Classifications

• • 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
• • 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
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/20—Heterocyclic amines; Salts thereof
• • 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
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
• • 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
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
• • 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
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/44—Polycarbonates
• • 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
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—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
  • D06N3/12—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

Definitions

• the present invention provides a method for producing a polyurethane foam sheet and a method for producing synthetic leather.
• the problem that the present invention aims to solve is to provide a method for producing a polyurethane foam sheet that has an increased biomass content using biomass raw materials, excellent foam retention properties, and a good texture.
• the present invention provides a method for producing a polyurethane foam sheet, which comprises mixing a moisture-curable polyurethane hot melt resin composition (X) containing a urethane prepolymer (i) which is a reaction product of a polyol (A) and a polyisocyanate (B) with a polyol composition (Y), applying the mixture obtained by mixing the mixture in the form of a sheet onto a substrate, and contacting the mixture in the form of a sheet with water vapor to water-foam the mixture, wherein the polyol (A) contains a biomass-derived polytetramethylene glycol or polycarbonate polyol (a1), a polyol (a2) having an aromatic ring, and a polyester polyol (a3) other than (a2) which is solid at room temperature, and the polyol composition (Y) contains an amine catalyst (y1) having a foaming constant (Kw) of 10 or more.
• the present invention also provides a method for producing synthetic leather having at least a substrate, an adhesive layer, and a skin layer, characterized in that the adhesive layer is obtained by the method for producing a polyurethane foam sheet.
• the method for producing a polyurethane foam sheet of the present invention can provide a polyurethane foam sheet with excellent foam retention and good texture.
• the polyurethane foam sheet of the present invention is made from biomass raw materials and has a high biomass content, making it an environmentally friendly sheet.
• the polyurethane foam sheet also has excellent adhesive properties, making it particularly suitable for use as an adhesive layer for synthetic leather.
• the method for producing a polyurethane foam sheet of the present invention comprises mixing a moisture-curable polyurethane hot melt resin composition (X) containing a urethane prepolymer (i) which is a reaction product of a polyol (A) and a polyisocyanate (B) with a polyol composition (Y), applying the mixture obtained by mixing the mixture in the form of a sheet onto a substrate, and contacting the mixture in the form of a sheet with water vapor to water-foam the mixture, and specific polyols (A) and polyol composition (Y) are used.
• the urethane prepolymer (i) can be a reaction product of a specific polyol (A) and a polyisocyanate (B).
• the polyol (A) contains, as essential components, polytetramethylene glycol or polycarbonate polyol (a1) derived from biomass, polyol (a2) having an aromatic ring, and polyester polyol (a3) other than (a2) that is solid at room temperature, in order to increase the biomass content of the resin and obtain excellent foam retention, texture, and adhesiveness.
• the biomass-derived polytetramethylene glycol or polycarbonate polyol (a1) is an essential component for increasing the biomass content of the resin and for realizing basic physical properties such as excellent mechanical strength of the adhesive film.
• the biomass-derived polytetramethylene glycol is commercially available as, for example, "Bio PTMG” manufactured by Mitsubishi Chemical Corporation.
• polycarbonate polyols made from biomass-derived glycols having 1 to 10 carbon atoms, more preferably 3 to 10, can be used.
• biomass-derived polycarbonate polyol polycarbonate polyols made from biomass-derived glycols having 1 to 10 carbon atoms, more preferably 3 to 10.
• commercially available products include “Benebiol NL-2010DB” manufactured by Mitsubishi Chemical Corporation, “Benebiol NL-3010DB” manufactured by Mitsubishi Chemical Corporation, “Benebiol NL-2000D” manufactured by Mitsubishi Chemical Corporation, and “PCDX222” manufactured by Asahi Kasei Corporation.
• These polycarbonate polyols may be used alone or in combination of two or more kinds.
• the number average molecular weight of the biomass-derived polytetramethylene glycol or polycarbonate polyol (a1) is preferably 500 to 100,000, and more preferably 700 to 50,000.
• the number average molecular weight of the biomass-derived polytetramethylene glycol or polycarbonate polyol (a1) is a value measured by gel permeation chromatography (GPC).
• the amount of the biomass-derived polytetramethylene glycol or polycarbonate polyol (a1) used is preferably 50 to 90% by mass, more preferably 60 to 80% by mass, in the polyol (A).
• the polyol (a2) having an aromatic ring provides excellent flexibility, texture, and adhesion to the film, and examples of the polyol that can be used include polyether polyols having an aromatic ring and polyester polyols having an aromatic ring.
• polyether polyol having an aromatic ring for example, bisphenol A, bisphenol F, and their alkylene oxide adducts can be used. These polyols may be used alone or in combination of two or more. Among these, polyether polyols which are alkylene oxide adducts of bisphenol A are preferred.
• alkylene oxide alkylene oxides having 2 to 8 carbon atoms are preferred, and the number of moles of the alkylene oxide added is preferably 2 to 10 moles, and more preferably 4 to 8 moles.
• polyester polyol having an aromatic ring for example, the reaction product of a compound having a hydroxyl group and a polybasic acid shown below can be used.
• Examples of the compound having a hydroxyl group include ethylene glycol, propylene glycol, 1,4-butanediol, pentanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, hexanediol, neopentyl glycol, hexamethylene glycol, glycerin, trimethylolpropane, bisphenol A, bisphenol F, and alkylene oxide adducts thereof.
• the alkylene oxide is preferably an alkylene oxide having 2 to 8 carbon atoms, and the number of moles of the alkylene oxide added is preferably 2 to 10 moles, and more preferably 4 to 8 moles.
• the polybasic acid may be adipic acid, glutaric acid, pimelic acid, suberic acid, dimer acid, sebacic acid, undecanedicarboxylic acid, hexahydroterephthalic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, etc.
• the number average molecular weight of the polyol (a2) having an aromatic ring is preferably 500 to 10,000, and more preferably 500 to 5,000.
• the number average molecular weight of the polyol (a2) having an aromatic ring is a value measured by gel permeation chromatography (GPC).
• the amount of the aromatic ring-containing polyol (a2) used is preferably 10 to 40% by mass, more preferably 20 to 30% by mass, in the polyol (A).
• the polyester polyol (a3) other than (a2) that is solid at room temperature is an essential component for fixing bubbles, inhibiting penetration of the adhesive into the fabric, and achieving an excellent texture.
• solid at room temperature means that the material does not exhibit fluidity at 25°C.
• the polyester polyol (a3) is preferably at least one selected from the group consisting of polyester polyol (a3-1) made from diethylene glycol and sebacic acid, polyester polyol (a3-2) made from 1,3-propanediol and sebacic acid, polyester polyol (a3-3) made from diethylene glycol, neopentyl glycol, and phthalic acid, and polyester polyol (a3-4) made from diethylene glycol and phthalic acid.
• polyester polyol (a3-1) made from diethylene glycol and sebacic acid
• polyester polyol (a3-2) made from 1,3-propanediol and sebacic acid
• polyester polyol (a3-3) made from diethylene glycol, neopentyl glycol, and phthalic acid
• polyester polyol (a3-4) made from diethylene glycol and phthalic acid.
• polyester polyol (a3) polyester polyol (a3-1) made from diethylene glycol and sebacic acid and/or polyester polyol (a3-2) made from 1,3-propanediol and sebacic acid are preferred in terms of increasing the biomass content of the resin.
• biomass raw materials for the polyester polyols include biomass-derived sebacic acid ("Bio Seb” manufactured by Toyokuni Oil Co., Ltd.), biomass-derived 1,3-propanediol (“SUSTERRA Propanediol” manufactured by Dupont Co., Ltd.), and biomass-derived diethylene glycol ("Bio DEG” manufactured by India Glycols Co., Ltd.), etc., which are commercially available.
• polyester polyol (a3) in terms of obtaining an even more excellent texture, polyester polyol (a3-3) made from diethylene glycol, neopentyl glycol, and phthalic acid, and/or polyester polyol (a3-4) made from diethylene glycol and phthalic acid are preferable, and polyester polyol (a3-3) made from diethylene glycol, neopentyl glycol, and phthalic acid is particularly preferable.
• the diethylene glycol may be derived from petroleum or biomass, but it is preferable to use biomass-derived diethylene glycol in order to increase the biomass content.
• the number average molecular weight of the polyester polyol (a3) is preferably 500 to 10,000, and more preferably 800 to 5,000.
• the number average molecular weight of the polyester polyol (a3) is a value measured by gel permeation chromatography (GPC).
• the amount of the polyester polyol (a3) used is preferably 10 to 30% by mass, more preferably 10 to 20% by mass, in the polyol (A).
• the polyol (A) essentially contains the components (a1) to (a3) described above, but may contain other polyols as necessary.
• the total content of the components (a1) to (a3) in the polyol (A) is preferably 20% by mass or more, and more preferably 50% by mass or more.
• the other polyols may be, for example, polyester polyols other than (a2) and (a3), polycarbonate polyols other than (a1), polyether polyols other than (a1), polybutadiene polyols, polyacrylic polyols, etc. These polyols may be used alone or in combination of two or more. These polyols may be used alone or in combination of two or more.
• the number average molecular weight of the other polyols is, for example, 500 to 100,000.
• the number average molecular weight of the other polyols is a value measured by gel permeation chromatography (GPC).
• polyisocyanate (B) for example, aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate can be used.
• aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate
• polyisocyanates may be used alone or in combination of two or more.
• aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred, in that good adhesiveness, reactivity, and mechanical properties can be obtained.
• the urethane prepolymer (i) can be produced, for example, by dropping the polyol (A) into a reaction vessel containing the polyisocyanate (B), heating the vessel, and reacting the polyisocyanate (B) under conditions in which the isocyanate groups of the polyisocyanate (B) are in excess of the hydroxyl groups of the polyol (A).
• the equivalent ratio ([NCO/OH]) of the isocyanate groups in the polyisocyanate (B) to the hydroxyl groups in the polyol (A) is preferably 1.1 to 5.0, more preferably 1.5 to 3.5, from the standpoints of adhesion, texture, and mechanical strength.
• the isocyanate group content (hereinafter abbreviated as "NCO %) of the urethane prepolymer (i) is preferably 1.1 to 5.0 mass %, more preferably 1.5 to 3.5 mass %, from the viewpoints of adhesion, texture, and mechanical strength.
• the isocyanate group content of the urethane prepolymer (i) is a value measured by potentiometric titration in accordance with JIS K1603-1:2007.
• the moisture-curable polyurethane hot melt composition (X) used in the present invention contains the urethane prepolymer (i) as an essential component, but may contain other additives as necessary.
• the other additives that can be used include, other than the polyol composition (Y) described below, for example, silane coupling agents, thixotropy imparting agents, antioxidants, plasticizers, fillers, dyes, pigments, waxes, etc. These additives may be used alone or in combination of two or more kinds.
• the isocyanate groups of the urethane prepolymer (i) react with the polyol in the polyol composition (Y), moderately increasing the viscosity and fixing the bubbles in the polyurethane foam sheet when foamed with water, and also contributing to the flexibility, mechanical strength, and durability of the resulting polyurethane foam sheet.
• polyol for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, etc. can be used. These compounds may be used alone or in combination of two or more.
• the content of the polyol in the polyol composition (Y) is preferably 0.1 to 10.0% by mass, and more preferably 0.5 to 5.0% by mass.
• the polyol composition (Y) contains an amine catalyst (y1) having a foaming constant (Kw) of 10 or more.
• Kw foaming constant
• the foaming constant (Kw) of the amine catalyst (y1) refers to the catalytic activity constant (L 2 /(wq.mol ⁇ hr)) of toluene diisocyanate (TDI) and water.
• TDI toluene diisocyanate
• the mass ratio is preferably 1/1 to 1/10, and more preferably 1/1 to 1/5, since this provides a more excellent texture.
• the amount of the amine catalyst (y1) used is preferably 1.0 to 20 mass % in the polyol composition (Y), and more preferably 1.0 to 10 mass %.
• the polyol composition (Y) may contain other additives in addition to the amine catalyst (y1).
• the other additives include catalysts other than (y1), foam stabilizers, flame retardants, antistatic agents, fillers, conductive agents, moisture absorbents, inert gases, silane coupling agents, thixotropic agents, tackifiers, waxes, plasticizers, heat stabilizers, light stabilizers, pigments, and hydrolysis inhibitors, which may be used alone or in combination. These additives may be used alone or in combination of two or more.
• the amount of the polyol composition (Y) used is preferably 1.0 to 50 parts by mass, and more preferably 1.0 to 35 parts by mass, per 100 parts by mass of the moisture-curable polyurethane hot-melt resin composition (X).
• the method for producing a polyurethane foam sheet of the present invention includes the steps of mixing the moisture-curable polyurethane hot-melt resin composition (X) that has been heated and melted at, for example, 70 to 150°C with the polyol composition (Y), applying the mixture obtained in the form of a sheet onto a substrate, and contacting the sheet-like mixture with water vapor to water-foam the mixture.
• the moisture-curable polyurethane hot melt resin composition (X) and the polyol composition (Y) can be mixed, for example, using a high-speed mixing head or a disperser.
• the mixture can be applied in the form of a sheet onto a substrate such as release paper using, for example, a roll coater, a spray coater, a T-die coater, a knife coater, etc.
• the thickness of the mixture applied in the form of a sheet can be, for example, 50 to 500 ⁇ m.
• water foaming means that the water contained in the water vapor is used as a foaming agent, and the isocyanate groups in the urethane prepolymer (i) used in this invention react with the water to generate carbon dioxide gas, resulting in foaming.
• the conditions for contacting the water vapor include, for example, setting the ambient temperature of the surface of the sheet-like mixture to, for example, 20 to 120°C, preferably less than 80°C, and more preferably 20 to 35°C, setting the ambient humidity of the surface of the sheet-like mixture to, for example, 50% or more, preferably 60% or more and less than 95%, and more preferably 60 to 85%, and setting the humidification time to, for example, 0.5 seconds to 10 minutes.
• the method of contacting with water vapor can be a method using a humidification chamber, a water vapor spraying device, etc., which can maintain constant conditions of the ambient temperature, ambient humidity, and humidification time on the surface of the mixture, and more preferably, a device that generates saturated water vapor is used, since the water vapor is less likely to cool and turn into water droplets while circulating in the production line.
• a pressure belt press, nip roll, flat press, etc. in combination after the humidification treatment.
• the material After contact with the water vapor, the material may be aged for 0.5 to 3 days, for example, at a temperature of 20 to 80°C and a relative humidity of 50 to 90%.
• the method for producing a polyurethane foam sheet of the present invention makes it possible to obtain a polyurethane foam sheet having a good texture. Furthermore, since the polyurethane foam sheet also has excellent adhesive properties, it can be particularly suitably used as an adhesive layer for synthetic leather.
• the synthetic leather has at least a base material, an adhesive layer, and a surface layer, and the adhesive layer is obtained by the manufacturing method of the polyurethane foam sheet.
• the substrate may be, for example, a fiber substrate such as a nonwoven fabric, woven fabric, knitted fabric, etc., made of polyester fiber, polyethylene fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, glass fiber, carbon fiber, or a blend of these fibers; a nonwoven fabric impregnated with a resin such as polyurethane resin; a nonwoven fabric further provided with a porous layer; a resin substrate such as thermoplastic urethane (TPU), as well as genuine leather, split leather, etc.
• a fiber substrate such as a nonwoven fabric, woven fabric, knitted fabric, etc., made of polyester fiber, polyethylene fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, glass fiber, carbon fiber, or a blend of these fibers
• a nonwoven fabric impregnated with a resin such as polyurethane resin
• Examples of materials that can be used to form the skin layer include water-based urethane resin, solvent-based urethane resin, solventless urethane resin, water-based acrylic resin, solvent-based acrylic resin, solventless acrylic resin, solvent-based silicone resin, water-based silicone resin, solventless silicone resin, vinyl chloride resin, thermoplastic polyurethane resin, thermoplastic polyester resin, thermoplastic amide resin, thermoplastic polyolefin resin, etc. These materials can be used alone or in combination of two or more.
• the synthetic leather can be produced, for example, by mixing the moisture-curable polyurethane hot melt resin composition (X) and the polyol composition (Y) to form a sheet-like mixture on a surface layer formed on release paper, contacting the sheet-like mixture with water vapor to foam the mixture as described above, and bonding the resulting foamed sheet to an adhesive layer and the substrate.
• a surface treatment layer (top coat layer) may be provided on the skin layer.
• the mixture was dried under reduced pressure at 110° C. and dehydrated until the moisture content was 0.05% by mass or less.
• 33 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110°C, and the reaction was continued for 2 hours until the isocyanate group content became constant, thereby obtaining a urethane prepolymer (i-1) having an NCO% of 3.32% by mass and a biomass degree of 60.2% by mass, which was used as a moisture-curable polyurethane hot-melt resin composition (X1).
• urethane prepolymer having an NCO% of 3.36% by mass and a biomass content of 80% by mass, which was used as a moisture-curable polyurethane hot-melt resin composition (XR2).
• the number average molecular weight of the polyols used in the synthesis examples and the like is a value measured by gel permeation chromatography (GPC) under the following conditions.
• Measurement device High-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used, connected in series. "TSKgel G5000” (7.8mm I.D. x 30cm) x 1 "TSKgel G4000” (7.8mm I.D. x 30cm) x 1 "TSKgel G3000” (7.8mm I.D. x 30cm) x 1 "TSKgel G2000" (7.8mm I.D.
• Preparation Example 1 ⁇ Method of producing skin film> A pigment (DILAC BLACK HS6001 (DIC)) and 0.3 parts by mass of an antifoaming agent (TEGO Foamex 800, EVONIK) were mixed with "HYDRAN WLS 230" (DIC), an aqueous urethane resin for the surface layer of synthetic leather, and the mixture was uniformly applied to a release paper ("EV 130TPD", LINTEC Corporation) using a comma coater so that the application amount was 100 g/ m2 (wet). The mixture was then dried at 70°C for 2 minutes and then at 120°C for 2 minutes to produce a surface film with a thickness of 30 ⁇ m.
• DIC DILAC BLACK HS6001
• EVONIK antifoaming agent
• Example 1 ⁇ Method of manufacturing polyurethane foam sheet>
• the moisture-curable polyurethane hot melt resin composition (X1) obtained in Synthesis Example 1 was heated to 120°C and melted, and 100 parts by mass of the urethane prepolymer (i-1) was mixed with 2.0 parts by mass of 1,4-butanediol (hereinafter abbreviated as "14BG"), 0.15 parts by mass of PMDETA, 0.15 parts by mass of TEDA, and 1.0 part by mass of a silicone foam stabilizer (manufactured by Dow Corning Corporation, "SF-2962", hereinafter abbreviated as "SF2962”) to prepare a resin.
• 14BG 1,4-butanediol
• PMDETA 0.15 parts by mass of PMDETA
• TEDA 0.15 parts by mass of TEDA
• a silicone foam stabilizer manufactured by Dow Corning Corporation
• 3.3 parts by mass of the polyol composition was stirred and mixed in a Homo Disper at 6,000 rpm for 20 seconds, and then immediately applied to a release paper ("DK-100" manufactured by Lintec Corporation) using an applicator to a thickness of 200 ⁇ m.
• a polyethylene film having a thickness of 50 ⁇ m was then laminated thereon, followed by humidifying with water vapor for 1 minute in an atmosphere at 30° C. and a humidity of 80%, and then allowing to stand for 1 day in an environment at a temperature of 23° C. and a humidity of 65% to obtain a polyurethane foam sheet.
• the mixture was stirred and mixed at 6,000 rpm for 20 seconds with a homodisper, and immediately applied to the surface film in a thickness of 200 ⁇ m using an applicator. After bonding a rayon napped cloth, the mixture was moistened with water vapor for 1 minute in an atmosphere of 30 ° C. and 80% humidity, and left for 1 day in an environment of 23 ° C. and 65% humidity to obtain a synthetic leather.
• Example 2 A polyurethane foam sheet and a synthetic leather were obtained in the same manner as in Example 1, except that the type of moisture-curable polyurethane hot-melt resin composition (X1) was changed to the moisture-curable polyurethane hot-melt resin composition (X2).
• Example 3 A polyurethane foam sheet and a synthetic leather were obtained in the same manner as in Example 1, except that the type of moisture-curable polyurethane hot-melt resin composition (X1) was changed to the moisture-curable polyurethane hot-melt resin composition (X3).
• Example 4 A polyurethane foam sheet and a synthetic leather were obtained in the same manner as in Example 1, except that the type of moisture-curable polyurethane hot-melt resin composition (X1) was changed to the moisture-curable polyurethane hot-melt resin composition (X4).
• Example 5 A polyurethane foam sheet and synthetic leather were obtained in the same manner as in Example 2, except that HMTETA was used instead of PMDETA.
• Example 6 A polyurethane foam sheet and synthetic leather were obtained in the same manner as in Example 2, except that PMDPTA was used instead of PMDETA.
• Comparative Example 2 A polyurethane foam sheet and synthetic leather were obtained in the same manner as in Comparative Example 1, except that the type of moisture-curable polyurethane hot-melt resin composition (XR1) was changed to the moisture-curable polyurethane hot-melt resin composition (XR2).
• Examples 1 to 6 polyurethane foam sheets were obtained that had a high biomass content, excellent foam retention, and excellent texture.
• Comparative Examples 1 and 2 which both use polyol (A) and polyol composition (Y) other than those specified in the present invention, had poor foam retention and texture.
• Comparative Example 3 is an embodiment in which a polyol (A) other than that specified in the present invention is used and no polyol composition (Y) is used, but the foam retention and texture were significantly poor.

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• Chemical & Material Sciences (AREA)
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• Health & Medical Sciences (AREA)
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• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Polyurethanes Or Polyureas (AREA)

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• 2023
  • 2023-06-08 JP JP2024555172A patent/JP7658518B2/ja active Active
  • 2023-06-08 WO PCT/JP2023/021300 patent/WO2024122084A1/ja not_active Ceased
  • 2023-06-08 CN CN202380065985.3A patent/CN119816535A/zh active Pending

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