Moisture-curable polyurethane resin composition, adhesive, and laminate

Abstract

The present invention provides a moisture-curable hot-melt polyurethane resin composition which contains a urethane prepolymer (i) having an isocyanate group, and which is characterized in that the urethane prepolymer (i) is a reaction product of a polyol (A) and a polyisocyanate (B), 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) that is solid at room temperature other than (a2). Furthermore, the present invention provides an adhesive which is characterized by containing the moisture-curable polyurethane resin composition. Furthermore, the present invention provides a laminate characterized by having at least a base material and a cured product of the moisture-curable polyurethane resin composition.

Description

Technical Field

[0001] The present invention relates to a moisture-curable polyurethane resin composition, an adhesive and a laminate. Background Art

[0002] The breathable and waterproof functional clothing having both breathable and waterproof properties is a structure formed by bonding a breathable film to a substrate with an adhesive. As the above-mentioned adhesive, a urethane adhesive is generally used from the aspect of good adhesion to both the breathable film and the substrate. In addition, among the above-mentioned urethane adhesives, due to the recent global restrictions on solvent emissions and residual solvents, the use of moisture-curable polyurethane resin compositions as solvent-free types is gradually increasing (for example, see Patent Document 1).

[0003] On the other hand, in view of the recent marine plastic problem, the attention to biomass resins aimed at getting rid of fossil resources has also been increasing, and moisture-curable polyurethane resin compositions are no exception. However, some people point out that when the biomass content is increased, the texture and adhesion are reduced, and it is a big issue to balance these properties.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2017-202608 Summary of the invention

[0007] Problems to be solved by the invention

[0008] The problem to be solved by the present invention is to provide a moisture-curable polyurethane resin composition having an increased biomass ratio by using a biomass raw material and having excellent texture and adhesiveness.

[0009] Means for solving problems

[0010] The present invention provides a moisture-curable polyurethane hot-melt resin composition, characterized in that it is a moisture-curable polyurethane hot-melt resin composition containing a urethane prepolymer (i) having an isocyanate group, wherein the urethane prepolymer (i) is a reaction product of a polyol (A) and a polyisocyanate (B), and the above-mentioned polyol (A) contains: polytetramethylene glycol or polycarbonate polyol (a1) derived from biomass, a polyol (a2) having an aromatic ring, and a polyester polyol (a3) ​​that is solid at room temperature other than the above-mentioned (a2).

[0011] The present invention also provides an adhesive comprising the moisture-curable polyurethane resin composition. The present invention also provides a laminate comprising at least a substrate and a cured product of the moisture-curable polyurethane resin composition.

[0012] Effects of the Invention

[0013] The moisture-curable polyurethane resin composition of the present invention uses a biomass raw material and has a high biomass content, and is an environmentally friendly material. In addition, the moisture-curable polyurethane resin composition of the present invention has both excellent texture and adhesiveness. DETAILED DESCRIPTION

[0014] The moisture-curable polyurethane hot-melt resin composition used in the present invention contains a urethane prepolymer (i) having an isocyanate group, and the urethane prepolymer (i) is a reaction product of a polyol (A) containing specific polyols and a polyisocyanate (B).

[0015] In order to increase the biomass content of the resin while achieving excellent texture and adhesion, the polyol (A) contains polytetramethylene glycol or polycarbonate polyol (a1) derived from biomass, a polyol (a2) having an aromatic ring, and a polyester polyol (a3) ​​that is solid at room temperature other than the above (a2) as essential components.

[0016] Biomass-derived polytetramethylene glycol or polycarbonate polyol (a1) is an essential component in order to increase the biomass content of the resin and to develop basic physical properties such as excellent mechanical strength of the adhesive film.

[0017] As the biomass-derived polytetramethylene glycol, for example, “Bio PTMG” manufactured by Mitsubishi Chemical Corporation can be obtained as a commercial item.

[0018] As the biomass-derived polycarbonate polyol, a polycarbonate polyol preferably derived from biomass and having a carbon number of 1 to 10, more preferably 3 to 10, can be used, and the like, for example, "Beneviol NL-2010DB" manufactured by Mitsubishi Chemical Corporation, "Beneviol NL-3010DB" manufactured by Mitsubishi Chemical Corporation, "Beneviol NL-2000D" manufactured by Mitsubishi Chemical Corporation, "PCDX222" manufactured by Asahi Kasei Corporation, etc. can be obtained as commercial products. These polycarbonate polyols may be used alone or in combination of two or more.

[0019] The number average molecular weight of the biomass-derived polytetramethylene glycol or polycarbonate polyol (a1) is preferably 500 to 100,000, 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).

[0020] 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).

[0021] The polyol (a2) having an aromatic ring can provide excellent film flexibility, texture, and adhesiveness, and examples of the polyol that can be used include polyether polyols having an aromatic ring and polyester polyols having an aromatic ring.

[0022] As the polyether polyol having an aromatic ring, for example, bisphenol A, bisphenol F, and alkylene oxide adducts thereof can be used. These polyols can be used alone or in combination of two or more. Among these, polyether polyols that are alkylene oxide adducts of bisphenol A are preferred. As the alkylene oxide, an alkylene oxide having 2 to 8 carbon atoms is preferred, and the number of moles of the alkylene oxide added is preferably 2 to 10 moles, and more preferably 4 to 8 moles.

[0023] As the polyester polyol having an aromatic ring, for example, a reaction product of a compound having a hydroxyl group described below and a polybasic acid can be used.

[0024] As the compound having a hydroxyl group, for example, ethylene glycol, propylene glycol, 1,4-butanediol, pentanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, hexanediol, neopentyl glycol, hexamethylene glycol, glycerol, trimethylolpropane, bisphenol A or bisphenol F, and alkylene oxide adducts thereof can be used. Among these, alkylene oxide adducts of bisphenol A are preferably used. In addition, as the alkylene oxide, an alkylene oxide having 2 to 8 carbon atoms is preferred, and the number of moles of the alkylene oxide added is preferably 2 to 10 moles, and more preferably 4 to 8 moles.

[0025] As the polybasic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, dimer acid, sebacic acid, undecanedicarboxylic acid, hexahydroterephthalic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid and the like can be used.

[0026] The number average molecular weight of the polyol (a2) having an aromatic ring is preferably 500 to 10,000, more preferably 500 to 5,000. The number average molecular weight of the polyol (a2) having an aromatic ring refers to a value measured by gel permeation chromatography (GPC).

[0027] The amount of the polyol (a2) having an aromatic ring to be used is preferably 10 to 40% by mass, more preferably 20 to 30% by mass, in the polyol (A).

[0028] The room temperature solid polyester polyol (a3) ​​other than the above (a2) is an essential component for suppressing the penetration of the adhesive into the substrate and developing excellent texture. The room temperature solid means that it does not exhibit fluidity at 25°C.

[0029] As the above-mentioned polyester polyol (a3), it is preferably selected from one or more of the polyester polyol (a3-1) made of diethylene glycol and sebacic acid, the polyester polyol (a3-2) made of 1,3-propylene glycol and sebacic acid, the polyester polyol (a3-3) made of diethylene glycol, neopentyl glycol and phthalic acid, and the polyester polyol (a3-4) made of diethylene glycol and phthalic acid.

[0030] In addition, as the polyester polyol (a3), in terms of increasing the biomass degree of the resin, polyester polyol (a3-1) using diethylene glycol and sebacic acid as raw materials and / or polyester polyol (a3-2) using 1,3-propylene glycol and sebacic acid as raw materials are preferred. It should be noted that as the biomass raw material of the polyester polyol, for example, sebacic acid derived from biomass ("Bio Seb" manufactured by Toyokuni Oil Co., Ltd.), 1,3-propylene glycol derived from biomass ("SUSTERRA Propanediol" manufactured by Dupont Co., Ltd.), diethylene glycol derived from biomass ("Bio DEG" manufactured by India Glycols Co., Ltd.), etc. can be obtained in the form of commercial products.

[0031] In addition, as the polyester polyol (a3), in terms of obtaining a more excellent texture, polyester polyol (a3-3) using diethylene glycol, neopentyl glycol and phthalic acid as raw materials and / or polyester polyol (a3-4) using diethylene glycol and phthalic acid as raw materials are preferred, and polyester polyol (a3-3) using diethylene glycol, neopentyl glycol and phthalic acid as raw materials is particularly preferred. In addition, as the diethylene glycol, it can be derived from petrochemicals or biomass, but in terms of increasing the biomass content, diethylene glycol derived from biomass is preferably used.

[0032] The number average molecular weight of the polyester polyol (a3) ​​is preferably 500 to 10,000, more preferably 800 to 5,000. The number average molecular weight of the polyester polyol (a3) ​​refers to a value measured by gel permeation chromatography (GPC).

[0033] 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).

[0034] The polyol (A) must contain the components (a1) to (a3) ​​but may contain other polyols as required. The total content of the components (a1) to (a3) ​​in the polyol (A) is preferably 20% by mass or more, more preferably 50% by mass or more.

[0035] As the above-mentioned other polyols, for example, polyester polyols other than the above-mentioned (a2) and (a3), polycarbonate polyols other than the above-mentioned (a1), polyether polyols other than the above-mentioned (a1), polybutadiene polyols, polyacrylic polyols, etc. can be used. These polyols can be used alone or in combination of two or more. These polyols can be used alone or in combination of two or more.

[0036] Examples of the number average molecular weight of the other polyols include 500 to 100,000. The number average molecular weight of the other polyols refers to a value measured by gel permeation chromatography (GPC).

[0037] As the above-mentioned polyisocyanate (B), it is possible to use: aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, xylene diisocyanate, phenylene diisocyanate, toluene diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylene diisocyanate. These polyisocyanates can be used alone or in combination of two or more. Among these, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred, from the perspective of obtaining more excellent reactivity, mechanical strength, and adhesion.

[0038] The amount of the polyisocyanate (B) is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on the total mass of the raw materials constituting the urethane prepolymer (i).

[0039] The hot-melt urethane prepolymer (i) is a product obtained by reacting the polyol (A) and the polyisocyanate (B), and has an isocyanate group that can react with moisture present in the air or in a substrate coated with a moisture-curable polyurethane hot-melt resin composition to form a cross-linked structure.

[0040] The biomass degree of the hot-melt urethane prepolymer (i) is preferably 40% or more, and more preferably 50 to 80% by mass or more. It should be noted that the biomass degree of the hot-melt urethane prepolymer (i) represents the total weight ratio of biomass-derived raw materials used in the production of the hot-melt urethane prepolymer (i) relative to the total weight of the hot-melt urethane prepolymer (i).

[0041] As a method for producing the hot-melt urethane prepolymer (i), for example, the polyisocyanate (B) is added to a reaction container to which the polyol (A) is added, and the polyisocyanate (B) is reacted under the condition that the isocyanate group of the polyisocyanate (B) is in excess relative to the hydroxyl group of the polyol (A).

[0042] The equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate group of the polyisocyanate (B) and the hydroxyl group of the polyol (A) when manufacturing the hot-melt urethane prepolymer (i) is preferably 1.2 to 5, and more preferably 1.5 to 3, from the perspective of obtaining better mechanical strength, texture and adhesion.

[0043] The isocyanate group content (hereinafter referred to 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, from the perspective of obtaining more excellent mechanical strength, texture and adhesiveness. The NCO% of the hot-melt urethane prepolymer (i) is a value measured by potentiometric titration in accordance with JISK 1603-1:2007.

[0044] The moisture-curable polyurethane hot-melt resin composition used in the present invention contains the above-mentioned urethane prepolymer (i) as an essential component, and other additives may be used as needed.

[0045] As the above-mentioned other additives, for example, light resistance stability, curing catalysts, adhesives, 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.

[0046] Next, the laminated body of the present invention will be described.

[0047] The laminated body of the present invention comprises at least a substrate and a cured product of the moisture-curable polyurethane hot-melt resin composition.

[0048] As the above-mentioned substrate, for example, there can be used: a plastic substrate; a glass substrate; wood; a fiber substrate such as non-woven fabrics, woven fabrics, knitted fabrics made of polyester fiber, polyethylene fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, linen, silk, wool, glass fiber, carbon fiber, and blended fibers thereof; a substrate formed by impregnating the above-mentioned non-woven fabric with a resin such as a polyurethane resin; a substrate formed by further providing a porous layer on the above-mentioned non-woven fabric, etc.

[0049] Examples of methods for applying the moisture-curable polyurethane hot-melt resin composition include methods using a roll coater, a knife coater, a spray coater, a gravure roll coater, a screen printing coater, a notch wheel coater, a T-die coater, an applicator, a dispenser, and the like.

[0050] After the moisture-curable polyurethane hot-melt resin composition is applied, it can be aged and aged by a known method.

[0051] The amount of the cured product of the moisture-curable urethane hot-melt resin composition applied is, for example, 5 to 100 g / m 2 range.

[0052] It should be noted that the moisture-curable polyurethane hot-melt resin composition of the present invention is most preferably used as an adhesive for moisture-permeable and waterproof functional clothing. In this case, the moisture-curable polyurethane hot-melt resin composition is preferably intermittently applied by a gravure roll coater, a rotary screen, or a dispenser to bond the substrate to a known moisture-permeable film. In this case, the amount of the moisture-curable polyurethane hot-melt resin composition applied is, for example, 5 to 100 g / m 2 range.

[0053] Example

[0054] Hereinafter, the present invention will be described in more detail using examples.

[0055] [Example 1]

[0056] In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 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 a 6-mol adduct of propylene oxide to 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 Co., Ltd.), number average molecular weight; 2,000) were placed, and dried under reduced pressure at 110° C. to dehydrate the mixture until the moisture content became 0.05% by mass or less. Next, after cooling to 60°C, 33 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110°C, and the reaction was carried out for 2 hours until the isocyanate group content became constant, thereby obtaining an urethane prepolymer (i-1) with an NCO% of 3.32% by mass and a biomass degree of 60.2% by mass, as a moisture-curable polyurethane hot-melt resin composition.

[0057] [Example 2]

[0058] In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 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 polyester polyol having an aromatic ring (a reaction product of 6 mol 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 a 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) were placed, and dried under reduced pressure at 110° C. to dehydrate the mixture until the moisture content became 0.05% by mass or less. Next, after cooling to 60°C, 23.5 parts by mass of diphenylmethane diisocyanate were added, the temperature was raised to 110°C, and the reaction was carried out for 2 hours until the isocyanate group content became constant, thereby obtaining an urethane prepolymer (i-2) with an NCO% of 3.33% by mass and a biomass degree of 65.4% by mass, as a moisture-curable polyurethane hot-melt resin composition.

[0059] [Example 3]

[0060] In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 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 6 mol 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 a biomass-derived polyester polyol (a reaction product of biomass-derived 1,3-propanediol ("SUSTERRA Propanediol" manufactured by Dupont Co., Ltd.) and biomass-derived sebacic acid ("Bio Seb" manufactured by Toyokuni Oil Co., Ltd., number average molecular weight: 2,000) were placed, and dried under reduced pressure at 110° C. to dehydrate the mixture until the moisture content became 0.05% by mass or less. Next, after cooling to 60°C, 23.5 parts by mass of diphenylmethane diisocyanate were added, the temperature was raised to 110°C, and the reaction was carried out for 2 hours until the isocyanate group content became constant, thereby obtaining an urethane prepolymer (i-3) with an NCO content of 3.33% by mass and a biomass content of 65.4% by mass, as a moisture-curable polyurethane hot-melt resin composition.

[0061] [Example 4]

[0062] In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 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 polyester polyol having an aromatic ring (a reaction product of 6 mol 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 a biomass-derived polyester polyol (a reaction product of biomass-derived diethylene glycol ("Bio DEG" manufactured by India Glycols Co., Ltd.), neopentyl glycol and phthalic acid, number average molecular weight: 1,000) were placed and dried under reduced pressure at 110° C. to dehydrate the mixture until the moisture content became 0.05% by mass or less. Next, after cooling to 60°C, 26.5 parts by mass of diphenylmethane diisocyanate were added, the temperature was raised to 110°C, and the reaction was carried out for 2 hours until the isocyanate group content became constant, thereby obtaining an urethane prepolymer (i-4) with an NCO% of 3.39% by mass and a biomass degree of 63.9% by mass, as a moisture-curable polyurethane hot-melt resin composition.

[0063] [Example 5]

[0064] In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 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 polyester polyol having an aromatic ring (a reaction product of 6 mol 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 a biomass-derived polyester polyol (a reaction product of biomass-derived diethylene glycol ("Bio DEG" manufactured by India Glycols Co., Ltd.) and phthalic acid, number average molecular weight; 1,000) were placed, and dried under reduced pressure at 110° C. to dehydrate the mixture until the moisture content became 0.05% by mass or less. Next, after cooling to 60°C, 23.5 parts by mass of diphenylmethane diisocyanate were added, the temperature was raised to 110°C, and the reaction was carried out for 2 hours until the isocyanate group content became constant, thereby obtaining an urethane prepolymer (i-5) with an NCO% of 3.33% by mass and a biomass degree of 65.4% by mass, as a moisture-curable polyurethane hot-melt resin composition.

[0065] [Example 6]

[0066] In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 70 parts by mass of a biomass-derived polycarbonate polyol ("Beneviol NL-2000D" manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000), 20 parts by mass of a polyester polyol having an aromatic ring (a reaction product of a 6-mol propylene oxide addition product 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 a 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) were placed, and dried under reduced pressure at 110° C. to dehydrate the mixture until the moisture content became 0.05% by mass or less. Next, after cooling to 60°C, 25.0 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110°C, and the reaction was carried out for 2 hours until the isocyanate group content became constant, thereby obtaining an urethane prepolymer (i-6) with an NCO% of 3.36% by mass and a biomass degree of 60.2% by mass, as a moisture-curable polyurethane hot-melt resin composition.

[0067] [Example 7]

[0068] In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 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 a polyester polyol having an aromatic ring (a reaction product of 6 mol 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 a 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) were placed, and dried under reduced pressure at 110° C. to dehydrate the mixture until the moisture content became 0.05% by mass or less. Next, after cooling to 60°C, 25.0 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110°C, and the reaction was carried out for 2 hours until the isocyanate group content became constant, thereby obtaining an urethane prepolymer (i-7) with an NCO% of 3.36% by mass and a biomass degree of 60.8% by mass, as a moisture-curable polyurethane hot-melt resin composition.

[0069] [Example 8]

[0070] In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 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 a polyester polyol having an aromatic ring (a reaction product of 6 mol 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 a 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) were placed, and dried under reduced pressure at 110° C. to dehydrate the mixture until the moisture content became 0.05% by mass or less. Next, after cooling to 60°C, 25.0 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110°C, and the reaction was carried out for 2 hours until the isocyanate group content became constant, thereby obtaining an urethane prepolymer (i-8) with an NCO% of 3.36% by mass and a biomass degree of 64.6% by mass, as a moisture-curable polyurethane hot-melt resin composition.

[0071] [Comparative Example 1]

[0072] In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 100 parts by mass of biomass-derived polytetramethylene glycol (Mitsubishi Chemical Corporation's "Bio PTMG", number average molecular weight: 2,000) was added, and the mixture was dried under reduced pressure at 110°C to dehydrate the mixture until the moisture content became 0.05% by mass or less. Next, after cooling to 60°C, 25.0 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110°C, and the reaction was carried out for 2 hours until the isocyanate group content became constant, thereby obtaining a urethane prepolymer (iR-1) with an NCO content of 3.36% by mass and a biomass content of 80% by mass, as a moisture-curable polyurethane hot-melt resin composition.

[0073] [Comparative Example 2]

[0074] In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 70 parts by mass of biomass-derived polytetramethylene glycol ("Bio PTMG" manufactured by Mitsubishi Chemical Corporation, 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) were placed, and dried under reduced pressure at 110° C. to dehydrate the mixture until the moisture content became 0.05% by mass or less. Next, after cooling to 60°C, 25.0 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110°C, and the reaction was carried out for 2 hours until the isocyanate group content became constant, thereby obtaining an urethane prepolymer (iR-2) with an NCO% content of 3.36% by mass and a biomass content of 80% by mass, as a moisture-curable polyurethane hot-melt resin composition.

[0075] [Comparative Example 3]

[0076] In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 70 parts by mass of biomass-derived polytetramethylene glycol (Mitsubishi Chemical Corporation's "Bio PTMG", number average molecular weight: 2,000) and 30 parts by mass of a polyether polyol having an aromatic ring (a polyether polyol which is a 6-mol adduct of propylene oxide to bisphenol A, number average molecular weight: 508) were placed, and the mixture was dried under reduced pressure at 110°C until the moisture content became 0.05% by mass or less. Next, after cooling to 60°C, 25.0 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110°C, and the reaction was carried out for 2 hours until the isocyanate group content became constant, thereby obtaining a urethane prepolymer (iR-3) with an NCO content of 3.36% by mass and a biomass content of 56% by mass, as a moisture-curable polyurethane hot-melt resin composition.

[0077] [Method for measuring number average molecular weight]

[0078] The number average molecular weight of the polyol used in Examples and Comparative Examples refers to a value measured by gel permeation chromatography (GPC) under the following conditions.

[0079] Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)

[0080] Column: The following columns manufactured by Tosoh Corporation were connected in series and used.

[0081] "TSKgel G5000" (7.8mm I. D. × 30cm) × 1 piece

[0082] "TSKgel G4000" (7.8mm I. D. × 30cm) × 1 piece

[0083] "TSKgel G3000" (7.8mm I. D. × 30cm) × 1 piece

[0084] "TSKgel G2000" (7.8mm I. D. × 30cm) × 1 piece

[0085] Detector: RI (differential refractometer)

[0086] Column temperature: 40°C

[0087] Eluent: Tetrahydrofuran (THF)

[0088] Flow rate: 1.0mL / min

[0089] Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass %)

[0090] Standard sample: The standard curve was prepared using the following standard polystyrene.

[0091] (Standard Polystyrene)

[0092] "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation

[0093] "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation

[0094] "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation

[0095] "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation

[0096] "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation

[0097] "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation

[0098] "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation

[0099] "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation

[0100] "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation

[0101] "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation

[0102] "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation

[0103] "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation

[0104] "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation

[0105] "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[0106] [Evaluation method of adhesiveness]

[0107] <Evaluation of Adhesion 1-Initial Adhesion Strength>

[0108] In a constant temperature and humidity chamber adjusted to 23°C and 50±5% humidity, a 100μm thick corona-treated PET was coated with the moisture-curable polyurethane hot-melt resin composition obtained in the examples and comparative examples melted at 100°C using a 50μm thick rod coater. The product bonded to the corona-treated PET was cut into 1 inch width at 23°C and 50±5% humidity. The initial bonding strength (N / inch) was measured using Tensilon (Tensilon Universal Testing Machine "RTC-1210A" manufactured by Orientec Co., Ltd.) at a crosshead speed of 200mm / min. It should be noted that the initial bonding strength was measured 1 minute, 10 minutes, and 30 minutes after the moisture-curable polyurethane hot-melt resin composition was applied to the entire surface.

[0109] <Evaluation of Adhesion 2>

[0110] In a constant temperature and humidity chamber adjusted to 23°C and 50±5%, a moisture permeable film (VENTEX manufactured by Kapyeong Co., Ltd.) was coated with a gravure coater to a thickness of 17.5±5 g / m 2 The moisture-curable polyurethane hot-melt resin composition obtained in the examples and comparative examples melted at 100°C was intermittently applied in a manner, and the product bonded to the polyester substrate was aged for 24 hours under the conditions of temperature 23°C and humidity 50±5% to obtain a processed cloth. The processed cloth was cut into 1 inch width, and the peel strength (kg / inch) was measured using Tensilon (Tensilon universal testing machine "RTC-1210A" manufactured by Orientec Co., Ltd.) at a crosshead speed of 200 mm / min.

[0111] [Texture evaluation method]

[0112] The softness of the processed fabric obtained in the above-mentioned [Evaluation 2 of Adhesiveness] when bent by hand was evaluated as follows.

[0113] “5”; rich in softness.

[0114] "4"; the softness is fully felt.

[0115] "3"; slightly soft.

[0116] “2”: poor softness.

[0117] “1”; hard.

[0118] [Table 1]

[0119]

[0120] [Table 2]

[0121]

[0122] [Table 3]

[0123]

[0124] It is found that the moisture-curable polyurethane hot-melt resin composition of the present invention has a high biomass content and has excellent adhesiveness and texture.

[0125] On the other hand, in Comparative Example 1, which is a method in which components (a2) and (a3) ​​were not used, adhesiveness and texture were poor.

[0126] Comparative Example 2 is a method in which the component (a2) was not used, and the adhesiveness and texture were poor.

[0127] Comparative Example 3 is a method in which the component (a3) ​​was not used, and the adhesiveness and texture were poor.

Claims

1. A moisture-curable polyurethane hot-melt resin composition, characterized in that: The present invention is a moisture-curable polyurethane hot-melt resin composition containing a urethane prepolymer (i) having an isocyanate group, wherein the urethane prepolymer (i) is a reaction product of a polyol (A) and a polyisocyanate (B). The polyol (A) contains: Polytetramethylene glycol or polycarbonate polyol (a1) derived from biomass, A polyol (a2) having an aromatic ring, and A polyester polyol (a3) ​​other than the above (a2) which is solid at room temperature.

2. The moisture-curable polyurethane hot-melt resin composition according to claim 1, wherein The polycarbonate polyol (a1) is made from a diol having 1 to 10 carbon atoms and derived from biomass.

3. The moisture-curable polyurethane hot-melt resin composition according to claim 1, wherein The polyol (a2) having an aromatic ring is a polyether polyol which is an alkylene oxide adduct of bisphenol A, or a polyester polyol using an alkylene oxide adduct of bisphenol A as a raw material.

4. The moisture-curable polyurethane hot-melt resin composition according to claim 1, wherein The polyester polyol (a3) ​​is one or more selected from the group consisting of a polyester polyol (a3-1) made from diethylene glycol and sebacic acid, a polyester polyol (a3-2) made from 1,3-propylene glycol and sebacic acid, a polyester polyol (a3-3) made from diethylene glycol, neopentyl glycol and phthalic acid, and a polyester polyol (a3-4) made from diethylene glycol and phthalic acid.

5. An adhesive, characterized in that: A moisture-curable polyurethane resin composition according to claim 1 is contained.

6. A laminated body, characterized in that: A cured product comprising at least a substrate and the moisture-curable polyurethane resin composition according to claim 1.

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