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
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • 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
• • 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
  • C09J175/06—Polyurethanes from polyesters
• • 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

Definitions

• the present invention relates to a moisture-curable polyurethane resin composition, an adhesive, and a laminate.
• Breathable waterproof functional clothing which has both moisture permeability and waterproofness, is a structure in which a moisture permeable film is bonded to fabric with an adhesive, and urethane adhesives are generally used as the adhesive because of their good adhesion to both the moisture permeable film and the fabric. Furthermore, among the urethane adhesives, the amount of use of solvent-free moisture-curing polyurethane resin compositions is gradually increasing due to recent global regulations on solvent emissions and residual solvents (see, for example, Patent Document 1).
• the problem that the present invention aims to solve is to provide a moisture-curable polyurethane resin composition that uses biomass raw materials to increase the biomass content and has excellent texture and adhesive properties.
• the present invention provides a moisture-curable polyurethane hot-melt resin composition containing a urethane prepolymer (i) having an isocyanate group, which is a reaction product of a polyol (A) and a polyisocyanate (B), characterized in that 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 the (a2) that is solid at room temperature.
• the present invention also provides an adhesive that contains the moisture-curable polyurethane resin composition. Furthermore, the present invention also provides a laminate that has at least a substrate and a cured product of the moisture-curable polyurethane resin composition.
• the moisture-curing polyurethane resin composition of the present invention is made using biomass raw materials, has a high biomass content, and is an environmentally friendly material.
• the moisture-curing polyurethane resin composition of the present invention combines excellent texture and adhesiveness.
• the moisture-curable polyurethane hot melt resin composition used in the present invention contains a urethane prepolymer (i) having an isocyanate group, which is a reaction product of a polyol (A) containing specific polyols and a polyisocyanate (B).
• the polyol (A) contains, as essential components, biomass-derived polytetramethylene glycol or polycarbonate polyol (a1), a polyol (a2) having an aromatic ring, and a polyester polyol (a3) other than (a2) that is solid at room temperature, in order to increase the biomass content of the resin and achieve both excellent 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 the following compound having a hydroxyl group and a polybasic acid 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 preventing the adhesive from penetrating into the fabric and for 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.), which are commercially available products.
• 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).
• aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate can be used.
• polyisocyanates can be used alone or in combination of two or more.
• aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred, in that they provide even better reactivity, mechanical strength, and adhesiveness.
• the amount of polyisocyanate (B) used is preferably 5 to 40 mass % of the total mass of the raw materials constituting the urethane prepolymer (i), and more preferably 10 to 30 mass %.
• the hot melt urethane prepolymer (i) is obtained by reacting the polyol (A) with the polyisocyanate (B), and has an isocyanate group that can form a crosslinked structure by reacting with moisture present in the air or in the substrate to which the moisture-curable polyurethane hot melt resin composition is applied.
• the biomass degree of the hot-melt urethane prepolymer (i) is preferably 40% or more, and more preferably 50 to 80% by mass.
• the biomass degree of the hot-melt urethane prepolymer (i) indicates the total weight ratio of the biomass-derived raw materials used in producing the hot-melt urethane prepolymer (i) to the total weight of the hot-melt urethane prepolymer (i).
• the hot melt urethane prepolymer (i) can be produced, for example, by adding the polyisocyanate (B) to a reaction vessel containing the polyol (A) and reacting them 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 (isocyanate group/hydroxyl group) of the isocyanate group in the polyisocyanate (B) to the hydroxyl group in the polyol (A) is preferably 1.2 to 5, and more preferably 1.5 to 3, in order to obtain even better mechanical strength, texture, and adhesiveness.
• the isocyanate group content (hereinafter abbreviated as "NCO%) of the hot melt urethane prepolymer (i) obtained by the above method is preferably 1.4 to 6, and more preferably 1.8 to 4.0, in order to obtain even better mechanical strength, texture, and adhesiveness.
• the NCO% of the hot melt urethane prepolymer (i) is a value measured by potentiometric titration in accordance with JIS K1603-1:2007.
• the moisture-curable polyurethane hot melt resin composition used in the present invention contains the urethane prepolymer (i) as an essential component, but other additives may also be used as necessary.
• the other additives that can be used include, for example, light resistance stabilizers, curing catalysts, tackifiers, plasticizers, stabilizers, fillers, dyes, pigments, fluorescent brighteners, foam stabilizers, silane coupling agents, waxes, thermoplastic resins, etc. These additives may be used alone or in combination of two or more.
• the laminate of the present invention has at least a fabric and a cured product of the moisture-curable polyurethane hot melt resin composition.
• the substrate may be, for example, a plastic substrate; a glass substrate; wood; 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 a polyurethane resin; or a nonwoven fabric further provided with a porous layer.
• a plastic substrate such as a plastic substrate; a glass substrate; wood; 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
• Methods for applying the moisture-curable polyurethane hot melt resin composition include, for example, methods using a roll coater, knife coater, spray coater, gravure roll coater, screen print coater, comma coater, T-die coater, applicator, dispenser, etc.
• the moisture-curable polyurethane hot melt resin composition After the moisture-curable polyurethane hot melt resin composition is applied, it can be aged and cured by known methods.
• the amount of the cured product of the moisture-curable urethane hot melt resin composition applied is, for example, in the range of 5 to 100 g/ m2 .
• the moisture-curable polyurethane hot melt resin composition of the present invention is used as an adhesive for moisture-permeable waterproof functional clothing.
• the moisture-curable polyurethane hot melt resin composition is preferably intermittently applied by a gravure roll coater, a rotary screen, or a dispenser, and the fabric and a known moisture-permeable film are bonded together.
• the amount of application of the moisture-curable polyurethane hot melt resin composition in this case is, for example, in the range of 5 to 100 g/ m2 .
• Example 1 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 70 parts by mass of biomass-derived polytetramethylene glycol ("Bio PTMG” manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000), 20 parts by mass of a polyether polyol having an aromatic ring (a polyether polyol which is an adduct of 6 moles of propylene oxide of bisphenol A, number average molecular weight: 508), and 10 parts by mass of a biomass-derived polyester polyol (a reaction product of biomass-derived sebacic acid ("Bio Seb” manufactured by Toyokuni Oil Co., Ltd., number average molecular weight: 2,000) and biomass-derived diethylene glycol ("Bio DEG” manufactured by India Glycols), number average molecular weight: 2,000), and dried under reduced pressure at 110° C.
• Bio PTMG biomass-derived polytetramethylene glycol
• Bio PTMG biomass
• Example 2 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 70 parts by mass of biomass-derived polytetramethylene glycol ("Bio PTMG” manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000), 20 parts by mass of polyester polyol having an aromatic ring (a reaction product of 6 moles of propylene oxide adduct of bisphenol A, isophthalic acid, and biomass-derived sebacic acid ("Bio Seb” manufactured by Toyokuni Oil Co., Ltd.), number average molecular weight: 2,000), and 10 parts by mass of biomass-derived polyester polyol (a reaction product of biomass-derived sebacic acid ("Bio Seb” manufactured by Toyokuni Oil Co., Ltd.) and biomass-derived diethylene glycol ("Bio DEG” manufactured by India Glycols Co., Ltd.), number average molecular weight: 2,000), and dried under reduced pressure at 110 ° C.
• Bio PTMG
• a urethane prepolymer (i-2) having an NCO% of 3.33% by mass and a biomass degree of 65.4% by mass was used as a moisture-curable polyurethane hot-melt resin composition.
• Example 3 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser was charged with 70 parts by mass of biomass-derived polytetramethylene glycol ("Bio PTMG” manufactured by Mitsubishi Chemical Corporation), 20 parts by mass of a polyester polyol having an aromatic ring (a reaction product of a propylene oxide 6-mol adduct of bisphenol A, isophthalic acid, and biomass-derived sebacic acid (“Bio Seb” manufactured by Toyokuni Oil Mills), number average molecular weight; 2,000), and 10 parts by mass of a biomass-derived polyester polyol (a reaction product of biomass-derived 1,3-propanediol (“SUSTERRA Propanediol” manufactured by DuPont) and biomass-derived sebacic acid (“Bio Seb” manufactured by Toyokuni Oil Mills), number average molecular weight; 2,000), and dried under reduced pressure at 110° C.
• Bio PTMG biomass-derived polyte
• Example 4 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 70 parts by mass of biomass-derived polytetramethylene glycol ("Bio PTMG” manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000), 20 parts by mass of polyester polyol having an aromatic ring (a reaction product of 6 moles of propylene oxide adduct of bisphenol A, isophthalic acid, and biomass-derived sebacic acid ("Bio Seb” manufactured by Toyokuni Oil Co., Ltd.), number average molecular weight: 2,000), and 10 parts by mass of biomass-derived polyester polyol (a reaction product of diethylene glycol derived from biomass ("Bio DEG” manufactured by India Glycols), neopentyl glycol, and orthophthalic acid, number average molecular weight: 1,000), and dried under reduced pressure at 110 ° C.
• Bio PTMG biomass-derived polytetramethylene glycol
• Example 5 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 70 parts by mass of biomass-derived polytetramethylene glycol ("Bio PTMG” manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000), 20 parts by mass of polyester polyol having an aromatic ring (a reaction product of 6 moles of propylene oxide adduct of bisphenol A, isophthalic acid, and biomass-derived sebacic acid ("Bio Seb” manufactured by Toyokuni Oil Co., Ltd.), number average molecular weight: 2,000), and 10 parts by mass of biomass-derived polyester polyol (a reaction product of biomass-derived diethylene glycol ("Bio DEG” manufactured by India Glycols) and orthophthalic acid, number average molecular weight: 1,000), and dried under reduced pressure at 110 ° C.
• Bio PTMG biomass-derived polytetramethylene glycol
• polyester polyol having an aromatic ring a reaction product of
• Example 6 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 70 parts by mass of biomass-derived polycarbonate polyol (Mitsubishi Chemical Corporation's "Benebiol NL2000D", number average molecular weight: 2,000), 20 parts by mass of polyester polyol having an aromatic ring (a propylene oxide 6 mole adduct of bisphenol A, isophthalic acid, and a reaction product of biomass-derived sebacic acid (Toyokuni Oil's "Bio Seb"), number average molecular weight: 2,000), and 10 parts by mass of biomass-derived polyester polyol (a reaction product of biomass-derived sebacic acid (Toyokuni Oil's "Bio Seb") and biomass-derived diethylene glycol (India Glycols'"BioDEG”), number average molecular weight: 2,000), and dried under reduced pressure at 110 ° C.
• biomass-derived polycarbonate polyol Mitsubishi Chemical
• Example 7 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 60 parts by mass of biomass-derived polytetramethylene glycol ("Bio PTMG” manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000), 20 parts by mass of polyester polyol having an aromatic ring (a reaction product of 6 moles of propylene oxide adduct of bisphenol A, isophthalic acid, and biomass-derived sebacic acid ("Bio Seb” manufactured by Toyokuni Oil Co., Ltd.), number average molecular weight: 2,000), and 20 parts by mass of biomass-derived polyester polyol (a reaction product of biomass-derived sebacic acid (“Bio Seb” manufactured by Toyokuni Oil Co., Ltd.) and biomass-derived diethylene glycol (“Bio DEG” manufactured by India Glycols Co., Ltd.), number average molecular weight: 2,000), and dried under reduced pressure at 110 ° C.
• Bio PTMG
• Example 8 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 50 parts by mass of biomass-derived polytetramethylene glycol ("Bio PTMG” manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000), 20 parts by mass of polyester polyol having an aromatic ring (a reaction product of 6 moles of propylene oxide adduct of bisphenol A, isophthalic acid, and biomass-derived sebacic acid ("Bio Seb” manufactured by Toyokuni Oil Co., Ltd.), number average molecular weight: 2,000), and 30 parts by mass of biomass-derived polyester polyol (a reaction product of biomass-derived sebacic acid ("Bio Seb” manufactured by Toyokuni Oil Co., Ltd.) and biomass-derived diethylene glycol (“Bio DEG” manufactured by India Glycols Co., Ltd.), number average molecular weight: 2,000), and dried under reduced pressure at 110 ° C.
• Bio PTMG
• urethane prepolymer having an NCO% of 3.36% by mass and a biomass degree of 80% by mass, which was used as a moisture-curable polyurethane hot-melt resin composition.
• the number average molecular weights of the polyols used in the examples and comparative examples are values 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.
• This processed fabric was cut to a width of 1 inch, and the peel strength (kg / inch) was measured using a Tensilon (Tensilon universal testing machine "RTC 1210A” manufactured by Orientec Co., Ltd.) at a crosshead speed of 200 mm / min.
• the moisture-curable polyurethane hot melt resin composition of the present invention was found to have a high biomass content, as well as excellent adhesion and texture.
• Comparative Example 1 which does not use components (a2) and (a3), had poor adhesion and texture.
• Comparative Example 2 is an embodiment that does not use component (a2), but the adhesion and texture were poor.
• Comparative Example 3 is an embodiment that does not use component (a3), but the adhesion and texture were poor.

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• Polyurethanes Or Polyureas (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Laminated Bodies (AREA)

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