be impregnated, a rubber-like texture can be avoided, a decrease in peel strength can be prevented, and a soft texture can be obtained.
  • the entangled nonwoven fabric X is impregnated with a solution or a dispersion of the polymer elastic bodies A and B, and then a coating layer Y is formed.
  • the polymer elastic bodies A, B and C used in the present invention known polymer elastic bodies can be used as long as they are conventionally used in the production of artificial leather.
  • polyurethane is preferably used from the viewpoint of obtaining natural leather-like feeling and physical properties.
  • Preferred examples of the polymer elastic bodies A to C that impregnate the entangled nonwoven fabric X and form the multilayer Y are one type of a polymer diol such as a polyester diol, a polyether diol, and a polyester ether diol. At least one of organic polyisocyanates, preferably aliphatic, aromatic or alicyclic organic diisocyanates; and having two active hydrogen atoms such as low molecular weight diols, low molecular weight diamines, and hydrazines And polyurethanes made from chain extenders.
  • a polymer diol such as a polyester diol, a polyether diol, and a polyester ether diol.
  • organic polyisocyanates preferably aliphatic, aromatic or alicyclic organic diisocyanates
  • having two active hydrogen atoms such as low molecular weight diols, low molecular weight diamines, and hydrazines And polyurethane
  • a polyurethane having a mass percentage of nitrogen atoms of isocyanate in an organic polyisocyanate unit present in the polyurethane (hereinafter referred to as N%) of 2.5 to 5% with respect to the total mass of the polyurethane, or the polyurethane or the polyurethane.
  • N% a mass percentage of nitrogen atoms of isocyanate in an organic polyisocyanate unit present in the polyurethane
  • a mixture mainly composed of When the N% is within the above range, the properties of the coating layer Y and the base layer such as abrasion resistance and pulling resistance are good, the bending shear becomes coarse and the texture becomes hard, and artificial leather is produced. It is preferable because it can be prevented from becoming cheap and the physical properties of the artificial leather such as flex fatigue resistance are good.
  • the elastic polymer C used for the coating layer Y of the present invention has a natural leather tone by embossing.
  • polyurethane capable of forming a grain pattern.
  • examples include hard segments mainly composed of polymer glycols having hydroxyl groups at both terminals and having a molecular weight of 500 to 5000, 4,4'-diphenylmethane diisocyanate, and lower alkylene glycols having 2 to 6 carbon atoms.
  • Polyurethanes or have hydroxyl groups at both ends And polymer polyurethanes having a molecular weight of 500 to 5,000, aliphatic or alicyclic diisocyanates, and polyurethanes having a hard segment mainly composed of organic diamine or organic acid dihydrazide.
  • a copolymer or a mixture of these may be used as long as the softness, flexibility, durability, workability, porous film forming property, and the like are sufficient.
  • polyester glycols such as polyethylene adipate glycol, polybutylene adipate glycol, polyhexamethylene adipate glycol, and polycaprolactone glycol
  • Polycarbonate glycols such as hexamethylene carbonate glycol
  • polyetherene glycols such as polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol and polyhexamethylene ether glycol
  • Particularly preferred are polyester glycols, polycarbonate glycols, mixed glycols of polyester glycols and polycarbonate glycols, and mixed dalicols of polyester glycols, polycarbonate glycols and polyether glycols.
  • Aliphatic diisocyanates include tetramethylene diisocyanate and hexamethylene diisocyanate, and alicyclic diisocyanates include cyclohexanediisocyanate and 4,4'-dicyclohexylmethane diisocyanate.
  • organic diamines include p-phenylenediamine, metaphenylenediamine, 4,4'-diaminediphenylmethane, ethylenediamine, propylenediamine, diethanolamine, 4,4'-diaminodicyclohexynolemethane, and isophoronediamine.
  • Examples of the organic acid dihydrazide include adipic acid dihydrazide, sebacic acid dihydrazide, terephthalic acid dihydrazide, and isophthalic acid dihydrazide.
  • Examples of lower alkylene glycols having 2 to 6 carbon atoms include ethylene glycol, butanediol, hexanediol, diethylene glycol and dipropylene glycol.
  • ethylene glycol can form a uniform grain pattern by embossing. Is preferred.
  • Thickness of the coating layer Y 0.02 ⁇ : L 50 mm force S preferred, 0.05 ⁇ : L OOmm force S preferred c
  • the polymer elastic body that forms the coating layer Y must be the same, that is, the polymer elastic body B.
  • the coating layer Y have reduced adhesiveness and are easily peeled off.
  • the 100% modulus of the elastic polymer B is preferably 20 to: L00 kgZcm 2 , more preferably 30 to 70 kgZcm 2 . Further, the polymer elastic body B is a polymer constituting the coating layer Y.
  • 100% modulus of the elastic polymer B is, 30 ⁇ 60kgZcm 2 high than that of the high-molecular elastic member C!, And more preferably! /,.
  • the polymer elastic body B forms a porous structure different from the polymer elastic body C, for example, the polymer elastic body B forms a denser porous structure than the polymer elastic body C.
  • the coating layer Y When observing the cross section in the thickness direction of C, the coating layer Y
  • the maximum diameter of the micropores in B and the upper layer B is preferably 1Z2 or less of the maximum diameter of the macropores (water droplet type or bottle type type holes) in the coating layer Y.
  • the coating layer Y is formed during embossing.
  • the pore diameter ratio can be controlled within the above range by a known method, for example, by appropriately adjusting the viscosity, concentration and type of the elastic polymer.
  • the polymer elastic body B is not particularly limited as long as it satisfies the above physical properties, but polyurethane is particularly preferably used in view of the feeling and physical properties of the resulting artificial leather with silver.
  • the type of the polyurethane is not particularly limited, and an ester type, an ether type, a carbonate type, a copolymer type thereof, or a mixture thereof can be used. It is more preferable to use an ether-based soft segment and an aromatic diisocyanate and an aromatic diamine as the hard segment, because they are less likely to be thermally deformed.
  • a polyurethane different from the above may be mixed with the polyurethane, or a copolymerized polyurethane having a strong force such as an aethenole-based polymer diol, a polycarbonate-based polymer diol, or a polyesternole-based polymer diol may be used.
  • the lower layer X of the entangled nonwoven fabric X is impregnated with a polymer elastic body A.
  • the elastic polymer A As the elastic polymer A,
  • polyurethane is preferably used in that it has a soft feeling and physical properties similar to those of artificial leather with silver tone.
  • the polymer elastic body B constituting the upper layer of the base is affected by heat through the coating layer Y at the time of embossing, and therefore is not easily thermally deformed.
  • the lower layer (the lower layer X is impregnated with the polymer elastic body A)
  • Layer is more embossed than the upper layer of the base (the layer in which the upper layer X is impregnated with the elastic polymer B).
  • the 100% modulus of the elastic polymer A is preferably 10 kg / cm 2 or less lower than that of the elastic polymer B, more preferably 10 to 60 kgZcm 2 .
  • the elastic polymer A is impregnated with an amount that emphasizes softness and does not impair the overall texture balance.
  • an amount that emphasizes softness and does not impair the overall texture balance for example, as a solid content with respect to the fiber mass Xa of the lower layer X, preferably 0.1
  • the impregnation amount is within the above range, a rubber-like texture can be avoided, a good overall texture balance can be obtained, and a high-quality natural leather-like texture with a sense of fulfillment can be obtained.
  • the polymer elastic body B impregnating the upper layer X and the polymer elastic body A impregnating the lower layer X can be formed.
  • embossing can impart a natural leather-like elegant appearance uniformly.
  • the layer of the polymer elastic body B impregnated in the upper layer X has a force preferably depending on the thickness of the base layer.
  • the artificial leather with silver of the present invention has the following formula 1:
  • Mass of synthetic nonwoven fabric a is mass of polymer elastic body A impregnated in lower layer X, Xa is lower layer X
  • Equation 1 Mass of the entangled nonwoven fabric constituting, the required peel strength can be obtained, it can withstand deformation during embossing sufficiently, and it can maintain sufficient softness even when embossed. preferable.
  • the upper limit of Equation 1 is more preferable in terms of the balance of the texture of the artificial leather with silver tone obtained to be 5.0.
  • Impregnation of the base material layer with the elastic polymer is not particularly limited as long as it is performed by a known treatment method.
  • a predetermined amount of a solution or a dispersion of the polymer elastic body B is applied to the upper surface of the entangled nonwoven fabric X and allowed to naturally penetrate or penetrate by rubbing with a roll or a knife.
  • a solution or a dispersion of the polymer elastic body A is penetrated by rubbing with a roll or a knife or the like, and the excess is rubbed with a knife or the like.
  • the entangled nonwoven fabric X is compressed in the thickness direction, and immediately thereafter, the solution or dispersion of the polymer elastic body B is impregnated.
  • the polymer elastic body B on the surface of the entangled nonwoven fabric X is scraped with a knife or the like so that the thickness after embossing is 1 to: LO m layer.
  • Coating layer Y And the base layer can be manufactured simultaneously. Coating layer Y
  • the coating layer Y may be manufactured separately as described below.
  • the texture becomes rubber-like.
  • the coating layer Y and the method of forming the coating layer Y include a high-density impregnated into the entangled nonwoven fabric X.
  • the adhesion between the base layer and the coating layer Y is defined as the surface of the base layer (other layers of the upper layer X).
  • the partial contact state means that the surface of the base layer and the coating layer are point-adhered, for example, when a gravure roll of a polymer elastic solution is applied to the surface of the base layer and the coating layer is bonded. Or a state in which the surface of the base layer and the coating layer are dry-bonded with an adhesive made of a crosslinked type polymer elastic body.
  • Examples of the method of solidifying the polymer elastic body include a method of immersing in a liquid containing a non-solvent of the polymer elastic body and wet-solidifying, or a method of gelling and then heating and drying.
  • the wet coagulation method is preferred in that the porous body easily forms a porous structure and a porous structure having a uniform pore size and distribution can be obtained.
  • additives such as a coloring agent, a coagulation regulator, an antioxidant, and a dispersant may be added to the polymer elastic body as needed.
  • a small amount of another resin such as an elastic polymer may be added as long as the effects of the invention can be obtained.
  • the ultrafine fiber-generating fibers are ultrafine and modified into ultrafine fiber bundles. Ultrafineness is achieved by treating with a dissolving agent or a decomposing agent to remove at least one component, or by exfoliating at the interface between the two components by mechanical or chemical treatment.
  • the ultrafine fiber bundle and the polymer elastic body are substantially adhered to each other in a state. Preferably it is. If the polymer elastic body is impregnated and coagulated after the ultrafine-graining, the polymer elastic body adheres to the microfine fiber bundle and the texture tends to be hard.
  • the polymer elastic body is applied after the dissolvable temporary filler such as polybutyl alcohol is applied so that the ultrafine fibers do not adhere to the polymer elastic body.
  • the temporary filler is subsequently removed.
  • a state in which the microfine fiber bundle and the polymer elastic body are not substantially bonded to each other means that the solidified polymer elastic body around the microfine fiber bundle has the microfibers at the intersection and non-intersection of the microfiber bundle. This refers to a state in which voids exist between the ultrafine fiber bundle that does not adhere to the bundle and the solidified polymer elastic body.
  • the coating layer Y is formed by the following method.
  • finishing layer Y By forming the finishing layer Y on the surface, it is possible to add silver having the appearance of the natural leather of the present invention.
  • Toned artificial leather is obtained.
  • An ink composed of a coloring agent such as a pigment or a dye and a known finishing resin is applied by a gravure roll, a reverse roll, a screen, or the like, and the surface of the coating layer Y is coated.
  • the heating temperature of the embossing roll is preferably from 100 to 230 ° C. in order to give a natural leather-like appearance by embossing. It is preferable for it to be within the above range, since a uniform grain pattern is formed and the polymer elastic body in the base layer is not thermally deformed.
  • the pressing pressure of the embossing roll is preferably in the range of 0.5 to 15 kgZcm 2 . Within the above range, a uniform grain pattern is formed and the lower layer X
  • the heating temperature is 120 to 190 ° C. and the pressing pressure is 1 to 6 kg / cm 2 , more preferably, because the obtained artificial leather has softness, flexibility, and natural leather appearance.
  • the thus obtained artificial leather with silver tone has a clear grain pattern of natural leather tone, a high-grade appearance and excellent softness, flexibility and fulfillment.
  • the thickness of the base layer is 0.2 to: LOmm
  • the thickness of the upper layer X is 0.01 to
  • the thickness of the coating layer Y is 0.01 mm or more. Is 1 ⁇ : ⁇ / ⁇ ⁇ ,
  • the thickness of the covering layer ⁇ should be 0.02 ⁇ : L 50mm, and the thickness of the finishing layer Y should be 1 ⁇ 100m.
  • the number of ultrafine fibers constituting the fiber bundle was counted.
  • the value obtained by dividing the total fineness of the fiber bundle by the number was defined as the single fiber fineness.
  • the distance to the line connecting is defined as the thickness of the coating layer Y.
  • the diameter (minor diameter) in the direction perpendicular to the thickness direction is measured.
  • the coating layer Y of the artificial leather with silver was sliced off. The remaining base layer was observed with an electron microscope, and the interface between the polymer elastic bodies A and B inside the base layer was confirmed.
  • the substrate layer was sliced along the interface and separated into an upper layer and a lower layer. And each slice The mass of the piece, the upper layer (Xb + b) and the lower layer (Xa + a) were measured.
  • the sliced pieces are separately washed with a solvent for the polymer elastic body A and a polymer elastic body B (DMF in the case of polyurethane), the polymer elastic body is removed, and the mass is dried (Xb and Xa). Was measured.
  • Xb and Xa were subtracted from Xb + b and Xa + a measured in advance to obtain b and a. The value of the above equation was calculated from the obtained mass.
  • the artificial leather with silver was cut to a width of 2.5 cm, affixed to a rubber plate using a polyurethane adhesive containing a crosslinking agent, pressed, dried, and then cured at 25 ° C for 24 hours.
  • the artificial leather and rubber plate were gripped and pulled by a tensile tester (pulling speed 100 mmZ, recording paper speed 50 mmZ), and the average peel strength was read from the recording paper. This average was divided by 2.5 and expressed in kgZcm.
  • a 13% dimethylformamide solution of a mixture of a polyether-based polyurethane and a polyester-based polyurethane (polyurethane A solution; 100% modulus of the mixed polyurethane: 40 kg Zcm 2 ) is impregnated into the entangled non-woven fabric XI, and a knife is pressed against the non-woven fabric to a thickness of 90%. % Compressed. Immediately thereafter, the N% obtained by polymerizing polyethylene propylene adipate glycol, 4,4'-diphenylmethane diisocyanate (MDI), and ethylene glycol (EG) on the surface of the entangled nonwoven fabric XI was 4.0%.
  • polyurethane A solution 100% modulus of the mixed polyurethane: 40 kg Zcm 2
  • polyester-based polyurethane (polyurethane B solution; 100% modulus of polyurethane: 70 kgZcm 2 ) is applied, and the entangled non-woven fabric XI is formed by utilizing the permeability of the solution and the suction force accompanying the recovery of the compressed state force.
  • the upper layer was impregnated.
  • a part of the polyurethane B solution layer covering the surface of the entangled nonwoven fabric XI was rubbed with a knife so that the thickness after coagulation became 12 / zm to form a coating layer Y. To form the coating layer Y
  • the surface of the coating layer Y is coated with polyhexacarbonate glycol and polymethylene propylene.
  • 18% dimethylformamide solution of polycarbonate polyurethane containing n-hexanediisocyanate, MDI, and EG in a mass ratio of 5: 2: 3 containing adipate and methylenediamine polyurethane C solution: polyurethane
  • the polyethylene was extracted and removed, and the conjugate fiber was converted into a 6-nylon ultrafine fiber bundle made of ultrafine fiber carpet having an average single fiber fineness of 0.007 decitex.
  • a polyurethane liquid containing a brown pigment was applied to the surface of the
  • the thickness of the base layer of the obtained artificial leather with silver is 1.3 mm, and the thickness of the upper layer X is 0.15 m.
  • XbZb was 50Z50, Xa / a «60/40, and the value of Equation 1 was 2.5.
  • the thickness of the coating layer Y was 0.2 mm, the thickness of the coating layer Y was 8 m, and the thickness of the coating layer Y was 0.18 mm.
  • the ratio of the maximum pore size of the layer Y and the upper layer X to the maximum pore size of the coating layer Y was 1Z25.
  • the peel strength of silver-toned artificial leather was 3.3 kgZcm, far exceeding the required peel strength.
  • sports shoes were produced using the above-mentioned artificial leather with silver, it was found to have a natural leather-like elegant appearance, excellent softness, flexibility and high peel strength.
  • a web Wa and a web Wb each having a basis weight of 350 g / m 2 were produced using a cross wrapper @ Eva. Web Wa and Web Wb are superimposed and punched with 1 parb-1 dollar needle-1 dollar.
  • An entangled nonwoven fabric having Zm 2 and a density of 0.15 gZcm 3 was obtained. After heating this non-woven fabric at 150 ° C, the surface was smoothed with a hot roll, and the basis weight was 600 gZm 2 and density.
  • a heat-set entangled nonwoven fabric X2 having a thickness of 30 gZcm 3 and a thickness of 2. Omm was obtained.
  • Both surfaces of the entangled nonwoven fabric X2 were mainly composed of microfine fiber-generating fibers A and microfine fiber-generating fibers B, respectively, and the inside of the nonwoven fabric had a structure in which the respective microfine fiber-generating fibers were entangled.
  • Example 1 After the polyurethane A solution used in Example 1 was impregnated into the entangled nonwoven fabric X2, a knife was pressed against the web Wa side to compress to 90% of the thickness of the nonwoven fabric. Immediately thereafter, the polyurethane B solution used in Example 1 was applied to the web Wb side, and the upper layer of the entangled nonwoven fabric X2 was used by utilizing the permeability of the polyurethane B solution and the suction force associated with the recovery of the force. (Mainly formed from web Wb). A part of the polyurethane B solution layer covering the surface of the entangled nonwoven fabric X2 was scraped with a knife to form a coating layer Y such that the thickness after solidification became 12 m. Coating
  • cover layer Y To form layer Y, cover layer Y
  • the upper layer (web Wb side) of the obtained substrate was mainly impregnated with polyurethane B, and the lower layer (web Wa side) was mainly impregnated with polyurethane A.
  • the polyethylene of the composite fiber is extracted and removed to obtain a 6-nylon ultrafine fiber bundle (upper layer X) having a single fiber fineness of 0.0001 deciters, and a single fiber fineness of 0.07 deci.
  • Example 2 a silver-tone artificial leather having a natural appearance and a soft feeling like a natural leather was obtained.
  • the thickness of the base layer of the obtained artificial leather with silver is 1.4 mm, and the thickness of the upper layer X is 0.3 mm.
  • XbZb was 50Z50
  • XaZa was 60 ⁇ 40
  • the value of Equation 1 was 2.5.
  • the thickness of the coating layer 0 was 0.15 mm
  • the thickness of the coating layer Y was 7 m
  • the thickness of the coating layer Y was 0.13 mm.
  • the ratio of the maximum pore diameter of the fine pore diameter of layer Y and upper layer X to the maximum pore diameter of coating layer Y is 1Z20.
  • the peel strength of artificial leather with silver tone was 2.8 kgZcm, which was much higher than the required peel strength. It was close to a natural leather with a fine crease. Above silver tone When sports shoes were manufactured using artificial leather, it was found to have a natural leather-like elegant appearance, excellent softness, flexibility and high peel strength.
  • a portion of the polyurethane B solution layer covering the surface of the entangled nonwoven fabric XI was scraped with a knife so that the thickness after solidification was 4 m, and a coating layer Y was formed in the same manner as in Example 1 except that the coating layer Y was formed.
  • the obtained artificial leather with silver tone had a natural appearance of natural leather tone and soft feeling, and the thickness of the coating layer Y was 1 ⁇ m. Peel strength is 2.9kgZcm
  • a silver-finished artificial leather was obtained in the same manner as in Example 1 except that a coating layer consisting only of E was formed.
  • the base layer consists of a bundle of 0.007 dtex 6-nylon microfibers, polyurethane A and polyurethane B, and the upper layer X is
  • Equation 1 The difference between the thickness of 0.151111111, 1) 715 and & 7 & was 60740, and the value of Equation 1 was 1.
  • Silver coating was performed in the same manner as in Example 1 except that the coating layer Y was formed using a polyurethane B solution.
  • Comparative Example 3 The entangled non-woven fabric X2 obtained in Example 2 was impregnated with the polyurethane A solution, the polyurethane A solution covering the surface was removed with a knife, and the polyurethane C solution was applied to the surface in the same manner as in Example 2 except that the polyurethane C solution was applied.
  • An artificial leather with silver tone was obtained.
  • the obtained artificial leather with silver tone was further rubbed with a kneader, it exhibited natural leather-like natural appearance and flexibility, but its peeling strength was low (1.8 kg / cm), and it was used for sports shoes. It was impossible.
  • a silver layer was formed in the same manner as in Example 1 except that a part of the polyurethane B solution layer covering the surface of the entangled nonwoven fabric XI was scraped off with a knife so that the thickness after solidification became 18 m, and the coating layer Y was formed.
  • a sticky artificial leather was obtained.
  • the obtained artificial leather with silver tone is 14 m thick.
  • the artificial leather with silver of the present invention has an elegant appearance of a natural leather, a soft surface, excellent flexibility, and high peel strength.
  • the artificial leather with silver tone of the present invention has a high-quality appearance of a natural leather tone with a clear grain pattern, a soft and cohesive feeling, and excellent peeling strength. It can be widely applied to applications.

Abstract

Il est prévu un cuir artificiel de ton argenté comprenant une couche de base et une couche de revêtement (Y) formée d'un côté de la couche de base. La couche de base comprend un tissu non tissé d’entrelacement (X) fait de faisceaux de fibres microfines d’une finesse de fibre simple moyenne inférieure ou égale à 0,07 dtex et un élastomère polymère (A) de même qu’un élastomère polymère (B) chacun infiltré dans des parties internes du tissu (X). Le tissu non tissé d’entrelacement (X) comprend une couche inférieure (XA) et une couche supérieure (XB). Principalement l’élastomère polymère (A) a été infiltré dans la couche inférieure (XA), essentiellement sans être accroché aux faisceaux de fibres microfines. Principalement l’élastomère polymère (B) a été infiltré dans la couche supérieure (XB), essentiellement sans être accroché aux faisceaux de fibres microfines. La couche de revêtement (Y) est composée d'une couche de revêtement de 1 à 10 µm d’épaisseur (YB) de l’élastomère polymère (B) formé sur la couche supérieure (XB), d’une couche de revêtement (YC) d’un élastomère polymère (C) formé sur la couche de revêtement (YB), et d’une couche de finition (YE) formée sur la couche de revêtement (YC). Le cuir artificiel d'un ton argenté, possédant une telle structure, combine un excellent aspect similaire à celui des cuirs naturels et une excellente douceur, une excellente souplesse et une résistance élevée au pelage.
PCT/JP2005/007863 2002-08-22 2005-04-26 Cuir artificiel de ton argente WO2005106108A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN2005800166129A CN1957136B (zh) 2004-04-28 2005-04-26 银色泽人造革
US11/587,593 US7442429B2 (en) 2002-08-22 2005-04-26 Grain-finished artificial leathers
EP05736597A EP1749920A4 (fr) 2004-04-28 2005-04-26 Cuir artificiel de ton argente
KR1020067022483A KR101166273B1 (ko) 2004-04-28 2005-04-26 은 부조 인공 피혁
JP2006512781A JP4560511B2 (ja) 2004-04-28 2005-04-26 銀付き調人工皮革

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JP2004132851 2004-04-28
JP2004-132851 2004-04-28

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JP (1) JP4560511B2 (fr)
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WO (1) WO2005106108A1 (fr)

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WO2008120702A1 (fr) * 2007-03-30 2008-10-09 Kuraray Co., Ltd. Feuille ressemblant à du cuir et possédant un apprêt granuleux, et procédé permettant de fabriquer cette feuille
US7932192B2 (en) * 2005-12-14 2011-04-26 Kuraray Co., Ltd. Base for synthetic leather and synthetic leathers made by using the same
JP2019151948A (ja) * 2018-03-02 2019-09-12 株式会社クラレ 銀付調皮革様シート、それを用いた鞄用持ち手、及び銀付調皮革様シートの評価方法

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KR101982372B1 (ko) * 2012-02-29 2019-05-27 주식회사 쿠라레 신축성 인공 피혁 및 그 제조 방법
CN105452559B (zh) * 2013-09-13 2017-11-21 东丽株式会社 片状物及其制造方法
RU2688910C1 (ru) * 2015-08-21 2019-05-22 Торэй Индастриз, Инк. Одежда
CN105482057B (zh) * 2015-12-21 2018-06-29 上海汇得科技股份有限公司 一种软质全聚醚型耐水解低泡湿法聚氨酯树脂及其制备方法
US11015288B2 (en) 2016-05-09 2021-05-25 Kuraray Co., Ltd. Grained artificial leather

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US7932192B2 (en) * 2005-12-14 2011-04-26 Kuraray Co., Ltd. Base for synthetic leather and synthetic leathers made by using the same
JP4847472B2 (ja) * 2005-12-14 2011-12-28 株式会社クラレ 人工皮革用基材およびその基材を用いた人工皮革
TWI386530B (zh) * 2005-12-14 2013-02-21 Kuraray Co 人造皮革用基材、其製法及使用其之人造皮革
WO2008120702A1 (fr) * 2007-03-30 2008-10-09 Kuraray Co., Ltd. Feuille ressemblant à du cuir et possédant un apprêt granuleux, et procédé permettant de fabriquer cette feuille
JP5159764B2 (ja) * 2007-03-30 2013-03-13 株式会社クラレ 銀付調皮革様シートおよびその製造方法
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KR101523394B1 (ko) * 2007-03-30 2015-05-27 가부시키가이샤 구라레 은 부조 피혁양 시트 및 그 제조 방법
JP2019151948A (ja) * 2018-03-02 2019-09-12 株式会社クラレ 銀付調皮革様シート、それを用いた鞄用持ち手、及び銀付調皮革様シートの評価方法
JP7112213B2 (ja) 2018-03-02 2022-08-03 株式会社クラレ 銀付調皮革様シート、及びそれを用いた鞄用持ち手

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JP4560511B2 (ja) 2010-10-13
CN1957136B (zh) 2010-05-05
EP1749920A4 (fr) 2009-07-22
KR20070006870A (ko) 2007-01-11
JPWO2005106108A1 (ja) 2008-03-21
KR101166273B1 (ko) 2012-07-17
CN1957136A (zh) 2007-05-02
TW200609411A (en) 2006-03-16
TWI372806B (en) 2012-09-21

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