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US20030039772A1 - Leather-like sheety product and production method therefor - Google Patents

Leather-like sheety product and production method therefor Download PDF

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Publication number
US20030039772A1
US20030039772A1 US09/958,026 US95802601A US2003039772A1 US 20030039772 A1 US20030039772 A1 US 20030039772A1 US 95802601 A US95802601 A US 95802601A US 2003039772 A1 US2003039772 A1 US 2003039772A1
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US
United States
Prior art keywords
sheet
elastic polymer
fibers
layer
sheet layer
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Abandoned
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US09/958,026
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English (en)
Inventor
Naohiko Takeyama
Masahisa Mimura
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Teijin Ltd
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Individual
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Assigned to TEIJIN LIMITED reassignment TEIJIN LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MIMURA, MASAHISA, TAKEYAMA, NAOHIKO
Publication of US20030039772A1 publication Critical patent/US20030039772A1/en
Abandoned legal-status Critical Current

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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
    • 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
    • D06N3/0013—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 multilayer webs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/4935—Impregnated naturally solid product [e.g., leather, stone, etc.]

Definitions

  • the present invention relates to a novel leather-like sheet product which has excellent stay properties and yet excellent balance between softness and buckling resistance and to a production process therefor. Particularly, it relates to a leather-like sheet product suitable for use in furniture and shoes and to a production process therefor.
  • JP-B 62-15673 and JP-B 62-38474 processes for laminating together two separately produced sheet layers are disclosed by JP-B 62-15673 and JP-B 62-38474 (the term “JP-B” as used herein means an “examined Japanese patent publication”).
  • JP-B as used herein means an “examined Japanese patent publication”.
  • the obtained sheet product has a difference between front and rear sides, when it is soft as a whole, it lacks tightness and when it has tightness, it is hard. Therefore, a sheet product as soft and tight as natural leather cannot be obtained by these processes.
  • the processes involve such a problem that when a treating solution is coated in the form of a film, the obtained sheet product becomes too hard because a resin or fiber constituting the sheet product is dissolved in a solvent and bonded.
  • the amount of a component dissolved in the treating solution is small on the adhesive surface, for example, a resin component of a sheet product which contains a large amount of a fiber and a small amount of an impregnating resin is dissolved and bonded, sufficient adhesive force is hardly obtained.
  • a fabric scrim and an elastomer sheet of rubber may be inserted into an intermediate layer as a reinforcement.
  • strength improves but anisotropy is seen in a weaving direction, whereby the obtained product cannot be round unlike natural leather.
  • the elastomer sheet is used, elastic recovery when it is greatly bent cannot be small and elastic recovery is large unlike natural leather.
  • a sheet product having a large width is now in demand to improve cutting yield.
  • the width of a sheet product is limited by machining equipment in each step and the existing equipment is designed to produce a hard substrate.
  • the substrate is elongated in length and shrunk in width by tension in a lengthwise direction, thereby making it possible to produce only products having a small width.
  • a huge amount of investment is needed to modify the equipment to increase the width and reduce tension in addition to the solving of the above quality problems. Therefore, a production process for a sheet product having soft substrate without reducing its quality as well as suppressing the shrinkage in width during processing has been strongly desired.
  • a leather-like sheet product which comprises (a) a sheet layer ( 1 ) composed of a fiber assembly ( 1 ) of fine fibers and an elastic polymer (A) existent in a space between fibers of the fiber assembly ( 1 ), (b) a sheet layer ( 2 ) essentially composed of a fiber assembly ( 2 ) or composed of a fiber assembly ( 2 ) and an elastic polymer (C) existent in a space between fibers of the fiber assembly ( 2 ), and (c) an adhesive layer, composed of an elastic polymer (B), for bonding together the sheet layer ( 1 ) and the sheet layer ( 2 ), wherein
  • the fibers of the sheet layer ( 1 ) and the fibers of the sheet layer ( 2 ) penetrate in the adhesive layer at the respective interfaces, the fibers of the sheet layer ( 1 ) are existent in the adhesive layer in a state that they are substantially not bonded to the elastic polymer (B), and the fibers of the sheet layer ( 2 ) are existent in the adhesive layer in a state that they are substantially bonded or not bonded to the elastic polymer (B); and (e) the elastic polymer (B) is existent in the adhesive layer in a state that it is bonded to at least the elastic polymer (A) contained in the sheet layer ( 1 ) at the interface.
  • a sheet layer ( 1 ′) composed of a fiber assembly of sea-island type fibers made from a mixture of at least two different polymers which differ from each other in solvent solubility and an elastic polymer (A) existent in a space between fibers of the fiber assembly and a sheet layer ( 2 ) essentially composed of a fiber assembly ( 2 ) or composed of a fiber assembly ( 2 ) and an elastic polymer (C) existent in a space between fibers of the fiber assembly ( 2 ) by an adhesive layer composed of an elastic polymer (B); and
  • the leather-like sheet product of the present invention substantially comprises a sheet layer ( 1 ) and a sheet layer ( 2 ) both of which are bonded together by an adhesive layer composed of an elastic polymer (B).
  • the sheet layer ( 1 ) of the present invention is composed of a fiber assembly ( 1 ) of fine fibers and an elastic polymer (A) existent in a space between fibers of the fiber assembly ( 1 ) and preferably contains a resin which comprises as an essential ingredient a high-molecular elastic polymer in a space between fibers of a finely entangled nonwoven fabric which is entangled inform of three dimensions.
  • the fine fiber is a fine fiber of 0.5 dtex or less, preferably 0.1 dtex or less, or a bundle of fine fibers of 0.5 dtex or less, preferably 0.1 dtex or less. Stated more specifically, it is (i) a fine fiber of 0.5 dtex or less obtained by spinning independently, or (ii) a fine fiber obtained by removing at least one component of a multi-component fiber obtained by spinning a polymer composition consisting of two or more components which differ from each other in solvent solubility by composite spinning or blend spinning as a sea-island type fiber, or a fine fiber obtained by splitting a composite fiber having a laminated section.
  • the surface of the fiber may be treated with a sizing agent such as silicone or polyvinyl alcohol.
  • a sizing agent such as silicone or polyvinyl alcohol.
  • a polyolefin such as polyethylene, polypropylene or polystyrene is preferably selected as an easily soluble component and when a polyamide is selected as an insoluble component, a polyester or polyolefin is preferably selected as an easily soluble component.
  • a known card, layer, needle rocker or fluid (water jet) entangling machine is preferably used to produce a finely entangled nonwoven fabric having a high density of entangled fibers.
  • the elastic polymer (A) existent in a space between fibers of the fiber assembly is a polyurethane-based elastomer such as polyurethane elastomer, polyurea elastomer or polyurethane-urea elastomer, polyester-based elastomer, synthetic rubber, natural rubber or polyacrylic acid resin, out of which a polyurethane-based elastomer is preferred.
  • the polyurethane-based elastomer is obtained by reacting a polyol with an organic diisocyanate in the presence of a low-molecular weight chain extender.
  • the polyurethane-based elastomer is obtained by reacting a polyol having a molecular weight of 500 to 4,000 such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene carbonate, polyhexamethylene carbonate, polyethylene adipate, polybutylene adipate or polyhexamethylene adipate with an organic diisocyanate such as diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate or 3,3,5-trimethyl-5-isocyanatemethylcyclohexyl isocyanate in the presence of a low-molecular weight chain extender such as ethylene glycol, butylene glycol, xylylene glycol, propylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane,
  • the hardness of the elastic polymer (A) is preferably 100 to 3,000 N/cm 2 , more preferably 300 to 1,500 N/cm 2 , the most preferably 400 to 1,000 N/cm 2 in terms of 100% elongation stress of a film formed from the elastic polymer (A) alone.
  • the fiber assembly is treated with an organic solvent solution or aqueous dispersion of the elastic polymer (A) and then the solution is coagulated on the fiber assembly by a conventionally known wet coagulation process or dry coagulation process.
  • Any compounding agents such as a porosity controlling agent and colorant may be added to the treating solution in limits that do not impair the elasticity of the elastic polymer (A). Since the softness and elastic recovery of the sheet product are adjusted by the amount of the elastic polymer (A) deposited on the fiber assembly, the amount of the elastic polymer is preferably 10 to 120 wt %, more preferably 25 to 80 wt % based on the fiber assembly.
  • a grain layer composed of an elastic polymer or a napped layer of fine fibers may be formed on the surface (surface opposite to the surface to which the sheet layer ( 2 ) is bonded) which is the exterior side of a leather-like sheet product of the sheet layer ( 1 ) by a conventionally known method.
  • the elastic polymer of the grain layer may be porous or non-porous, or a single layer or laminate.
  • the formation of the grain layer or napped layer may be carried out before or after the step of bonding the sheet layers by the adhesive layer composed of the elastic polymer (B).
  • the thickness and density of the sheet layer ( 1 ) of the leather-like sheet product of the present invention are preferably as follows.
  • the thickness t 1 (mm) of the sheet layer ( 1 ) is preferably 0.2 to 1.5 mm, more preferably 0.3 to 1.3 mm.
  • the layer is too thin and not strong enough, or may be difficult to be processed substantially.
  • the thickness is larger than 1.5 mm, the layer is too thick, has a hard feel and may be limited in application.
  • the apparent density pi (g/cm 3 ) of the sheet layer ( 1 ) is preferably 0.20 to 0.48 g/cm 3 , more preferably 0.25 to 0.45 g/cm 3 .
  • the layer When the apparent density of the sheet layer ( 1 ) is smaller than 0.20 g/cm 3 , the layer has a soft feel but not tight feel and may not be strong enough. When the apparent density is larger than 0.48 g/cm 3 , the layer may have a hard feel.
  • the sheet layer ( 2 ) is composed of a fiber assembly ( 2 ) and an elastic polymer (e) existent in a space between fibers of the fiber assembly ( 2 ).
  • the fibers constituting the fiber assembly ( 2 ) of the sheet layer ( 2 ) may be ordinary fibers, for example, natural fibers such as cotton, flax or wool fibers, chemical fibers such as rayon, nylon, polyester or polyurethane fibers, or blend fibers thereof.
  • the fiber assembly may be a fabric such as a knitted fabric other than a entangled nonwoven fabric.
  • the surface of the fiber In order to obtain a non-bonding structure with the elastic polymer (C), it is preferred to treat the surface of the fiber with a sizing agent such as silicone or polyvinyl alcohol in advance or to use a sea-island type fiber from which a sea component can be removed after the sheet layers ( 1 ) and ( 2 ) are bonded together. It is also preferred to impregnate the fiber with a resin which contains the elastic polymer (C) as an essential ingredient.
  • the amount of the elastic polymer is preferably 2 to 120 wt %, more preferably 10 to 80 wt % based on the fiber assembly ( 2 ).
  • the sheet layer ( 2 ) is preferably composed of a fiber assembly of fine fibers and the elastic polymer (C) existent in a space between fibers of the fiber assembly like the sheet layer ( 1 ).
  • the elastic polymer (C) is identical to the above elastic polymer (A) used in the sheet layer ( 1 ).
  • a grain layer composed of an elastic polymer or a napped layer of fine fibers may be formed on the surface (surface opposite to the surface to which the sheet layer ( 1 ) is bonded) which is the exterior side of a leather-like sheet product of the sheet layer ( 2 ) by a conventionally known method like the sheet layer ( 1 ).
  • the thickness and density of the sheet layer ( 2 ) are preferably as follows.
  • the thickness t 2 (mm) of the sheet layer ( 2 ) is preferably 0.2 to 2.5 mm, more preferably 0.3 to 2.0 mm.
  • the layer is too thin and not strong enough, or may be difficult to be processed substantially.
  • the thickness is larger than 2.5 mm, the layer is too thick, has a hard feel and may be limited in application.
  • the apparent density ⁇ 2 (g/cm 3 ) of the sheet layer ( 2 ) is preferably 0.20 to 0.48 g/cm 3 , more preferably 0.23 to 0.45 g/cm 3 .
  • the layer When the apparent density of the sheet layer ( 2 ) is smaller than 0.20 g/cm 3 , the layer has a soft feel but not tight feel and may not be strong enough. When the apparent density is larger than 0.48 g/cm 3 , the layer may have a hard feel.
  • the thicknesses and densities of the sheet layer ( 1 ) and the sheet layer ( 2 ) preferably satisfy the following expressions (1) to (6) at the same time.
  • the expressions (1), (2), (4) and (5) show the thicknesses t 1 and t 2 (mm) and apparent densities ⁇ 1 and ⁇ 2 (g/cm 3 ) of the sheet layer ( 1 ) and the sheet layer ( 2 ), respectively.
  • the expression (6) shows the total (t 1 +t 2 ) of the thickness t 1 (mm) of the sheet layer ( 1 ) and the thickness t 2 (mm) of the sheet layer ( 2 ), which is preferably 0.4 to 4.0, more preferably 0.4 to 3.6.
  • (t 1 +t 2 ) is smaller than 0.4, these layers are too thin and not strong enough, and may be difficult to be laminated together.
  • (t 1 +t 2 ) is larger than 4.0, these layer are too thick, have a hard feel and may be limited in application.
  • the expression (3) shows the ratio ⁇ 1 / ⁇ 2 of the apparent density ⁇ 1 (g/cm 3 ) of the sheet layer ( 1 ) to the apparent density ⁇ 2 (g/cm 3 ) of the sheet layer ( 2 ), which is preferably 0.50 to 2.4, more preferably 1.00 to 2.0, particularly preferably 1.05 to 2.00.
  • ⁇ 1 / ⁇ 2 is smaller than 0.50 or larger than 2.4, a dense feel of a low-density side decreases, the number of wrinkles may increase and a sense of difference is easily given due to a big difference in density.
  • the sheet layers ( 1 ) and ( 2 ) may be produced by preparing two thick sheets and slicing them into two or more layers or by slicing a single thick sheet. Since a thin nonwoven fabric having a thickness of 1 mm or less generally has low strength and low processability and cannot increase the line speed, its productivity is low. Therefore, it is preferred to form a thick sheet and slice it into the sheet layers ( 1 ) and ( 2 ) having a desired thickness.
  • the sheet layer ( 1 ) and the sheet layer ( 2 ) are bonded together by the adhesive layer composed of the elastic polymer (B).
  • an organic solvent solution or aqueous dispersion of the elastic polymer (B) is applied to the surface of one of the sheet layers and the coated sheet layer is laminated with the other sheet layer.
  • the coating solution may contain various additives in limits that do not impair bonding.
  • the amount of coating which depends on permeability into the substrate is preferably 20 to 500 g/m 2 in terms of dry weight.
  • the elastic polymer (B) for forming this adhesive layer may be an elastic material of a polyurethane resin, polyacrylic acid resin, synthetic rubber or polyvinyl acetate resin.
  • the polyurethane resin is the most preferred from the viewpoint of the application of the leather-like sheet product of the present invention.
  • the polyurethane resin is obtained by reacting a polyol with an organic diisocyanate in the presence of a low-molecular chain extender as will be described hereinafter.
  • the polyurethane resin is obtained by reacting a polyol having a molecular weight of 500 to 4,000 such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene carbonate, polyhexamethylene carbonate, polyethylene adipate, polybutylene adipate or polyhexamethylene adipate with an organic diisocyanate such as diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate or 3,3,5-trimethyl-5-isocyanatemethylcyclohexyl isocyanate in the presence of a low-molecular chain extender such as ethylene glycol, butylene glycol, xylylene glycol, propylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 3,3,5-trimethyl-5
  • a polyfunctional isocyanate obtained by an addition reaction between tolylene diisocyanate or diphenylmethane diisocyanate and trimethylol propane as an organic isocyanate to obtain a crosslinked polyurethane resin in order to improve adhesion strength and solvent resistance.
  • a polyfunctional isocyanate obtained by an addition reaction between tolylene diisocyanate or diphenylmethane diisocyanate and trimethylol propane
  • aging is carried out until crosslinking ends to complete bonding.
  • various catalysts may be added to the coating solution.
  • the adhesive layer in the present invention means not only a layer composed of the elastic polymer (B) alone but also a layer having a higher density than other portions of the sheet layers which do not take part in bonding due to the existence of the elastic polymer (B) in some of spaces in the sheet layers ( 1 ) and ( 2 ).
  • a layer composed of the elastic polymer (B) alone should not exist although there is an adhesive layer between the sheet layers ( 1 ) and ( 2 ).
  • the average thickness of the adhesive layer composed of this elastic polymer (B) is preferably 0.01 to 0.5 mm.
  • the 100% elongation stress of the film is preferably 200 to 3,000 N/cm 2 .
  • the coating solution preferably contains a low-density substance such as air.
  • the apparent density of a sheet formed from the coating solution is preferably 0.5 to 0.8 g/cm 3 .
  • the fibers of the sheet layer ( 1 ) and fibers of the sheet layer ( 2 ) penetrate in the adhesive layer at the respective interfaces the fibers of the sheet layer ( 1 ) are existent in a state that they are substantially not bonded to the elastic polymer (B), the fibers of the sheet layer ( 2 ) are existent in a state that they are substantially bonded or not bonded to the elastic polymer (B), and further in the adhesive layer, the elastic polymer (B) is existent in a state that it is bonded to at least the elastic polymer (A) contained in the sheet layer ( 1 ) at the interface.
  • the elastic polymer (B) must be existent in the adhesive layer in a state that it is substantially not bonded to the fibers constituting the sheet layer ( 1 ). Meanwhile, the elastic polymer (B) may be bonded or not bonded to the fibers constituting the sheet layer ( 2 ) but preferably not bonded to the fibers.
  • the state that the elastic polymer (B) of the layer of the elastic polymer (B) is substantially not bonded to the fibers is a state that fine fibers or ordinary fibers which are not in contact with the elastic polymer (B) or not bonded to the elastic polymer (B) even when they are in contact with the elastic polymer (B) account for at least 50% or more, preferably 80% or more, more preferably 95% or more of the total of all the fibers in the section of the sheet.
  • the elastic polymer (B) should not exist in the inside space of the bundle of fine fibers and should not be in contact with fine monofilaments contained in the bundle of fine fibers although the bundle of fine fibers penetrates in the elastic polymer (B) of the adhesive layer.
  • This structure is obtained by the following method, for example. That is, the sheet layer ( 1 ) composed of a sea-island type fiber from which a fine fiber can be made is formed, bonded by the adhesive layer composed of the elastic polymer (B), and treated with a solvent which does not dissolve the island component of the fine fiber and the elastic polymers of the sheet layers and the layer of the elastic polymer (B) and selectively dissolves the sea component of the fiber to remove the sea component of the sea-island type fiber.
  • the sea component around the sea-island type fiber is dissolved and removed, whereby a structure that the elastic polymer (B) is not bonded to the fine fiber of the island component is formed though the elastic polymer (B) in the adhesive layer composed of the elastic polymer (B) is bonded to the elastic polymer (A) or (C) of the sheet layer.
  • the elastic polymer (A) is not bonded to the fine fiber of the island component in the sheet layer as well, thereby improving a feel.
  • the sheet layer ( 2 ) should be composed of a fiber assembly of sea-island type fibers made from at least two different polymer compositions which differ from each other in solvent solubility and the elastic polymer (C) existent in a space between fibers of the fiber assembly, like the sheet layer ( 1 ). Since the fine fiber of the island component of each of the sheet layers ( 1 ) and ( 2 ) is not bonded to the elastic polymers (A), (B) and (C) in this case, a structure that all the elastic polymers of the leather-like sheet product are not bonded to the fine fibers is thus formed.
  • Other methods for bonding not to the fiber but to other elastic polymer include one in which the surface of the fiber is treated with a silicone-based softening water repellent to prevent bonding between the elastic polymer and the fiber before the elastic polymer is applied and one in which a substance between the elastic polymer and the surface of the fiber is removed after the elastic polymer is bonded to other elastic polymer.
  • the substance to be removed is a polyvinyl alcohol when the surface of the fiber is treated with the polyvinyl alcohol in advance or a sea component when a sea-island type fiber is used as the above fiber.
  • the elastic polymer (B) of the adhesive layer is preferably bonded to the elastic polymer (A) of the sheet layer ( 1 ) and the elastic polymer (C) of the sheet layer ( 2 ) which is impregnated with a resin at the respective interfaces to increase adhesive force between the sheet layer ( 1 ) and the sheet layer ( 2 ).
  • the leather-like sheet product of the present invention is preferably the following sheet product (I) or (II):
  • a leather-like sheet product comprising (a) a sheet layer ( 1 ) composed of a fiber assembly ( 1 ) of fine fibers and an elastic polymer (A) existent in a space between fibers of the fiber assembly ( 1 ), (b) a sheet layer ( 2 ) composed of a fiber assembly ( 2 ) of fine fibers and an elastic polymer (C) existent in a space between fibers of the fiber assembly ( 2 ), and (c) an adhesive layer, composed of an elastic polymer (B), for bonding together the sheet layer ( 1 ) and the sheet layer ( 2 ), wherein
  • a leather-like sheet product comprising (a) a sheet layer ( 1 ) composed of a fiber assembly ( 1 ) of fine fibers and an elastic polymer (A) existent in a space between fibers of the fiber assembly ( 1 ), (b) a sheet layer ( 2 ) composed of a fiber assembly ( 2 ) of fine fibers and an elastic polymer (C) existent in a space between fibers of the fiber assembly ( 2 ), and (c) an adhesive layer, composed of an elastic polymer (B), for bonding together the sheet layer ( 1 ) and the sheet layer ( 2 ), wherein
  • the fibers of the sheet layer ( 1 ) and the fibers of the sheet layer ( 2 ) penetrate in the adhesive layer at the respective interfaces, the fibers of the sheet layer ( 1 ) are existent in the adhesive layer in a state that they are substantially not bonded to the elastic polymer (B), and the fibers of the sheet layer ( 2 ) are existent in the adhesive layer in a state that they are substantially bonded to the elastic polymer (B); and (e) the elastic polymer (B) is existent in the adhesive layer in a state that it is bonded to at least the elastic polymer (A) contained in the sheet layer ( 1 ) at the interface and to the elastic polymer (C) contained in the sheet layer ( 2 ) at the interface.
  • the leather-like sheet product of the present invention preferably has a leather-likeness index of 0.5 to 2.0.
  • the term “leather-likeness index” is a value calculated from the following equation by measuring flexural resistance (RB), compressive stress (P 3 ) and elastic recovery (ER) in accordance with measurement methods which will be described hereinafter.
  • leather-likeness index compression stress(P 3 )/(flexural resistance( RB ) ⁇ elastic recovery( ER ))
  • the meaning of the leather-likeness index As this value becomes greater, the product is softer and has larger compressive stress (higher tightness) and smaller elastic recovery.
  • a large leather-likeness index means that the product has properties closer to natural leather.
  • flexural resistance (RB) and elastic recovery (ER) must be reduced and compressive stress (P 3 ) must be increased.
  • the elastic polymer (A) and the elastic polymer (C) should be existent in states that they are not bonded to the fibers of the sheet layer ( 1 ) and the fibers of the sheet layer ( 2 ), respectively, and that the elastic polymer (B) of the adhesive layer should interpose between the sheet layer ( 1 ) and the sheet layer ( 2 ).
  • the apparent densities of the sheet layer ( 1 ) and the sheet layer ( 2 ), the thickness of the adhesive layer and the modulus of the resin should be set to the above appropriate values. Further, in order to reduce elastic recovery, it is preferred that the elastic polymer (A) and the fiber assembly in the sheet layer ( 1 ) should not be bonded to each other and/or the elastic polymer (C) and fibers in the sheet layer ( 2 ) should not be bonded to each other.
  • the peel strength of the surface of the sheet product is preferably 20 N/cm or more, more preferably 25 N/cm or more.
  • This peel strength is a value per 1 cm in width of peel strength obtained by laminating together two 2.5 cm ⁇ 9.0 cm sample pieces by a polyurethane adhesive in such a manner that their front surfaces become adjacent to each other and by making a peel test on the obtained laminate.
  • the elastic polymer (B) of the adhesive layer may be infiltrated into the sheet layer ( 1 ) and the sheet layer ( 2 ).
  • the surface of this leather-like sheet product may be napped by a conventionally known method, provided with a grain layer, dyed or the like. Although these treatments may be carried out in any step, they may be carried out after the sheet layers are bonded together by the adhesive layer to avoid the deformation of the substrate caused by tension. For example, when the surface is to be napped, it Is preferred to buff and dye the product in the final step so as to protect the soft sheet and fine nap. When a grain surface structure is to be provided, it is effective to form a porous elastic polymer layer upon the impregnation of the surface of the sheet layer with the elastic polymer and/or to form a non-porous elastic polymer layer by coating in the final step.
  • the present invention is not limited to these and the order may be changed, or other embossing and rubbing steps may be combined.
  • the thus obtained leather-like sheet product has excellent stay properties like natural leather and yet good balance between softness and buckling resistance and is deformed round with fine wrinkles when it is bent and particularly suitable for use in furniture and shoes.
  • the process of the present invention is a production process which suppresses shrinkage in width during processing without reducing the quality of a soft substrate.
  • the present invention provides a leather-like sheet product having leather-like properties with a large leather-likeness index in which a sheet layer ( 1 ) and a sheet layer ( 2 ) both containing a fiber assembly are bonded together by an adhesive layer composed of an elastic polymer (B) so that the adhesive layer is existent as an intermediate layer of the leather-like sheet product and functions as an intermediate layer against the bending deformation of the sheet, and tensile stress and compressive stress (P 3 ) upon large deformation can be made large without increasing flexural resistance (RB) and elastic recovery (ER) upon small deformation, compared with a sheet product composed of only a fiber assembly and an elastic polymer without an adhesive layer.
  • RB flexural resistance
  • ER elastic recovery
  • flexural resistance is expressed by an integral value of the product of the distance from the intermediate layer and stress at that position on the flexural section of the sheet, even if a high-modulus and high-density layer is existent near the intermediate layer, flexural resistance (RB) upon small deformation is not impaired.
  • the elastic polymer (B) of the adhesive layer penetrates in the sheet layer ( 1 ) but is not bonded to the fibers of the sheet layer ( 1 ), it is possible to obtain a leather-like sheet product retaining softness and adhesive strength.
  • a 2.5 cm ⁇ 9.0 cm sample piece was fixed to a fixing tool at a position 2.0 cm away from one end thereof.
  • the resiliency of the sample when the sample was bent at 90° to a curvature radius of 2 cm at a position 2.0 cm away from the other end of the sample was measured and a value per 1 cm in width of the sample piece was obtained from this value and taken as flexural resistance (unit; N/cm).
  • a 2.5 cm ⁇ 9.0 cm sample piece was bent into two at the center and set in a constant-speed compression tester.
  • the head of the compression tester was lowered at a rate of 1 cm/min to bend, compress and deform the sample and measure compression when the sample was compressed to an interval 3 times its thickness, and a value per 1 cm in width calculated from the measurement value was taken as compression force (unit; N/cm).
  • a 1 cm (width) ⁇ 9 cm (length) sample piece was bent into two and placed under a load of 49.03 N/cm, the load was removed after 1 hour, and the opening angle ⁇ of the sample piece after 30 seconds was measured to obtain elastic recovery from the following equation.
  • an adhesive Ulock 420 of Hirono Kagaku Kogyo Co., Ltd., containing 2 wt % of Coronate L of Nippon Polyurethane Industry Co., Ltd.
  • the thickness of an adhesive layer was measured at 5 points from a photo of the section of the layer taken by a scanning electron microscope and the mean value of these measurement data was taken as the average thickness of the adhesive layer.
  • a photo of the section of a sample was taken by a scanning electron microscope to observe a space between fibers and the elastic polymer. Bonding between the elastic polymer (A), the elastic polymer (C) contained in the substrate or the elastic polymer (B) of the adhesive layer and the fiber was observed. When the elastic polymer is adhered to the entire surface of the fiber, it is considered that the elastic polymer is bonded to the fiber. When the area of the space is larger than the section of the fiber, it is considered that the elastic polymer is not bonded to the fiber even though the elastic polymer is contacted to part of the fiber.
  • the fiber is a bundle of fine fibers
  • a photo of the section of the fiber is taken by a scanning electron microscope to observe the existence of the elastic polymer in the bundle of fine fibers.
  • the expression “in the bundle of fine fibers” means a space surrounded by the outermost fine fibers out of a large number of fine fibers produced from a single fiber before a fine fiber are made.
  • Nylon-6 and low-density polyethylene were mixed in a ratio of 50:50, the obtained mixture was spun into fiber, the fiber was stretched in a hot water bath at 60° C. to 3 times its original size, mechanically crimped and cut to obtain a fiber having a fineness of 4.4 dtex and a size of 51 mm.
  • This fiber was carded, cross layered or needle punched to obtain a needle punched web having a weight of 412 g/m 2 .
  • This web was heated in the chamber of a hot air drier set at 140° C. for 3 minutes and let pass between cooling rolls at 35° C. to prepare a nonwoven fabric ( 1 ) having a thickness shown in Table 1. The web weight, thickness and apparent density of the fabric are shown in Table 1.
  • a hydrophilic coagulation modifier FG-10 of Matsumoto Yushi-Seiyaku Co., Ltd.
  • the above nonwoven fabric ( 1 ) was immersed in the above impregnating solution, an excess of the impregnating solution was removed by squeezing, and the impregnating solution was wet coagulated in a 15% aqueous solution of dimethylformamide heated at 40° C.
  • the impregnated fabric was washed in water and dried to obtain an impregnated substrate ( 1 ).
  • the amount of the impregnating resin after drying is also shown in Table 1.
  • This impregnated substrate ( 1 ) was sliced into two sheets at a position where the thickness was 1 ⁇ 2. These were designated as unextracted sheets ( 1 ).
  • the nonwoven fabric ( 1 ) obtained in Reference Example 1 was immersed in the impregnating solution prepared in Reference Example 1, an excess of the impregnating solution was removed by squeezing, the above coating solution was applied to the fabric to a wet weight of 300 g/m 2 and wet coagulated in a 15% aqueous solution of dimethylformamide heated at 40° C.
  • the fabric was washed in water and dried to obtain an impregnated substrate ( 5 ) having a grain layer, This substrate was sliced into two sheets at a position where the thickness was 1 ⁇ 2 and these sheets were designated as the upper layer and lower layer of the unextracted sheet ( 5 ).
  • a peel and division type composite fiber which comprised polyethylene terephthalate as a first component and nylon-6 as a second component and had a 16 divided gear-like cross section was melt spun, stretched to 2.0 times in hot water heated at 40° C., mechanically crimped and cut to obtain a thermally shrunk, peel and division type composite fiber having a fineness of 3.3 dtex, a size of 45 mm and a hot water shrinkage factor of 9.5%.
  • the volume ratio of the both components was 50:50 and each of the both components was divided into 16 segments by the other component. This was carded, cross-layered, needle punched or entangled by a jet stream to obtain a web having a weight of 286 g/m 2 .
  • this web was immersed in a hot water tank heated at 75° C. for 20 seconds to shrink a polyethylene terephthalate fiber to reduce its area by 21% and dried with a hot air drier heated at 110° C. to obtain a nonwoven fabric ( 8 ) having a thickness shown in Table 3.
  • an impregnating solution comprising 100 parts of a dimethylformamide solution (resin concentration of 10%) of a polyether-ester polyurethane resin (corresponding to the elastic polymer (A) or the elastic polymer (C)) having a 100% elongation stress of 1,030 N/cm 2 , 0.5 part of a hydrophilic coagulation modifier (FG-10 of Matsumoto Yushi-Seiyaku Co., Ltd.) and 0.5 part of a hydrophobic coagulation modifier (FG-12 of Matsumoto Yushi-Seiyaku Co., Ltd.) was prepared.
  • the nonwoven fabric ( 8 ) was immersed in the above impregnating solution, an excess of the impregnating solution was removed by squeezing, and the fabric was wet coagulated in a 15% aqueous solution of dimethylformamide heated at 40° C. This fabric was washed in water and dried to obtain an impregnated substrate ( 8 ).
  • the amount of the impregnating resin after drying is shown in Table 3.
  • sheet (8) used nonwoven fabric* web weight (g/m 2 ) 500/2 362/2 thickness (mm) 1.50/2 1.08/2 density (g/cm 3 ) 0.333 0.335 amount of impregnating resin 126.2 76/2 (dry)* (g/m 2 ) sliced/not sliced sliced sliced physical properties of sheet web weight (g/m 2 ) 313 219 layer after sliced thickness (mm) 0.75 0.54 density (g/cm 3 ) 0.417 0.406 physical properties of sheet web weight (g/m 2 ) 188 — layer after extraction thickness (mm) 0.61 — density (g/cm 3 ) 0.294 —
  • An adhesive composition ( 1 ) comprising 50 parts of Crisbon TA-290 (polyurethane resin of Dainippon Ink and Chemicals, Inc., concentration of 45%), 50 parts of Crisbon TA-265 (polyurethane resin of Dainippon Ink and Chemicals, Inc., concentration of 65%), 12 parts of Coronate 2094 (crosslinking agent of Nippon Polyurethane Industry Co., Ltd.), 3 parts of Crisbon Accel-T (catalyst of Dainippon Ink and Chemicals, Inc.) and 20 parts of methyl ethyl ketone was prepared as an adhesive essentially composed of polyurethane resins (corresponding to the elastic polymer (B)).
  • the apparent density of a film formed by applying this adhesive composition ( 1 ) to release paper, drying and aging was 1.15 g/cm 3 and 100% elongation stress thereof was 294 N/cm 2 .
  • Dimethylformamide was applied to one side of the obtained sheet by a 200-mesh gravure roll, dried and buffed by a polisher having 400-mesh emery paper to obtain a napped substrate which was then dyed by a jet dyeing machine.
  • the obtained sheet was soft and anti-buckling, had a high leather-likeness index, fine nap on the surface and an excellent writing effect and was very similar to natural leather nubuck.
  • the elastic polymer (B) penetrated in the sheet layer ( 1 ) and the sheet layer ( 2 ) and all the elastic polymers including the elastic polymer (B) were substantially not bonded to the fibers constituting the sheet layer ( 1 ) and the sheet layer ( 2 ).
  • the elastic polymer (B) was bonded to the elastic polymers constituting the sheet layers.
  • Example 1 The procedure of Example 1 was repeated except that the two sliced unextracted sheets ( 2 ) of Reference Example 2 or the two sliced unextracted sheets ( 3 ) of Reference Example 3 were used in place of the two unextracted sheets ( 1 ) of Reference Example 1.
  • An adhesive composition ( 2 ) comprising 30 parts of Crisbon TA-290 (polyurethane resin of Dainippon Ink and Chemicals, Inc., concentration of 45%), 30 parts of Crisbon TA-265 (polyurethane resin of Dainippon Ink and Chemicals, Inc., concentration of 65%), 40 parts of Crisbon NB-765 (polyurethane resin of Dainippon Ink and Chemicals Inc., concentration of 30%), 10 parts of Coronate 2094 (crosslinking agent of Nippon Polyurethane Industry Co., Ltd.), 3 parts of Crisbon Accel-T (catalyst of Dainippon Ink and Chemicals, Inc.) and 20 parts of methyl ethyl ketone was prepared as an adhesive essentially composed of polyurethane resins (corresponding to the elastic polymer (B)).
  • the 100% elongation stress of a film formed by applying this adhesive composition ( 2 ) to release paper, drying and aging was 588 N/cm 2 .
  • the laminate was obtained in the same manner as in Example 1 except that the unextracted sheet ( 3 ) of Reference Example 3 as an upper layer and the unextracted sheet ( 4 ) of Reference Example 4 as a lower layer were laminated together by the above adhesive composition ( 2 ), and the obtained laminate was extracted, napped and dyed.
  • the obtained sheet was anti-buckling and had a high leather-likeness index and was therefore excellent as a material for shoes.
  • the characteristic property values of the obtained sheet are shown in Table 5.
  • An adhesive composition ( 3 ) comprising 15 parts of Crisbon TA-290 (polyurethane resin of Dainippon Ink and Chemicals, Inc., concentration of 45%), 15 parts of Crisbon TA-265 (polyurethane resin of Dainippon Ink and Chemicals, Inc., concentration of 65%), 80 parts of Crisbon NB-765 (polyurethane resin of Dainippon Ink and Chemicals Inc., concentration of 30%), 8 parts of Coronate 2094 (crosslinking agent of Nippon Polyurethane Industry Co., Ltd.), 3 parts of Crisbon Accel-T (catalyst of Dainippon Ink and Chemicals, Inc.) and 20 parts of methyl ethyl ketone was prepared as an adhesive essentially composed of polyurethane resins (corresponding to the elastic polymer (B)). The 100% elongation stress of a film formed by applying this adhesive composition ( 3 ) to release paper, drying and aging was 883 N/cm 2 .
  • the laminate was obtained in the same manner as in Example 1 except that the unextracted sheet ( 3 ) of Reference Example 3 as an upper layer and the unextracted sheet ( 4 ) of Reference Example 4 as a lower layer were laminated together by the above adhesive composition ( 3 ), and the obtained laminate was extracted, napped and dyed.
  • the obtained sheet was anti-buckling and had a high leather-likeness index and was therefore excellent as a material for shoes.
  • the characteristic property values of the obtained sheet are shown in Table 5.
  • Example 1 The procedure of Example 1 was repeated except that the unextracted sheet ( 3 ) of Reference Example 3 was used as an upper layer and the unextracted sheet ( 2 ) of Reference Example 2 was used as a lower layer in place of the two unextracted sheets ( 1 ) of Reference Example 1.
  • the average thickness of the elastic polymer (B) layer was 0.08 mm, and the obtained sheet had a fine nubuck-like surface appearance and was very soft and suitable for use in shoes and furniture as a leather-like sheet product.
  • the relationship between the elastic polymers and fibers constituting the sheet layers was the same as in Example 1.
  • the characteristic properties of the obtained sheet are shown in Table 5.
  • Example 6 The procedure of Example 6 was repeated except that an adhesive containing air bubbles was prepared by stirring at a high speed at the same time of blowing air into an adhesive composition with using an air foamer and was used in place of the adhesive composition ( 1 ).
  • the average thickness of the elastic polymer (B) layer was 0.10 mm and the apparent density of a sheet formed only from this adhesive containing air bubbles was 0.6 g/cm 3 .
  • the relationship between the elastic bodies and fibers constituting the sheet layers was the same as in Example 1.
  • the characteristic properties of the obtained sheet are shown in Table 5.
  • Example 6 The procedure of Example 6 was repeated except that a sheet having a thickness of 0.45 mm and a substrate density of 0.44 g/cm 3 was formed by processing the unextracted sheet ( 3 ) of Reference Example 3 with a press roll heated at 100° C. and used as an upper layer in stead of using the unextracted sheet ( 3 ) of Reference Example 3 directly.
  • the obtained sheet had slight surface hardness but was anti-buckling and was excellent as a material for shoes.
  • the relationship between the elastic polymers and fibers constituting the sheet layers was the same as in Example 1.
  • the characteristic properties of the obtained sheet are shown in Table 5. TABLE 5 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex.
  • Bonding and extraction were carried out in the same manner as in Example 1 except that the two sliced unextracted sheets ( 5 ) of Reference Example 5 were used in place of the two sliced unextracted sheets ( 1 ) of Reference Example 1.
  • the obtained sheet had large resistance to tension with a shrinkage in width of 3% or less and an elongation in length of 2% or less in the extraction step and had excellent production stability.
  • the surface having coating layer of the obtained sheet was embossed to provide a grain pattern, the surface finished with a polyurethane resin having a 100% elongation stress of 392 N/cm 2 by a 200-mesh gravure roll and rubbed after adding a softening agent.
  • the obtained sheet having a grain layer was soft and anti-buckling, had a high leather-likeness index, finely wrinkles on the surface when it was bent and was very similar to natural leather having a high-grade grain layer.
  • the characteristic property values of the obtained sheet are shown in Table 5.
  • the sheet was inferior as a sheet having a grain layer because large wrinkles were formed on the surface when it was bent.
  • the characteristic property values of this sheet are shown in Table 6.
  • Dimethylformamide was applied to the surface corresponding to the sheet layer ( 1 ) (unextracted sheet ( 7 )) of the obtained sheet by a 200-mesh gravure roll, dried and buffed by a polisher having 400-mesh emery paper to form a napped substrate which was then dyed by a jet dyeing machine.
  • the obtained sheet was soft and anti-buckling, had a high leather-likeness index, fine nap on the surface and an excellent writing effect, and was similar to natural leather nubuck.
  • the present invention there is obtained a leather-like sheet product which has good balance between softness and buckling resistance like natural leather and is deformed round with fine wrinkles when it is bent. According to the production process of the present invention, shrinkage in width can be suppressed in the production process, thereby making it easy to produce a product having a large width.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Laminated Bodies (AREA)
  • Telescopes (AREA)
US09/958,026 2000-02-03 2001-01-29 Leather-like sheety product and production method therefor Abandoned US20030039772A1 (en)

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US20050125907A1 (en) * 2003-12-12 2005-06-16 Kuraray Co., Ltd. Substrate for artificial leathers, artificial leathers and production method of substrate for artificial leathers
US20070169887A1 (en) * 2004-02-26 2007-07-26 Dainippon Ink And Chemicals, Inc. Process for producing leather-like sheet
US20100035023A1 (en) * 2008-08-05 2010-02-11 Matthew Boyd Lake Zoned Elastic Laminate and Method to Manufacture Same
US20110103915A1 (en) * 2007-08-06 2011-05-05 Eyeego, Llc Screw With Breakaway and Methods of Using The Same
US20150050460A1 (en) * 2012-02-29 2015-02-19 Kuraray Co., Ltd. Elastic artificial leather and production method therefor
US12173200B2 (en) 2019-04-04 2024-12-24 Avery Dennison Corporation Reinforced label assembly

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US20060008631A1 (en) * 2002-08-22 2006-01-12 Naohiko Takeyama Leather-like sheet and process for production thereof
KR101173995B1 (ko) 2007-12-11 2012-08-16 코오롱인더스트리 주식회사 복합시트
IT1403385B1 (it) * 2010-12-24 2013-10-17 Polifloor S R L Suporto rivestito tipo finta pelle.
CN103031735B (zh) * 2011-10-08 2015-02-18 隆芳兴业股份有限公司 仿皮革触感织布的制造方法及由其制得的仿皮革触感织布
JP5905716B2 (ja) * 2011-12-26 2016-04-20 株式会社クラレ 加飾成形用シート、加飾成形体、及び、加飾成形体の製造方法
WO2014156557A1 (ja) * 2013-03-25 2014-10-02 東レ株式会社 接着加工品
CN108215401A (zh) * 2017-12-29 2018-06-29 合肥市安山涂层织物有限公司 一种伸缩性人造革的制造方法

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US20050125907A1 (en) * 2003-12-12 2005-06-16 Kuraray Co., Ltd. Substrate for artificial leathers, artificial leathers and production method of substrate for artificial leathers
US20070169887A1 (en) * 2004-02-26 2007-07-26 Dainippon Ink And Chemicals, Inc. Process for producing leather-like sheet
US7431794B2 (en) * 2004-02-26 2008-10-07 Dainippon Ink And Chemicals, Inc. Process for producing leather-like sheet
US20110103915A1 (en) * 2007-08-06 2011-05-05 Eyeego, Llc Screw With Breakaway and Methods of Using The Same
US20100035023A1 (en) * 2008-08-05 2010-02-11 Matthew Boyd Lake Zoned Elastic Laminate and Method to Manufacture Same
WO2010015982A3 (en) * 2008-08-05 2010-05-27 Kimberly-Clark Worldwide, Inc. Zoned elastic laminate and method to manufacture same
US8222169B2 (en) 2008-08-05 2012-07-17 Kimberly-Clark Worldwide, Inc. Zoned elastic laminate and method to manufacture same
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US10465338B2 (en) * 2012-02-29 2019-11-05 Kuraray Co., Ltd. Elastic artificial leather and production method therefor
US11268237B2 (en) 2012-02-29 2022-03-08 Kuraray Co., Ltd. Elastic artificial leather and production method therefor
US12173200B2 (en) 2019-04-04 2024-12-24 Avery Dennison Corporation Reinforced label assembly

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DE60100527D1 (de) 2003-09-04
KR100648871B1 (ko) 2006-11-24
EP1167619A1 (en) 2002-01-02
CN1183290C (zh) 2005-01-05
ES2203600T3 (es) 2004-04-16
WO2001057307A1 (en) 2001-08-09
TW528826B (en) 2003-04-21
KR20020000788A (ko) 2002-01-05
CN1363005A (zh) 2002-08-07

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