WO2021131590A1 - 銀付皮革様シート - Google Patents

銀付皮革様シート Download PDF

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Publication number
WO2021131590A1
WO2021131590A1 PCT/JP2020/045140 JP2020045140W WO2021131590A1 WO 2021131590 A1 WO2021131590 A1 WO 2021131590A1 JP 2020045140 W JP2020045140 W JP 2020045140W WO 2021131590 A1 WO2021131590 A1 WO 2021131590A1
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WIPO (PCT)
Prior art keywords
polyurethane
adhesive layer
silver
leather
sulfate
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2020/045140
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English (en)
French (fr)
Japanese (ja)
Inventor
真人 割田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
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 US17/757,783 priority Critical patent/US12312740B2/en
Priority to EP20908124.9A priority patent/EP4083314A4/en
Priority to CN202080090255.5A priority patent/CN114867908B/zh
Priority to JP2021567144A priority patent/JP7550172B2/ja
Priority to KR1020227020604A priority patent/KR102860170B1/ko
Publication of WO2021131590A1 publication Critical patent/WO2021131590A1/ja
Anticipated expiration legal-status Critical
Ceased 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
    • C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium groups or groups forming them
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B5/02—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 structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0025—Rubber threads; Elastomeric fibres; Stretchable, bulked or crimped fibres; Retractable, crimpable fibres; Shrinking or stretching of fibres during manufacture; Obliquely threaded fabrics
    • D06N3/0027—Rubber or elastomeric fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0036—Polyester fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0065—Organic pigments, e.g. dyes, brighteners
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
    • 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
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
    • 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
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

Definitions

  • the present invention relates to a leather-like sheet with silver having excellent yellowing resistance.
  • a phenolic antioxidant such as butylated hydroxytoluene (BHT) is blended in order to prevent resin deterioration due to oxidation.
  • BHT butylated hydroxytoluene
  • Patent Document 1 discloses a polyurethane product in which a polyurethane product composed of a polymer mainly composed of a polyurethane elastomer is treated with an organic acid or an inorganic acid and the pH of the polyurethane is in the range of 6.9 to 3.5. To do. Further, Patent Document 1 describes that phenolic yellowing is likely to be caused in alkalinity. It is also stated that the addition of antioxidants and light-resistant stabilizers tends to make polyurethane alkaline.
  • Patent Document 2 yellowing is suppressed by applying an aqueous apple acid solution to white shoes made of white canvas (fiber) or synthetic resin, leather, shoelaces, and soles made of polyurethane. Disclose that it will be done.
  • Patent Document 3 is a polyurethane foam obtained by reacting a polyol and a polyisocyanate in the presence of water and an amine catalyst, and the hydrolyzable ester which was a component of the compounding raw material is hydrolyzed.
  • a refractory polyurethane foam containing an acid component and exhibiting a pH in an acidic range.
  • Patent Document 1 describes a polyurethane product in which the pH of polyurethane is adjusted to the range of 6.9 to 3.5 by wet-coagulating polyurethane from an organic solvent solution of solvent-based polyurethane and then treating it with an organic acid or an inorganic acid. Disclose that it manufactures.
  • a method is a technique applied to solid polyurethanes. Therefore, when a polyurethane adhesive layer is formed by applying a polyurethane aqueous solution and drying it, and another base material is attached to the polyurethane adhesive layer for adhesion, an organic acid or an inorganic acid permeates into the inside of the polyurethane adhesive layer. It was difficult to get it done.
  • Patent Document 2 discloses a method of applying an aqueous apple acid solution to white shoes made of white canvas or synthetic resin, a shoelace, and a sole made of polyurethane.
  • aqueous solution of malic acid is directly applied to the polyurethane product, there is a concern that the polyurethane product is attacked by malic acid and causes discoloration. Further, it cannot be applied to a step of forming a polyurethane adhesive layer by applying a polyurethane aqueous liquid and drying it, and adhering another base material to the polyurethane adhesive layer.
  • Patent Document 3 is a polyurethane foam obtained by reacting a polyol and a polyisocyanate in the presence of water and an amine catalyst, in which a hydrolyzable ester, which is a component of the compounding raw material, is hydrolyzed.
  • a refractory polyurethane foam containing an acid component and exhibiting a pH in an acidic range.
  • the applicable process of such a method is also limited, and a polyurethane adhesive layer is formed by applying a polyurethane aqueous liquid and drying, and another base material is attached to and adhered to the polyurethane adhesive layer. It could not be applied to various processes.
  • the water-based polyurethane formed from the polyurethane aqueous liquid used for coating and laminating adhesives is required to have high cohesive force in order to maintain high adhesiveness with the base material.
  • urethane bonds and urea bonds for increasing the proportion of hard segments tended to be contained in a high proportion.
  • Urethane bonds and urea bonds contain nitrogen atoms with unshared electron pairs. Therefore, when the ratio of urethane bond or urea bond is too high, the basicity of the aqueous polyurethane becomes high, and there is a tendency that phenolic yellowing is more likely to occur.
  • no means has been proposed for effectively suppressing the phenolic yellowing of water-based polyurethanes used in such coatings and laminate adhesives.
  • the present invention provides a leather-like sheet with silver that can suppress the phenolic yellowing of the polyurethane adhesive layer in a leather-like sheet with silver having a polyurethane adhesive layer mainly containing water-based polyurethane formed by using an aqueous polyurethane liquid.
  • the purpose is to do.
  • One aspect of the present invention is a silver-coated leather-like sheet including a fiber base material, a polyurethane skin layer bonded to one surface of the fiber base material, and a polyurethane adhesive layer for bonding the fiber base material and the polyurethane skin layer.
  • the polyurethane adhesive layer mainly contains water-based polyurethane, contains at least one selected from sulfates and alkyl sulfates in a total of 0.01 to 0.45% by mass in terms of sulfur atoms, and contains BCG ( It is a leather-like sheet with silver whose coloration by the (bromocresol green) solution is equivalent to pH 4.8 or less.
  • Aqueous polyurethane is a polyurethane formed by drying and coagulating a polyurethane aqueous liquid such as a polyurethane emulsion or an aqueous dispersion.
  • a sulfate or an alkyl sulfate hereinafter, also simply referred to as a sulfate compound
  • the aqueous polyurethane dried and coagulated from the aqueous polyurethane solution becomes acidic.
  • the polyurethane adhesive layer forming the leather-like sheet with silver contains a sulfate compound so that the coloration by the BCG solution is equivalent to pH 4.8 or less, the phenolic yellowing of polyurethane, which is likely to be caused in alkalinity, is suppressed. Can be done.
  • at least one selected from sulfates and alkyl sulfates is contained in a total of 0.45% by mass or more in terms of sulfur atoms, water absorption is likely to occur, water resistance is lowered, and adhesive strength is lowered. ..
  • the sodium content of the polyurethane adhesive layer is preferably 0.1% by mass or less.
  • Sodium contained in the polyurethane adhesive layer enhances the basicity of the polyurethane adhesive layer and causes phenolic yellowing.
  • the sodium content of the polyurethane adhesive layer is 0.1% by mass or less, it is difficult to increase the basicity and the phenolic yellowing of the polyurethane is suppressed.
  • the water-based polyurethane is an anionic self-emulsifying type polyurethane because the sodium content ratio is easily reduced and the water-based polyurethane is more easily acidified.
  • the leather-like sheet 10 with silver of the present embodiment has a fiber base material 1, a polyurethane skin layer 2 adhered to one surface of the fiber base material 1, a fiber base material 1 and a polyurethane skin layer 2. It is provided with a polyurethane adhesive layer 3 for adhering to.
  • the polyurethane adhesive layer 3 contains mainly water-based polyurethane, contains at least one selected from sulfates and alkyl sulfates in an amount of 0.01 to 0.45% by mass in terms of sulfur atoms, and contains BCG (BCG).
  • BCG BCG
  • the coloration by the bromocresol green) solution is equivalent to pH 4.8 or less.
  • the sodium content is preferably 0.1% by mass or less.
  • the polyurethane skin layer 2 is formed on the paper pattern R.
  • the polyurethane skin layer (hereinafter, also simply referred to as the skin layer) is a polyurethane layer that forms the grain-like skin of a leather-like sheet with silver.
  • the type of polyurethane for forming the skin layer is not particularly limited, and even if the polyurethane layer is mainly composed of water-based polyurethane, which is formed by applying a polyurethane aqueous solution and then drying and solidifying, the organic solvent of the solvent-based polyurethane is used. It may be a solvent-based polyurethane formed by applying a solution and so-called wet coagulation. Of these, water-based polyurethane is preferable because it has a low impact on the environment.
  • the epidermis layer may contain a coloring pigment and other additives, if necessary.
  • the thickness of the epidermis layer is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 20 to 100 ⁇ m. Further, the epidermis layer may have a single-layer structure or a multi-layer structure composed of a plurality of polyurethane layers laminated and formed in separate steps.
  • the process of forming the polyurethane adhesive layer (hereinafter, also simply referred to as the adhesive layer) will be described.
  • the surface of the skin layer 2 formed on the release paper R is coated with the polyurethane aqueous liquid 3a to which the sulfate compound is added.
  • the coating method of the polyurethane aqueous liquid 3a is not particularly limited. Specifically, for example, a knife coater, a bar coater, a roll coater and the like are appropriately used. Then, the coating film of the coated polyurethane aqueous liquid 3a is dried using an infrared dryer or the like to form the adhesive layer 3.
  • the thickness of the adhesive layer is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 20 to 100 ⁇ m.
  • the adhesive layer 3 formed on the release paper R is bonded and pressed on the surface of the fiber base material 1 prepared in advance, and then the adhesive layer is formed. By curing 3, the skin layer 2 is adhered to the fiber base material 1.
  • the fiber base material is mainly non-woven fabric, woven fabric, knitted fabric, or a sheet combining them, which has been conventionally used in the production of leather-like sheets such as artificial leather and synthetic leather, and is further higher if necessary.
  • a fiber base material impregnated with a molecular elastic material is used without particular limitation.
  • a non-woven fabric particularly a fiber base material containing a non-woven fabric containing ultrafine fibers having a fineness of 0.5 dtex or less impregnated with a polymer elastic body, provides a dense and highly mechanically strong leather-like sheet. It is preferable because it is easy.
  • the type of resin forming the fiber is not particularly limited.
  • Specific examples of the resin forming the fiber include polyester resins such as polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate (PBT), and polyester elastomer; polyamide 6, polyamide 66, polyamide 610, and aromatic polyamide.
  • Polyamide resin such as polyamide elastomer; Acrylic resin; Olefin resin; Synthetic fibers such as polyvinyl alcohol resin, various natural fibers, semi-synthetic fibers and the like can be mentioned. These may be used alone or in combination of two or more.
  • the fiber base material may contain a polymer elastic body impregnated with impregnation.
  • the type of the polymer elastic body impregnated and applied to the fiber base material is not particularly limited, but specifically, for example, acrylic such as polyurethane, acrylonitrile-butadiene copolymer, acrylic acid ester, or methacrylic acid ester copolymer.
  • acrylic such as polyurethane, acrylonitrile-butadiene copolymer, acrylic acid ester, or methacrylic acid ester copolymer.
  • examples thereof include various polymer elastic bodies such as system elastic bodies, polyamide elastic bodies, and silicone rubbers.
  • the content ratio is not particularly limited, but is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
  • the thickness of the fiber base material is not particularly limited, but is preferably about 0.3 to 2 mm, more preferably about 0.5 to 1 mm.
  • the silver-coated leather-like sheet 10 of the present embodiment can be obtained by peeling the release paper R from the surface of the polyurethane skin layer 2.
  • the water-based polyurethane for forming the adhesive layer of the leather-like sheet with silver in the present embodiment is a polyurethane that has been dried and solidified from a polyurethane aqueous liquid such as a polyurethane emulsion or polyurethane suspension using water as a dispersion medium.
  • the dispersion medium may contain a small amount of an aqueous solvent.
  • the polyurethane adhesive layer contains polyurethane mainly composed of water-based polyurethane.
  • the term "mainly” means that 80% by mass or more, more 90% by mass or more, preferably 100% of the contained polyurethane is water-based polyurethane.
  • the aqueous polyurethane liquid has a molecular structure in which a hydrophilic group-containing monomer unit containing an anionic hydrophilic group such as a carboxyl group or a sulfo group, a cationic hydrophilic group such as an ammonium group, or a nonionic hydrophilic group is used as a constituent unit of polyurethane.
  • Self-emulsifying polyurethane emulsion introduced into the body and emulsified by self-emulsification; forced emulsified polyurethane emulsion emulsified by forced emulsification using a nonionic, cationic or anionic surfactant as an emulsifier.
  • a polyurethane emulsion in which an ionic group introduced into polyurethane and an emulsifier are used in combination can be mentioned.
  • the self-emulsifying polyurethane emulsion is particularly preferable because it is less likely to cause an adverse effect due to the bleeding of the emulsifier.
  • the aqueous polyurethane obtained from the anionic self-emulsifying polyurethane emulsion containing an anionic acidic functional group such as a carboxyl group or a sulfo group as a hydrophilic group-containing monomer unit as a hydrophilic group is more acidic. It is particularly preferable because it is easy to take on.
  • Aqueous polyurethanes can be used, for example, in high molecular weight polyols, organic polyisocyanates, and chain extenders having an average molecular weight of 200 to 6000, as needed, as part of high molecular weight polyols and chain extenders, or as end-capping groups. It is obtained by blending a hydrophilic group-containing monomer in a predetermined molecular ratio and reacting. In addition, the water-based polyurethane has a crosslinked structure, if necessary.
  • high polymer polyol examples include polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and poly (methyltetramethylene glycol) and their copolymers; polybutylene adipatediol and polybutylene sebacate.
  • Polyester-based polyols such as diol, polyhexamethylene adipate diol, poly (3-methyl-1,5-pentylene adipate) diol, poly (3-methyl-1,5-pentylene sebacate) diol, polycaprolactone diol, and The copolymer; a polycarbonate-based polyol such as polyhexamethylene carbonate diol, poly (3-methyl-1,5-pentylene carbonate) diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol, and a copolymer thereof; polyester. Examples thereof include carbonate polyol.
  • a polyfunctional alcohol such as a trifunctional alcohol or a tetrafunctional alcohol, or a short chain alcohol such as ethylene glycol may be used in combination. These may be used alone or in combination of two or more.
  • organic polyisocyanate examples include, for example, hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, aliphatic diisocyanate such as 4,4'-dicyclohexylmethane diisocyanate, and non-yellowing diisocyanate such as alicyclic diisocyanate; 2,4 Examples thereof include aromatic diisocyanates such as -tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate.
  • a polyfunctional isocyanate such as a trifunctional isocyanate may be used in combination. These may be used alone or in combination of two or more. Among these, hexamethylene diisocyanate is preferable because it has an excellent balance between yellowing resistance and mechanical properties.
  • chain extender examples include hydrazine, ethylenediamine, propylenediamine, hexamethylenediamine, nonamethylenediamine, xylylenediamine, isophoronediamine, piperazine and its derivatives, diamines such as adipate dihydrazide and isophthalate dihydrazide; and diethylenetriamine.
  • Triamines such as; tetramines such as triethylenetetramine; ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis ( ⁇ -hydroxyethoxy) benzene, 1,4- Examples thereof include diols such as cyclohexanediol; triols such as trimethylolpropane; pentaols such as pentaerythritol; aminoalcohols such as aminoethyl alcohol and aminopropyl alcohol. These may be used alone or in combination of two or more.
  • triamines such as hydrazine, piperazine, ethylenediamine, hexamethylenediamine, isophoronediamine and its derivatives, and diethylenetriamine in combination from the viewpoint of excellent mechanical properties.
  • monoamines such as ethylamine, propylamine, and butylamine; carboxyl group-containing monoamine compounds such as 4-aminobutanoic acid and 6-aminohexanoic acid; methanol, ethanol, propanol, butanol, etc.
  • Monoamines may be used in combination.
  • the hydrophilic group-containing monomer compounds used for introducing an ionic group for self-emulsification into polyurethane include 2,2-bis (hydroxymethyl) propionic acid and 2,2-bis (hydroxymethyl) butanoic acid. , 2,2-Bis (hydroxymethyl) valeric acid and other carboxyl group-containing diols, and sulfonic acid group-containing diols such as dihydroxyalkyl sulfonic acid can be mentioned.
  • the anionic self-emulsifying polyurethane contains a base as a neutralizing agent for neutralizing the carboxyl group, the sulfo group, etc., which are hydrophilic groups, to improve the hydrophilicity.
  • a neutralizing agent include non-volatile bases such as sodium hydroxide and potassium hydroxide; amines such as trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine and triethanolamine, and volatilization of ammonia and the like.
  • sexual bases can be mentioned.
  • volatile amines having a boiling point of 120 ° C.
  • the neutralizing agent volatilizes and the aqueous polyurethane tends to become acidic. Especially preferable.
  • the acid value of self-emulsifying polyurethane is an index showing the content of hydrophilic groups.
  • the acid value of the self-emulsifying polyurethane is preferably 5 to 40 mgKOH / g, more preferably 10 to 30 mgKOH / g from the viewpoint of excellent balance between water dispersibility and water resistance.
  • Aqueous polyurethane has a sea-island structure having a sea region which is a soft segment having a weak cohesive force mainly formed from a polyol and an island region which is a hard segment having a strong cohesive force mainly formed from a urethane bond or a urea bond. Since the water-based polyurethane is required to have a high cohesive force for maintaining high adhesiveness to the fiber base material, it is preferable to contain a high proportion of urethane bonds and urea bonds that increase the proportion of hard segments. However, since urethane bonds and urea bonds contain nitrogen atoms having unshared electron pairs, if the proportion of urethane bonds and urea bonds is too high, the basicity of polyurethane is increased.
  • the ratio of nitrogen atoms of the water-based polyurethane which is an index of the ratio of the hard segment, is 2.0 to 6.0% by mass, and further 2.5 to 5.0% by mass of the water-based polyurethane. It is preferable because it has an excellent balance between cohesive force and suppression of basicization.
  • the water-based polyurethane may have a crosslinked structure in order to improve water resistance, heat resistance, adhesiveness, mechanical properties and the like.
  • the cross-linked structure of the aqueous polyurethane may be an internal cross-linking, an external cross-linking, or a cross-linked structure combining them.
  • Examples of internal cross-linking include an internal cross-linking structure formed by blending a small amount of a polyfunctional self-crosslinking compound such as a polyisocyanate compound or a polyfunctional blocked isocyanate compound as a copolymerization component.
  • an external cross-linking agent that can react with a functional group such as a carboxyl group of a monomer unit forming polyurethane is added to carry out a cross-linking agent containing two or more functional groups in the molecule.
  • a crosslinked structure can be mentioned.
  • the cross-linking agent include a bifunctional polyisocyanate compound which is a cross-linking agent that forms a cross-linked structure with a hydroxyl group or an amino group, and other functional isocyanate compounds such as biuret type, adduct type, and isocyanurate type; carboxyl group.
  • examples thereof include compounds having a carbodiimide group, an oxazoline group, an epoxy group, a cyclocarbonate group, and an isocyanate group, and a hydrazine derivative or a hydrazide derivative, which are crosslinking agents that form a crosslinked structure.
  • a cross-linking agent which is a compound having a carbodiimide group or an oxazoline group, which is excellent in reactivity and pot life is particularly preferable.
  • cross-linking agent having a carbodiimide group examples include water-dispersed carbodiimide compounds such as “carbodilite E-01”, “carbodilite E-02", and “carbodilite V-04" manufactured by Nisshinbo Holdings.
  • Specific examples of the cross-linking agent having an oxazoline group include water-dispersed oxazoline compounds such as "Epocross K-2010E”, “Epocross K-2020E”, and "Epocross WS-500” manufactured by Nippon Shokubai Co., Ltd. be able to.
  • the blending ratio of the cross-linking agent is selected according to the purpose and the composition of the resin.
  • the active ingredient of the cross-linking agent is preferably 3 to 15% by mass and 5 to 12% by mass with respect to the aqueous polyurethane. Is more preferable.
  • a cross-linking agent is blended, a cross-linking accelerator may be used in combination.
  • it is preferable to complete the cross-linking reaction by drying and coagulating the water-based polyurethane from the aqueous polyurethane liquid and then performing an aging treatment by heat treatment.
  • surfactant compounded for forced emulsification examples include sodium lauryl sulfate, ammonium lauryl sulfate, sodium polyoxyethylene tridecyl ether acetate, sodium dodecylbenzene sulfone, sodium alkyldiphenyl ether disulfonate, and the like.
  • Anionic surfactants such as sodium dioctyl sulfosuccinate; polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene-polyoxypropylene block copolymer, etc.
  • Nonionic surfactants and the like can be mentioned.
  • a so-called reactive surfactant having reactivity may be used.
  • the average dispersed particle size of the aqueous polyurethane dispersed in the aqueous polyurethane liquid is not particularly limited, but may be 0.01 to 1 ⁇ m, more preferably 0.01 to 0.2 ⁇ m, and particularly 0.03 to 0.5 ⁇ m. It is preferable from the viewpoint of dispersion stability.
  • the total content is 0.01 to 0.45% by mass. Any one of these may be used alone or in combination.
  • Examples of the sulfate or alkyl sulfate ester salt to be blended in the aqueous polyurethane solution include sulfuric acid or a salt of an alkyl sulfate ester such as lauryl sulfate and laureth sulfate, preferably an ammonia salt, a volatile amine salt, and a sodium salt.
  • sulfuric acid or a salt of an alkyl sulfate ester such as lauryl sulfate and laureth sulfate, preferably an ammonia salt, a volatile amine salt, and a sodium salt.
  • ammonium sulfate, salts of sulfate and volatile amines such as triethylamine sulfate, ammonium alkylsulfates such as ammonium lauryl sulfate and ammonium laureth sulfate, alkyl sulfates and volatile amines such as triethylamine lauryl sulfate and triethylamine laureth sulfate.
  • Examples thereof include salts with and sodium sulfate, and sodium salts of alkyl sulfates such as sodium lauryl sulfate and sodium laureth sulfate. These may be used alone or in combination of two or more.
  • sulfates or alkyl sulfates give the polyurethane adhesive layer, which is formed after drying and solidification, a strong acidity. Further, since the polyurethane aqueous liquid is weakly acidic, it is difficult to reduce the dispersion stability of the aqueous polyurethane.
  • salts of sulfuric acid or alkyl sulfates and ammonia or volatile amines are removed by volatilizing ammonia and volatile amines during dry coagulation by heating aqueous polyurethane. Therefore, it is preferable because it tends to be more acidic.
  • sodium sulfate or a non-volatile amine salt the basic component of the water-based polyurethane remains even after drying and solidifying by heating the water-based polyurethane, so that the basicity of the adhesive layer tends to be high.
  • the total ratio of the sulfate and the alkyl sulfate in the formed polyurethane adhesive layer is 0.01 to 0.45% by mass and 0.03 to 0.35% by mass in terms of sulfur atoms. Is preferable.
  • the content ratio of these sulfate compounds contained in the polyurethane adhesive layer is less than 0.01% by mass in terms of sulfur atoms, the polyurethane adhesive layer is less likely to be sufficiently acidified. Further, when the content ratio of these sulfate compounds contained in the polyurethane adhesive layer exceeds 0.45% by mass in terms of sulfur atoms, the water resistance of the polyurethane adhesive layer is lowered.
  • the polyurethane adhesive layer to be formed preferably has a sodium content of 0.1% by mass or less, more preferably 0.07% by mass or less.
  • Aqueous polyurethanes may contain sodium derived from the raw material. Specifically, for example, sodium contained in a hydrophilic group-containing monomer compound such as sodium dihydroxyalkylsulfonate used for producing anionic self-emulsifying polyurethane; sodium lauryl sulfate, polyoxyethylene tridecyl ether sodium acetate, dodecylbenzene.
  • Sodium contained in surfactants such as sodium sulfonate, sodium alkyldiphenyl ether disulfonate, sodium dioctyl sulfosuccinate; sodium contained in thickeners such as sodium polyacrylate; may contain sodium such as.
  • sodium content of the polyurethane adhesive layer exceeds 0.1% by mass, the effect of improving the acidity by containing the sulfate compound is reduced.
  • the sodium content of the polyurethane adhesive layer is low or when sodium is not substantially contained, the polyurethane adhesive layer is likely to be acidified, and the phenolic yellowing of the polyurethane adhesive layer is less likely to occur. Therefore, it is preferable that the polyurethane adhesive layer does not contain sodium (0% by mass), and the content ratio of sodium inevitably contained is 0.1% by mass or less, and further 0.07% by mass or less. Is preferable.
  • the acidity of the polyurethane adhesive layer thus formed is such that the coloration by the BCG (bromocresol green) solution evaluated as described later is equivalent to pH 4.8 or less, pH 3.8 to 4.7, and further. Is preferably equivalent to pH 3.9 to 4.6. When the coloration exceeds pH 4.8, the effect of suppressing phenolic yellowing becomes insufficient. Further, when the pH equivalent of the coloration is too low, the polyurethane adhesive layer tends to be easily deteriorated by the acid.
  • BCG bromocresol green
  • the solid content concentration of the aqueous polyurethane liquid is not particularly limited, but 20 to 65% by mass, more preferably 30 to 60% by mass is preferable from the viewpoint of excellent balance between dispersion stability and high concentration.
  • the leather-like sheet with silver of the present embodiment formed in this way includes a polyurethane adhesive layer that is less likely to cause phenolic yellowing.
  • the polyurethane adhesive layer includes antioxidants, ultraviolet absorbers, pigments, dyes, antistatic agents, flame retardants, anti-adhesive agents, etc., if necessary. It may contain various additives such as a filler.
  • the BCG solution has a yellow to blue color gamut in the pH range of 3.8 to 5.4.
  • a 1 cm square test piece was cut out from the leather-like sheet with silver produced in each example.
  • the immersion time was set in the range of 5 to 60 minutes while observing the colored state.
  • the test piece after immersion was taken out, washed lightly with water, wiped off excess water, and dried at room temperature for 24 hours. Then, the cross section of the test piece colored by immersion was observed with a microscope. Then, the corresponding pH of the polyurethane adhesive layer was specified by comparing the color of the polyurethane adhesive layer with the color of the BCG solution measured by the pH meter.
  • test pieces were prepared from each leather-like sheet with silver.
  • Peeling strength retention rate (%) Peeling strength (Wet) / Peeling strength (Dry) x 100
  • aqueous polyurethane emulsion, cross-linking agent, auxiliary agent, etc. used in this example will be collectively described below.
  • Crosslinking agent Carbodilite V-04 manufactured by Nisshinbo Chemical Co., Ltd.
  • -Isocyanate-based cross-linking agent Hydran Assistor C5 manufactured by DIC Corporation
  • Defoamer SN Deformer 1310 (manufactured by San Nopco Ltd.)
  • Leveling agent BKY-348 (manufactured by Big Chemie Japan Co., Ltd.)
  • Thickener Adecanol UH-541VF (manufactured by ADEKA Corporation)
  • White pigment titanium oxide aqueous dispersion, solid content concentration 65%
  • Example 1 Each component was mixed with the following composition to prepare a coating liquid for the epidermis layer and a coating liquid 1 for the adhesive layer.
  • (Epidermis layer coating liquid) 100 parts of polyurethane emulsion for forming the epidermis layer (parts by mass, the same applies hereinafter) ⁇ Defoamer 0.3 parts ⁇ Leveling agent 0.3 parts ⁇ White pigment 10 parts ⁇ Thickener 2.0 parts (Coating liquid 1 for adhesive layer) ⁇ 100 parts of anionic self-emulsifying polyurethane A ⁇ 15 parts of carbodiimide-based cross-linking agent ⁇ 4.6 parts of ammonium sulfate (10% by mass aqueous solution) ⁇ 0.8 parts of thickener
  • the epidermis layer coating liquid is applied to the release surface of the release paper at a WET adhesion amount of 120 g / m 2 , and the film is dried by heating in a dryer at 90 ° C. for 5 minutes to dry the epidermis layer film having a thickness of 40 ⁇ m. It was created.
  • the adhesive layer coating liquid 1 is applied to the surface of the skin layer film at a WET adhesion amount of 130 g / m 2 , heated in a dryer at 90 ° C. for 5 minutes to dry, and then on the surface of the fiber base material. It was pressed with a flat plate heat press and bonded.
  • the fiber base material contains a non-woven fabric of 0.1 dtex polyethylene terephthalate (PET) fiber and polyurethane (PU) impregnated in the non-woven fabric, has a PET / PU ratio of 90/10, and has a grain size of 530 g / m 2 . It was a fiber base material having a thickness of 1 mm.
  • the press was performed under the conditions of a temperature of 100 ° C., a pressure of 5 kgf / cm, and 10 seconds. After pressing, the water-based polyurethane A was further crosslinked by aging at 70 ° C. for 72 hours.
  • Example 2 A leather-like sheet with silver was prepared and evaluated in the same manner as in Example 1 except that the adhesive layer coating liquid 2 prepared as follows was used instead of the adhesive layer coating liquid 1. The results are shown in Table 1. (Coating liquid for adhesive layer 2) ⁇ 100 parts of anionic self-emulsifying polyurethane A ⁇ 15 parts of carbodiimide-based cross-linking agent ⁇ 4.0 parts of ammonium lauryl sulfate (25% by mass aqueous solution) ⁇ 0.8 parts of thickener
  • Example 3 A leather-like sheet with silver was prepared and evaluated in the same manner as in Example 1 except that the adhesive layer coating liquid 3 prepared as follows was used instead of the adhesive layer coating liquid 1. The results are shown in Table 1. (Coating liquid for adhesive layer 3) ⁇ 100 parts of anionic self-emulsifying polyurethane A ⁇ 15 parts of carbodiimide-based cross-linking agent ⁇ 0.5 parts of ammonium sulfate (10% by mass aqueous solution) ⁇ 0.8 parts of thickener
  • Example 4 A leather-like sheet with silver was prepared and evaluated in the same manner as in Example 1 except that the adhesive layer coating liquid 4 prepared as follows was used instead of the adhesive layer coating liquid 1. The results are shown in Table 1. (Coating liquid composition for adhesive layer 4) ⁇ 100 parts of anionic self-emulsifying polyurethane A ⁇ 15 parts of carbodiimide-based cross-linking agent ⁇ 9.5 parts of ammonium sulfate (10% by mass aqueous solution) ⁇ 1.2 parts of thickener
  • Example 5 A leather-like sheet with silver was prepared and evaluated in the same manner as in Example 1 except that the adhesive layer coating liquid 5 prepared as follows was used instead of the adhesive layer coating liquid 1. The results are shown in Table 1. (Coating liquid for adhesive layer 5) ⁇ 100 parts of anionic self-emulsifying polyurethane B ⁇ 10 parts of isocyanate-based cross-linking agent ⁇ 0.5 parts of ammonium sulfate (10% by mass aqueous solution) ⁇ 0.8 parts of thickener
  • Example 6 A leather-like sheet with silver was prepared and evaluated in the same manner as in Example 1 except that the adhesive layer coating liquid 6 prepared as follows was used instead of the adhesive layer coating liquid 1. The results are shown in Table 1. (Coating liquid for adhesive layer 6) ⁇ 100 parts of forced emulsified polyurethane C ⁇ 10 parts of isocyanate-based cross-linking agent ⁇ 0.8 parts of thickener
  • Example 7 A leather-like sheet with silver was prepared and evaluated in the same manner as in Example 1 except that the adhesive layer coating liquid 7 prepared as follows was used instead of the adhesive layer coating liquid 1. The results are shown in Table 1. (Coating liquid for adhesive layer 7) ⁇ Forced emulsification type polyurethane D 100 parts ⁇ Isocyanate cross-linking agent 10 parts ⁇ Thickener 0.8 parts
  • Example 1 A leather-like sheet with silver was prepared and evaluated in the same manner as in Example 1 except that the adhesive layer coating liquid 8 prepared as follows was used instead of the adhesive layer coating liquid 1. The results are shown in Table 1. (Coating liquid for adhesive layer 8) ⁇ 100 parts of anionic self-emulsifying polyurethane A ⁇ 15 parts of carbodiimide-based cross-linking agent ⁇ 3 parts of sodium laurate (20% by mass) ⁇ 0.8 parts of thickener
  • Example 3 A leather-like sheet with silver was prepared and evaluated in the same manner as in Example 1 except that the adhesive layer coating liquid 10 prepared as follows was used instead of the adhesive layer coating liquid 1. The results are shown in Table 1. (Coating liquid 10 for adhesive layer) ⁇ 100 parts of anionic self-emulsifying polyurethane A ⁇ 15 parts of carbodiimide-based cross-linking agent ⁇ 12 parts of ammonium sulfate (10% by mass) ⁇ 1.5 parts of thickener
  • Example 5 A leather-like sheet with silver was prepared and evaluated in the same manner as in Example 1 except that the adhesive layer coating liquid 12 prepared as follows was used instead of the adhesive layer coating liquid 1. The results are shown in Table 1. (Coating liquid 12 for adhesive layer) ⁇ 100 parts of forced emulsified polyurethane C ⁇ 10 parts of isocyanate-based cross-linking agent ⁇ 1.0 part of sodium lauryl sulfate (30% by mass) ⁇ 0.8 parts of thickener
  • the sulfate compound obtained in Examples 1 to 7 according to the present invention was contained in the range of 0.01 to 0.45% by mass in terms of sulfur atom, and the sodium content ratio was 0.
  • the retention rate of Wet / Dry peeling strength in the water resistance evaluation was 70% or more, and the water resistance was also maintained.
  • the silver-coated artificial leather provided with the polyurethane adhesive layer obtained in Comparative Example 1 containing sodium laurate which is not a sulfate compound as a salt and having a sodium content of 0.1% by mass is colored by a BCG solution.
  • the silver-coated artificial leather provided with the polyurethane adhesive layer obtained in Comparative Example 2 containing no salt compound has a coloration equivalent to pH 4.9 by the BCG solution, and has a ⁇ b * value of 4 in the evaluation of phenolic yellowing. Phenolic yellowing was remarkable.
  • the artificial leather with silver provided with the polyurethane adhesive layer obtained in Comparative Example 3 in which the content ratio of the sulfate compound was 0.5% by mass in terms of sulfur atoms was difficult to yellow, but Wet / Dry.
  • the retention rate of peeling strength was less than 70%, and the water resistance was low.
  • the silver-coated artificial leather provided with the polyurethane adhesive layer obtained in Comparative Example 4 containing sodium lauryl sulfate as a sulfate compound and having a sodium content of 0.15% by mass has a pH of 5.2 due to the BCG solution. It was considerable, and the phenolic yellowing was remarkable.
  • the silver-coated artificial leather provided with the polyurethane adhesive layer obtained in Comparative Example 5 containing sodium lauryl sulfate as an emulsifier and a sulfate compound and having a sodium content of 0.15% by mass has a pH 5 coloration with a BCG solution. It was equivalent to 0.0, and the phenolic yellowing was remarkable.
  • Fiber base material Polyurethane skin layer 3 Polyurethane adhesive layer 3a Polyurethane aqueous liquid 10 Leather-like sheet with silver R Paper pattern

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CN114867908B (zh) 2024-11-08
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