WO2024084729A1 - Moisture-curable polyurethane hot melt resin composition, adhesive, and synthetic leather - Google Patents

Moisture-curable polyurethane hot melt resin composition, adhesive, and synthetic leather Download PDF

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Publication number
WO2024084729A1
WO2024084729A1 PCT/JP2023/019460 JP2023019460W WO2024084729A1 WO 2024084729 A1 WO2024084729 A1 WO 2024084729A1 JP 2023019460 W JP2023019460 W JP 2023019460W WO 2024084729 A1 WO2024084729 A1 WO 2024084729A1
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mass
hot melt
parts
moisture
resin composition
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PCT/JP2023/019460
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French (fr)
Japanese (ja)
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宏之 千々和
善典 金川
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Dic株式会社
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Priority to JP2024536474A priority Critical patent/JPWO2024084729A1/ja
Publication of WO2024084729A1 publication Critical patent/WO2024084729A1/en

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    • 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
    • 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
    • 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
    • C08G18/48—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 relates to a moisture-curable polyurethane hot melt resin composition, an adhesive, and synthetic leather.
  • Synthetic leather uses polyurethane (PU), polyvinyl chloride (PVC), olefin-based thermoplastic elastomer (TPO), etc. as the surface material, and these surface materials are generally bonded to a base fabric such as cloth or nonwoven fabric with an adhesive (see, for example, Patent Document 1).
  • solvent-based adhesives have been the most widespread and commonly used up until now, but as part of environmental efforts, regions, countries, and companies are calling for a reduction in VOCs, and it is becoming necessary to replace solvent-based with water-based or solvent-free adhesives.
  • the problem that the present invention aims to solve is to provide a moisture-curable polyurethane hot melt resin composition that has excellent adhesion, low-temperature flexibility, and flame retardancy.
  • the present invention provides a moisture-curable polyurethane hot-melt resin composition containing a hot-melt urethane prepolymer (A) having an isocyanate group and a flame retardant (B), characterized in that the hot-melt prepolymer (A) is made from a polyol (a) containing 50 mass% or more of a polyether polyol (a1), and the content of the flame retardant (B) is more than 15 mass parts per 100 mass parts of the hot-melt urethane prepolymer (A).
  • the present invention also provides an adhesive that contains the moisture-curable polyurethane hot melt resin composition.
  • the present invention also provides synthetic leather that has at least a thermoplastic resin layer and the adhesive layer.
  • the moisture-curable polyurethane hot melt resin composition of the present invention has excellent adhesion, low-temperature flexibility, and flame retardancy. Therefore, the moisture-curable polyurethane hot melt resin composition of the present invention can be particularly suitably used in the manufacture of synthetic leather that uses a thermoplastic resin as the skin material.
  • the moisture-curable polyurethane hot melt resin composition of the present invention contains a hot melt urethane prepolymer (A) having an isocyanate group, which is made from a specific polyol (a), and a specific amount of a flame retardant (B).
  • A hot melt urethane prepolymer having an isocyanate group, which is made from a specific polyol (a), and a specific amount of a flame retardant (B).
  • the hot melt urethane prepolymer (A) having isocyanate groups is made from polyol (a) containing 50% by mass or more of polyether polyol (a1).
  • the amount of polyether polyol (a1) used is preferably 50 to 90% by mass, and more preferably 55 to 70% by mass, of the polyol (a) in order to obtain even better low-temperature flexibility.
  • polyether polyol (a1) for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, etc. can be used. These polyols may be used alone or in combination of two or more. Among these, polypropylene glycol and/or polytetramethylene glycol are preferred because they provide even better low-temperature flexibility, and polytetramethylene glycol is more preferred because they provide even better heat resistance and wet heat resistance.
  • the polyether polyol may be derived from a plant.
  • plant-derived polyether polyol for example, "Bio PTMG” manufactured by Mitsubishi Chemical Corporation, “Bio PTG” manufactured by Hodogaya Chemical Co., Ltd., biomass polypropylene glycol manufactured by Vithal Castor Polyols, etc. can be obtained as commercially available products.
  • polyol (a) other polyols can be used in combination with the polyether polyol (a).
  • other polyols for example, commercially available polyols such as polyester polyols, polycarbonate polyols, polybutadiene polyols, silicone diols, and acrylic diols can be used. These polyols may be used alone or in combination of two or more, and may be derived from petroleum or plants.
  • polyester polyols are preferred because they provide even better adhesion.
  • the number average molecular weight of the polyol (a) is preferably 500 to 10,000, and more preferably 1,000 to 6,000, in order to obtain even better adhesion, low-temperature flexibility, and mechanical strength.
  • the number average molecular weight of the polyol (a) is a value measured by gel permeation chromatography (GPC).
  • the hot melt urethane prepolymer (A) having an isocyanate group can be, for example, a reaction product of the polyol (a) and the polyisocyanate (b).
  • polyisocyanate (b) for example, aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate can be used.
  • aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphen
  • polyisocyanates may be used alone or in combination of two or more, and may be derived from petroleum or plants.
  • aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred, in that they provide even better reactivity and adhesion.
  • the hot melt urethane prepolymer (A) has isocyanate groups at the polymer terminals or within the molecule that can react with moisture present in the air or in the substrate or adherend to which the urethane prepolymer is applied to form a crosslinked structure.
  • the hot melt urethane prepolymer (A) 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 molar ratio [NCO/OH] of the hydroxyl groups in the polyol (a) to the isocyanate groups in the polyisocyanate (b) is preferably 1.3 to 2.5, and more preferably 1.5 to 2.0, in order to obtain even better hot melt properties, adhesive properties, and low-temperature flexibility.
  • the isocyanate group content (hereinafter abbreviated as "NCO%) of the hot melt urethane prepolymer (A) is preferably 1.2 to 5.0 mass%, more preferably 1.7 to 3.5 mass%, in order to obtain even better hot melt properties, adhesion, and low-temperature flexibility.
  • the NCO% of the hot melt urethane prepolymer (A) is a value measured by potentiometric titration in accordance with JIS K1603-1:2007.
  • the flame retardant (B) is an essential component for obtaining excellent flame retardancy, and its content must exceed 15 parts by mass per 100 parts by mass of the hot-melt urethane prepolymer (A).
  • the content of the flame retardant (B) is preferably 17.5 to 55 parts by mass per 100 parts by mass of the hot-melt urethane prepolymer (A) in order to maintain a high level of low-temperature flexibility and adhesion and obtain even better flame retardancy.
  • the flame retardant (B) may be, for example, a phosphate ester, a phosphate-containing flame retardant, red phosphorus, a bromine-containing flame retardant, a boron-containing flame retardant, an antimony-containing flame retardant, a metal hydroxide, graphite, a phosphorus-boron compound, a vinyl polymer, or the like.
  • These flame retardants may be used alone or in combination of two or more.
  • a phosphate ester having three or more aromatic rings is preferred, and a phosphate ester having four or more aromatic rings is more preferred, in that it maintains a high level of low-temperature flexibility and adhesion, and provides even more excellent flame retardancy.
  • the moisture-curable polyurethane hot-melt resin composition of the present invention contains the hot-melt urethane prepolymer (A) and the flame retardant (B) as essential components, but may contain other additives as necessary.
  • additives examples include urethane catalysts, neutralizing agents, crosslinking agents, silane coupling agents, thickeners, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, light resistance stabilizers, fluorescent whitening agents, foaming agents, pigments, dyes, conductivity agents, antistatic agents, moisture permeability enhancers, water repellents, oil repellents, hollow foams, water absorbents, moisture absorbents, deodorizers, foam stabilizers, plasticizers, antiblocking agents, hydrolysis inhibitors, etc. These additives may be used alone or in combination of two or more.
  • the moisture-curable polyurethane hot melt resin composition of the present invention has excellent adhesion, low-temperature flexibility, and flame retardancy. Therefore, the moisture-curable polyurethane hot melt resin composition of the present invention can be particularly suitably used in the manufacture of synthetic leather that uses a thermoplastic resin as the skin material.
  • the synthetic leather has at least a thermoplastic resin layer and an adhesive layer containing the moisture-curable polyurethane hot melt resin composition, and may be, for example, a layer of a substrate, the adhesive layer, and a thermoplastic resin layer laminated in that order.
  • the substrate may be, for example, a nonwoven fabric, woven fabric, or knitted fabric 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.
  • the thermoplastic resin layer may be formed from, for example, known polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, polystyrene, TPO (thermoplastic olefinic elastomer), thermoplastic ester elastomer, thermoplastic polyurethane, etc.
  • TPO thermoplastic olefinic elastomer
  • thermoplastic ester elastomer thermoplastic polyurethane
  • thermoplastic polyurethane etc.
  • it has excellent adhesion and low-temperature flexibility, and in particular, for polyvinyl chloride, which is difficult to adhere to, it has excellent adhesion and low-temperature flexibility whether it is foamed or unfoamed.
  • the adhesive layer is formed from the moisture-curable polyurethane hot melt resin composition of the present invention, and examples of the method for forming the adhesive layer include a method in which the moisture-curable polyurethane hot melt resin composition is melted at 100 to 140°C, and then coated onto the thermoplastic resin layer or the substrate using a coater method such as a roll coater, spray coater, T-die coater, knife coater, or comma coater; a precision method such as a dispenser, inkjet printing, screen printing, or offset printing; or a nozzle coater, and then the layers are bonded together.
  • a coater method such as a roll coater, spray coater, T-die coater, knife coater, or comma coater
  • a precision method such as a dispenser, inkjet printing, screen printing, or offset printing
  • a nozzle coater a method in which the moisture-curable polyurethane hot melt resin composition is melted at 100 to 140°C, and then coated onto the thermoplastic resin
  • the adhesive can be dried and cured as necessary using known methods.
  • the synthetic leather may further have a surface treatment layer on top of the thermoplastic resin layer.
  • the surface treatment layer may be formed from, for example, a known solvent-based urethane resin, water-based urethane resin, solvent-based acrylic resin, water-based acrylic resin, etc.
  • Example 1 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser was charged with 171 parts by mass of polytetramethylene glycol (number average molecular weight: 2,000, hereinafter abbreviated as "PEt-1”), 78 parts by mass of polyester polyol (residued by reacting 1,6-hexanediol and orthophthalic acid, number average molecular weight: 2,000, hereinafter abbreviated as "PEs-1”), and 62 parts by mass of polyester polyol (residued by reacting 1,6-hexanediol and sebacic acid, number average molecular weight: 3,500, hereinafter abbreviated as "PEs-2”), mixed, and heated at 100°C under reduced pressure to dehydrate the water in the flask until the water content was 0.05% by mass or less.
  • PEt-1 polytetramethylene glycol
  • PET
  • MDI 4,4'-diphenylmethane diisocyanate
  • Example 2 In a four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 74 parts by mass of PEt-1, 31 parts by mass of PEs-1, and 18 parts by mass of PEs-2 were added, mixed, and heated under reduced pressure at 100 ° C., and the moisture in the flask was dehydrated until it was 0.05% by mass or less. Next, the flask was cooled to 90 ° C., 27 parts by mass of MDI melted at 70 ° C. was added, and the mixture was reacted at 110 ° C.
  • Example 3 In a four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 48 parts by mass of polypropylene glycol (number average molecular weight: 2,000, hereinafter abbreviated as "PEt-2”), 17 parts by mass of PEs-1, and 22 parts by mass of polyester polyol (ethylene glycol, neopentyl glycol, 16-hexanediol, and adipic acid reacted, number average molecular weight: 5,500, hereinafter abbreviated as "PEs-3”) were placed, mixed, and heated under reduced pressure at 100 ° C.
  • PEt-2 polypropylene glycol
  • polyester polyol ethylene glycol, neopentyl glycol, 16-hexanediol, and adipic acid reacted, number average molecular weight: 5,500
  • Example 4 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 133 parts by mass of PEt-1, 56 parts by mass of PEs-1, and 33 parts by mass of PEs-2, mixed, and heated under reduced pressure at 100 ° C. to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90 ° C., 49 parts by mass of MDI melted at 70 ° C. was added, and the mixture was reacted at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot melt urethane prepolymer. 30 parts by mass of flame retardant (B1) was blended with 100 parts by mass of this hot melt urethane prepolymer to obtain a moisture-curable polyurethane hot melt resin composition (4).
  • B1 flame retardant
  • Example 5 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 139 parts by mass of PEt-2, 32 parts by mass of PEs-1, and 43 parts by mass of PEs-3, mixed, and heated under reduced pressure at 100 ° C. to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90 ° C., 47 parts by mass of MDI melted at 70 ° C. was added, and the mixture was reacted at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot melt urethane prepolymer. 35 parts by mass of flame retardant (B1) was blended with 100 parts by mass of this hot melt urethane prepolymer to obtain a moisture-curable polyurethane hot melt resin composition (5).
  • Example 6 In a four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 83 parts by mass of PEt-1, 19 parts by mass of PEs-1, and 26 parts by mass of PEs-3 were added, mixed, and heated under reduced pressure at 100 ° C. to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90 ° C., 26 parts by mass of MDI melted at 70 ° C. was added, and the mixture was reacted at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot melt urethane prepolymer. 40 parts by mass of flame retardant (B1) was blended with 100 parts by mass of this hot melt urethane prepolymer to obtain a moisture-curable polyurethane hot melt resin composition (6).
  • B1 flame retardant
  • Example 7 A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 121 parts by mass of PEt-1, 121 parts by mass of PEt-2, 81 parts by mass of PEs-1, and 81 parts by mass of PEs-2, mixed, and heated under reduced pressure at 100 ° C. to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90 ° C., 87 parts by mass of MDI melted at 70 ° C. was added, and the mixture was reacted at 110 ° C.
  • Example 8 A moisture-curable polyurethane hot melt resin composition (8) was obtained in the same manner as in Example 1, except that PEt-1 was replaced with biomass polytetramethylene glycol ("Bio PTMG” manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000).
  • the number average molecular weights of the polyols used in the examples and comparative examples are values measured by gel permeation column 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.
  • Test pieces that did not ignite or self-extinguished before the A-marked line, those that self-extinguished within a burning distance of 51 mm (and within 60 seconds), and those with a burning rate of 102 mm/min or less were marked as " ⁇ ", and those that did not were marked as " ⁇ ".
  • Examples 1 to 8 which are moisture-curable polyurethane hot melt resin compositions of the present invention, have excellent adhesion, low-temperature flexibility, and flame retardancy.
  • Comparative Example 2 is an embodiment in which flame retardant (B) is not used, but the flame retardancy was poor.
  • Comparative examples 3 and 4 are examples in which the amount of polyether polyol (a1) used is below the range specified in the present invention, but the low-temperature flexibility and other properties were poor.

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

Abstract

The present invention provides a moisture-curable polyurethane hot melt resin composition which contains (A) a hot melt urethane prepolymer having an isocyanate group and (B) a flame retardant, and which is characterized in that: the hot melt prepolymer (A) uses, as a starting material, a polyol (a) that contains 50% by mass or more of a polyether polyol (a1); and the content of the flame retardant (B) is more than 15 parts by mass relative to 100 parts by mass of the hot melt urethane prepolymer (A). In addition, the present invention provides an adhesive which is characterized by containing the moisture-curable polyurethane hot melt resin composition. It is preferable that the flame retardant (B) is a phosphoric acid ester that has three or more aromatic rings.

Description

湿気硬化型ポリウレタンホットメルト樹脂組成物、接着剤、及び、合成皮革Moisture-curable polyurethane hot melt resin composition, adhesive, and synthetic leather
　本発明は、湿気硬化型ポリウレタンホットメルト樹脂組成物、接着剤、及び、合成皮革に関する。 The present invention relates to a moisture-curable polyurethane hot melt resin composition, an adhesive, and synthetic leather.
　合成皮革には、表皮材としてポリウレタン（ＰＵ）、ポリ塩化ビニル（ＰＶＣ）、オレフィン系熱可塑性エラストマー（ＴＰＯ）等が使用されており、これらの表皮材を布地や不織布などの基布と接着剤で貼り合せた物が一般的に使用されている（例えば、特許文献１を参照。）。中でも接着剤はこれまで溶剤系のものが広く普及し一般的に使用されてきたが、環境に向けた取り組みとして地域・国・企業からＶＯＣの低減が求められており、溶剤系から水系や無溶剤の接着剤への置き換えが必要となっている。 Synthetic leather uses polyurethane (PU), polyvinyl chloride (PVC), olefin-based thermoplastic elastomer (TPO), etc. as the surface material, and these surface materials are generally bonded to a base fabric such as cloth or nonwoven fabric with an adhesive (see, for example, Patent Document 1). Among these, solvent-based adhesives have been the most widespread and commonly used up until now, but as part of environmental efforts, regions, countries, and companies are calling for a reduction in VOCs, and it is becoming necessary to replace solvent-based with water-based or solvent-free adhesives.
　一方で車輛内装材や屋内用家具に用いられる合成皮革には防炎上の観点から難燃性が要求されているが、寒冷地域での使用を想定した低温での屈曲性の要求レベルも上がっている。しかしながら、これらの特性を全て兼ね備える材料は未だ見出されていない。 On the other hand, synthetic leather used in vehicle interior materials and indoor furniture is required to be flame retardant from a fire prevention perspective, but the level of flexibility required at low temperatures is also increasing in anticipation of use in cold regions. However, a material that combines all of these properties has yet to be found.
特表２００８－５１４４０３号公報JP 2008-514403 A
　本発明が解決しようとする課題は、接着性、低温屈曲性、及び、難燃性に優れる湿気硬化型ポリウレタンホットメルト樹脂組成物を提供することである。 The problem that the present invention aims to solve is to provide a moisture-curable polyurethane hot melt resin composition that has excellent adhesion, low-temperature flexibility, and flame retardancy.
　本発明は、イソシアネート基を有するホットメルトウレタンプレポリマー（Ａ）、及び、難燃剤（Ｂ）を含有する湿気硬化型ポリウレタンホットメルト樹脂組成物であって、前記ホットメルトプレポリマー（Ａ）が、ポリエーテルポリオール（ａ１）を５０質量％以上含むポリオール（ａ）を原料とするものであり、前記難燃剤（Ｂ）の含有量が、前記ホットメルトウレタンプレポリマー（Ａ）１００質量部に対して、１５質量部を超えるものであることを特徴とする湿気硬化型ポリウレタンホットメルト樹脂組成物を提供するものである。 The present invention provides a moisture-curable polyurethane hot-melt resin composition containing a hot-melt urethane prepolymer (A) having an isocyanate group and a flame retardant (B), characterized in that the hot-melt prepolymer (A) is made from a polyol (a) containing 50 mass% or more of a polyether polyol (a1), and the content of the flame retardant (B) is more than 15 mass parts per 100 mass parts of the hot-melt urethane prepolymer (A).
　また、本発明は、前記湿気硬化型ポリウレタンホットメルト樹脂組成物を含有することを特徴とする接着剤を提供するものである。また、本発明は、少なくとも、熱可塑性樹脂層、及び、前記接着剤層とを有することを特徴とする合成皮革を提供するものである。 The present invention also provides an adhesive that contains the moisture-curable polyurethane hot melt resin composition. The present invention also provides synthetic leather that has at least a thermoplastic resin layer and the adhesive layer.
　本発明の湿気硬化型ポリウレタンホットメルト樹脂組成物は、接着性、低温屈曲性、及び、難燃性に優れるものである。よって、本発明の湿気硬化型ポリウレタンホットメルト樹脂組成物は、熱可塑性樹脂を表皮材とする合成皮革の製造に特に好適に用いることができる。 The moisture-curable polyurethane hot melt resin composition of the present invention has excellent adhesion, low-temperature flexibility, and flame retardancy. Therefore, the moisture-curable polyurethane hot melt resin composition of the present invention can be particularly suitably used in the manufacture of synthetic leather that uses a thermoplastic resin as the skin material.
　本発明の湿気硬化型ポリウレタンホットメルト樹脂組成物は、特定のポリオール（ａ）を原料とするイソシアネート基を有するホットメルトウレタンプレポリマー（Ａ）、及び、特定量の難燃剤（Ｂ）を含有するものである。 The moisture-curable polyurethane hot melt resin composition of the present invention contains a hot melt urethane prepolymer (A) having an isocyanate group, which is made from a specific polyol (a), and a specific amount of a flame retardant (B).
　前記イソシアネート基を有するホットメルトウレタンプレポリマー（Ａ）は、優れた低温屈曲性を得るうえで、ポリエーテルポリオール（ａ１）を５０質量％以上含むポリオール（ａ）を原料とすることが必須である。このように設計することで、接着剤をガラス転移温度を低下させることができるため、優れた低温屈曲性を得ることができる。前記ポリエーテルポリオール（ａ１）の使用量としては、より一層優れた低温屈曲性が得られる点から、ポリオール（ａ）中５０～９０質量％が好ましく、５５～７０質量％がより好ましい。 In order to obtain excellent low-temperature flexibility, it is essential that the hot melt urethane prepolymer (A) having isocyanate groups is made from polyol (a) containing 50% by mass or more of polyether polyol (a1). By designing in this way, the glass transition temperature of the adhesive can be lowered, and therefore excellent low-temperature flexibility can be obtained. The amount of polyether polyol (a1) used is preferably 50 to 90% by mass, and more preferably 55 to 70% by mass, of the polyol (a) in order to obtain even better low-temperature flexibility.
　前記ポリエーテルポリオール（ａ１）としては、例えば、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ポリオキシエチレンポリオキシプロピレングリコール、ポリオキシエチレンポリオキシテトラメチレングリコール、ポリオキシプロピレンポリオキシテトラメチレングリコール等を用いることができる。これらのポリオールは単独でも２種以上を併用してもよい。これらの中でも、より一層優れた低温屈曲性が得られる点から、ポリプロピレングリコール及び／又はポリテトラメチレングリコールが好ましく、更により一層優れた耐熱性及び湿熱性が得られる点から、ポリテトラメチレングリコールがより好ましい。なお、前記ポリエーテルポリオールとしては、植物由来のものを用いてもよい。前記植物由来のポリエーテルポリオールとしては、例えば、三菱ケミカル株式会社製「Ｂｉｏ　ＰＴＭＧ」、保土ヶ谷化学社製「バイオ ＰＴＧ」、Ｖｉｔｈａｌ　Ｃａｓｔｏｒ　Ｐｏｌｙｏｌｓ社製のバイオマスポリポリプロピレングリコール等を市販品として入手することができる。 As the polyether polyol (a1), for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, etc. can be used. These polyols may be used alone or in combination of two or more. Among these, polypropylene glycol and/or polytetramethylene glycol are preferred because they provide even better low-temperature flexibility, and polytetramethylene glycol is more preferred because they provide even better heat resistance and wet heat resistance. The polyether polyol may be derived from a plant. As the plant-derived polyether polyol, for example, "Bio PTMG" manufactured by Mitsubishi Chemical Corporation, "Bio PTG" manufactured by Hodogaya Chemical Co., Ltd., biomass polypropylene glycol manufactured by Vithal Castor Polyols, etc. can be obtained as commercially available products.
　前記ポリオール（ａ）としては、前記ポリエーテルポリオール（ａ）以外にもその他のポリオールを併用することができる。前記その他のポリオールとしては、例えば、ポリエステルポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール、シリコンジオール、アクリルジオールなど市販のポリオールを用いることができる。これらのポリオールは単独でも２種以上を併用してもよく、石油由来のものでも、植物由来のものでもよい。前記その他のポリオールとしては、より一層優れた接着性が得られる点から、ポリエステルポリオールが好ましい。 As the polyol (a), other polyols can be used in combination with the polyether polyol (a). As the other polyols, for example, commercially available polyols such as polyester polyols, polycarbonate polyols, polybutadiene polyols, silicone diols, and acrylic diols can be used. These polyols may be used alone or in combination of two or more, and may be derived from petroleum or plants. As the other polyols, polyester polyols are preferred because they provide even better adhesion.
　前記ポリオール（ａ）の数平均分子量としては、より一層優れた接着性、低温屈曲性、及び、機械的強度が得られる点から、それぞれ５００～１０，０００が好ましく、１，０００～６，０００がより好ましい。なお、前記ポリオール（ａ）の数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により測定した値を示す。 The number average molecular weight of the polyol (a) is preferably 500 to 10,000, and more preferably 1,000 to 6,000, in order to obtain even better adhesion, low-temperature flexibility, and mechanical strength. The number average molecular weight of the polyol (a) is a value measured by gel permeation chromatography (GPC).
　前記イソシアネート基を有するホットメルトウレタンプレポリマー（Ａ）は、例えば、前記ポリオール（ａ）及びポリイソシアネート（ｂ）との反応物を用いることができる。 The hot melt urethane prepolymer (A) having an isocyanate group can be, for example, a reaction product of the polyol (a) and the polyisocyanate (b).
　前記ポリイソシアネート（ｂ）としては、例えば、ポリメチレンポリフェニルポリイソシアネート、ジフェニルメタンジイソシアネート、カルボジイミド変性ジフェニルメタンジイソシアネートイソシアネート、フェニレンジイソシアネート、トリレンジイソシアネート、ナフタレンジイソシアネート等の芳香族ポリイソシアネート；ヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキサンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート等の脂肪族又は脂環族ポリイソシアネートなどを用いることができる。これらのポリ伊孑志はネートは単独でも２種以上を併用してもよく、石油由来のものでも、植物由来のものでもよい。これらの中でも、より一層優れた反応性および接着性が得られる点から、芳香族ポリイソシアネートが好ましく、ジフェニルメタンジイソシアネートがより好ましい。 As the polyisocyanate (b), for example, aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more, and may be derived from petroleum or plants. Among these, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred, in that they provide even better reactivity and adhesion.
　前記ホットメルトウレタンプレポリマー（Ａ）は、空気中やウレタンプレポリマーが塗布される基材や被着体中に存在する水分と反応して架橋構造を形成しうるイソシアネート基をポリマー末端や分子内に有するものである。 The hot melt urethane prepolymer (A) has isocyanate groups at the polymer terminals or within the molecule that can react with moisture present in the air or in the substrate or adherend to which the urethane prepolymer is applied to form a crosslinked structure.
　前記ホットメルトウレタンプレポリマー（Ａ）の製造方法としては、例えば、前記ポリイソシアネート（ｂ）の入った反応容器に、前記ポリオール（ａ）を滴下した後に加熱し、前記ポリイソシアネート（ｂ）の有するイソシアネート基が、前記ポリオール（ａ）の有する水酸基に対して過剰となる条件で反応させることによって製造することができる。 The hot melt urethane prepolymer (A) 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).
　　前記ポリオール（ａ）及び前記ポリイソシアネート（ｂ）を反応させる際の、前記ポリオール（ａ）が有する水酸基と、前記ポリイソシアネート（ｂ）含有するイソシアネート基とのモル比［ＮＣＯ／ＯＨ］としては、より一層優れたホットメルト性、接着性、及び、低温屈曲性が得られる点から、１．３～２．５が好ましく、１．５～２．０がより好ましい。 When reacting the polyol (a) and the polyisocyanate (b), the molar ratio [NCO/OH] of the hydroxyl groups in the polyol (a) to the isocyanate groups in the polyisocyanate (b) is preferably 1.3 to 2.5, and more preferably 1.5 to 2.0, in order to obtain even better hot melt properties, adhesive properties, and low-temperature flexibility.
　前記ホットメルトウレタンプレポリマー（Ａ）のイソシアネート基含有率（以下、「ＮＣＯ％」と略記する。）としては、より一層優れたホットメルト性、接着性、及び、低温屈曲性が得られる点から、１．２～５．０質量％が好ましく、１．７～３．５質量％がより好ましい。なお、前記ホットメルトウレタンプレポリマー（Ａ）のＮＣＯ％は、ＪＩＳＫ１６０３－１：２００７に準拠し、電位差滴定法により測定した値を示す。 The isocyanate group content (hereinafter abbreviated as "NCO%) of the hot melt urethane prepolymer (A) is preferably 1.2 to 5.0 mass%, more preferably 1.7 to 3.5 mass%, in order to obtain even better hot melt properties, adhesion, and low-temperature flexibility. The NCO% of the hot melt urethane prepolymer (A) is a value measured by potentiometric titration in accordance with JIS K1603-1:2007.
　前記難燃剤（Ｂ）は優れた難燃性を得るうえで必須の成分であり、かつ、その含有量が、前記ホットメルトウレタンプレポリマー（Ａ）１００質量部に対して、１５質量部を超えるものであることが必須である。前記難燃剤（Ｂ）の含有量としては、低温屈曲性、及び、接着性を高いレベルで維持し、かつ、より一層優れた難燃性を得る上で、前記ホットメルトウレタンプレポリマー（Ａ）１００質量部に対して、１７．５～５５質量部が好ましい。 The flame retardant (B) is an essential component for obtaining excellent flame retardancy, and its content must exceed 15 parts by mass per 100 parts by mass of the hot-melt urethane prepolymer (A). The content of the flame retardant (B) is preferably 17.5 to 55 parts by mass per 100 parts by mass of the hot-melt urethane prepolymer (A) in order to maintain a high level of low-temperature flexibility and adhesion and obtain even better flame retardancy.
　前記難燃剤（Ｂ）としては、例えば、リン酸エステル、リン酸塩含有難燃剤、赤リン、臭素含有難燃剤、ホウ素含有難燃剤、アンチモン含有難燃剤、金属水酸化物、黒鉛、リン・ホウ素系化合物、ビニル重合体等を用いることができる。これらの難燃剤は単独で用いても２種以上を併用してもよい。これらの中でも、低温屈曲性、及び、接着性を高いレベルで維持し、かつ、より一層優れた難燃性が得られる点から、芳香環を３つ以上有するリン酸エステルが好ましく、芳香環を４つ以上有するリン酸エステルがより好ましい。 The flame retardant (B) may be, for example, a phosphate ester, a phosphate-containing flame retardant, red phosphorus, a bromine-containing flame retardant, a boron-containing flame retardant, an antimony-containing flame retardant, a metal hydroxide, graphite, a phosphorus-boron compound, a vinyl polymer, or the like. These flame retardants may be used alone or in combination of two or more. Among these, a phosphate ester having three or more aromatic rings is preferred, and a phosphate ester having four or more aromatic rings is more preferred, in that it maintains a high level of low-temperature flexibility and adhesion, and provides even more excellent flame retardancy.
　本発明の湿気硬化型ポリウレタンホットメルト樹脂組成物は、前記ホットメルトウレタンプレポリマー（Ａ）及び前記難燃剤（Ｂ）を必須成分として含有するが、必要に応じてその他の添加剤を含有してもよい。 The moisture-curable polyurethane hot-melt resin composition of the present invention contains the hot-melt urethane prepolymer (A) and the flame retardant (B) as essential components, but may contain other additives as necessary.
　前記その他の添加剤としては、例えば、ウレタン化触媒、中和剤、架橋剤、シランカップリング剤、増粘剤、充填剤、チキソ付与剤、粘着付与剤、ワックス、熱安定剤、耐光安定剤、蛍光増白剤、発泡剤、顔料、染料、導電性付与剤、帯電防止剤、透湿性向上剤、撥水剤、撥油剤、中空発泡体、吸水剤、吸湿剤、消臭剤、整泡剤、可塑剤、ブロッキング防止剤、加水分解防止剤等を用いることができる。これらの添加剤は単独で用いても２種以上を併用してもよい。 Examples of the other additives that can be used include urethane catalysts, neutralizing agents, crosslinking agents, silane coupling agents, thickeners, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, light resistance stabilizers, fluorescent whitening agents, foaming agents, pigments, dyes, conductivity agents, antistatic agents, moisture permeability enhancers, water repellents, oil repellents, hollow foams, water absorbents, moisture absorbents, deodorizers, foam stabilizers, plasticizers, antiblocking agents, hydrolysis inhibitors, etc. These additives may be used alone or in combination of two or more.
　以上、本発明の湿気硬化型ポリウレタンホットメルト樹脂組成物は、接着性、低温屈曲性、及び、難燃性に優れるものである。よって、本発明の湿気硬化型ポリウレタンホットメルト樹脂組成物は、熱可塑性樹脂を表皮材とする合成皮革の製造に特に好適に用いることができる。 As described above, the moisture-curable polyurethane hot melt resin composition of the present invention has excellent adhesion, low-temperature flexibility, and flame retardancy. Therefore, the moisture-curable polyurethane hot melt resin composition of the present invention can be particularly suitably used in the manufacture of synthetic leather that uses a thermoplastic resin as the skin material.
　次に、本発明の合成皮革について説明する。 Next, we will explain the synthetic leather of the present invention.
　前記合成皮革は、少なくとも熱可塑性樹脂層、及び、前記の湿気硬化型ポリウレタンホットメルト樹脂組成物を含有する接着剤層を有するものであり、例えば、基材、前記接着剤層、及び、熱可塑性樹脂層を順次積層したものが挙げられる。 The synthetic leather has at least a thermoplastic resin layer and an adhesive layer containing the moisture-curable polyurethane hot melt resin composition, and may be, for example, a layer of a substrate, the adhesive layer, and a thermoplastic resin layer laminated in that order.
　前記基材としては、例えば、ポリエステル繊維、ポリエチレン繊維、ナイロン繊維、アクリル繊維、ポリウレタン繊維、アセテート繊維、レーヨン繊維、ポリ乳酸繊維、綿、麻、絹、羊毛、グラスファイバー、炭素繊維、それらの混紡繊維等による不織布、織布、編み物などを用いることができる。 The substrate may be, for example, a nonwoven fabric, woven fabric, or knitted fabric 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.
　前記熱可塑性樹脂層としては、例えば、公知のポリ塩化ビニル、ポリ酢酸ビニル、ポリ塩化ビニリデン、ポリスチレン、ＴＰＯ（Ｔｈｅｒｍｏｐｌａｓｔｉｃ　Ｏｌｅｆｉｎｉｃ　Ｅｌａｓｔｏｍｅｒ）、熱可塑性エステル系エラストマー、熱可塑性ポリウレタン等により形成されたものを用いることができる。本発明においては、前記熱可塑性樹脂として、ポリ塩化ビニル、ＴＰＯ、熱可塑性エステル系エラストマー、熱可塑性ポリウレタンを用いた場合であっても優れた接着性、及び、低温屈曲性を有し、特に、難密着であるポリ塩化ビニルについては、発泡体でも未発泡体であっても優れた接着性、及び、低温屈曲性を有する。 The thermoplastic resin layer may be formed from, for example, known polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, polystyrene, TPO (thermoplastic olefinic elastomer), thermoplastic ester elastomer, thermoplastic polyurethane, etc. In the present invention, even when polyvinyl chloride, TPO, thermoplastic ester elastomer, or thermoplastic polyurethane is used as the thermoplastic resin, it has excellent adhesion and low-temperature flexibility, and in particular, for polyvinyl chloride, which is difficult to adhere to, it has excellent adhesion and low-temperature flexibility whether it is foamed or unfoamed.
　前記接着剤層は、本発明の湿気硬化型ポリウレタンホットメルト樹脂組成物により形成されるが、その形成方法としては、例えば、前記湿気硬化型ポリウレタンホットメルト樹脂組成物を１００～１４０℃で溶融した後、ロールコーター、スプレーコーター、Ｔ－ダイコーター、ナイフコーター、コンマコーター等のコーター方式；ディスペンサー、インクジェット印刷、スクリーン印刷、オフセット印刷等の精密方式；ノズル塗布などを使用して前記熱可塑性樹脂層又は前記基材に塗布し、その後貼り合わせる方法が挙げられる。 The adhesive layer is formed from the moisture-curable polyurethane hot melt resin composition of the present invention, and examples of the method for forming the adhesive layer include a method in which the moisture-curable polyurethane hot melt resin composition is melted at 100 to 140°C, and then coated onto the thermoplastic resin layer or the substrate using a coater method such as a roll coater, spray coater, T-die coater, knife coater, or comma coater; a precision method such as a dispenser, inkjet printing, screen printing, or offset printing; or a nozzle coater, and then the layers are bonded together.
　また、前記接着剤により２つの叢を貼り合わせた後は、必要に応じて接着剤を乾燥、養生を公知の方法で行うことができる。 After the two bunches are attached with the adhesive, the adhesive can be dried and cured as necessary using known methods.
　前記合成皮革としては、前記熱可塑性樹脂層のうえに、更に表面処理層を設けてもよい。前記表面処理層としては、例えば、公知の溶剤系ウレタン樹脂、水系ウレタン樹脂、溶剤系アクリル樹脂、水系アクリル樹脂等により形成されたものを用いることができる。 The synthetic leather may further have a surface treatment layer on top of the thermoplastic resin layer. The surface treatment layer may be formed from, for example, a known solvent-based urethane resin, water-based urethane resin, solvent-based acrylic resin, water-based acrylic resin, etc.
　以下、実施例を用いて、本発明をより詳細に説明する。 The present invention will now be described in more detail using examples.
［実施例１］
　温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四ツ口フラスコに、ポリテトラメチレングリコール（数平均分子量；２、０００、以下「ＰＥｔ－１」と略記する。）を１７１質量部、ポリエステルポリオール（１，６－ヘキサンジオール、及びオルトフタル酸を反応させたもの、数平均分子量；２、０００、以下「ＰＥｓ－１」と略記する。）を７８質量部、ポリエステルポリオール（１，６－ヘキサンジオール、及びセバシン酸を反応させたもの、数平均分子量；３，５００、以下「ＰＥｓ－２」と略記する。）を６２質量部入れ、混合し、１００℃で減圧加熱することにより、フラスコ内の水分が０．０５質量％以下となるまで脱水した。次いで、フラスコ内を９０℃に冷却し、７０℃で溶融した４，４’－ジフェニルメタンジイソシアネート（以下「ＭＤＩ」と略記する。）を７１質量部加え、窒素雰囲気下でイソシアネート基含有量が一定となるまで１１０℃で約３時間反応させ、ホットメルトウレタンプレポリマーを得た。このホットメルトウレタンプレポリマー１００質量部に対し、リン酸エステル（１，３－フェニレンビス（２，６－ジメチルフェニル＝ホスファート）、以下「難燃剤（Ｂ１）」と略記する。）３５質量部を配合し、湿気硬化型ポリウレタンホットメルト樹脂組成物（１）を得た。 [Example 1]
A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser was charged with 171 parts by mass of polytetramethylene glycol (number average molecular weight: 2,000, hereinafter abbreviated as "PEt-1"), 78 parts by mass of polyester polyol (residued by reacting 1,6-hexanediol and orthophthalic acid, number average molecular weight: 2,000, hereinafter abbreviated as "PEs-1"), and 62 parts by mass of polyester polyol (residued by reacting 1,6-hexanediol and sebacic acid, number average molecular weight: 3,500, hereinafter abbreviated as "PEs-2"), mixed, and heated at 100°C under reduced pressure to dehydrate the water in the flask until the water content was 0.05% by mass or less. The flask was then cooled to 90°C, and 71 parts by mass of 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") melted at 70°C was added, and the mixture was allowed to react at 110°C for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, yielding a hot-melt urethane prepolymer. 35 parts by mass of a phosphate ester (1,3-phenylenebis(2,6-dimethylphenyl=phosphate), hereinafter abbreviated as "flame retardant (B1)") was blended with 100 parts by mass of this hot-melt urethane prepolymer to obtain a moisture-curable polyurethane hot-melt resin composition (1).
［実施例２］
　温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四ツ口フラスコに、ＰＥｔ－１を７４質量部、ＰＥｓ－１を３１質量部、ＰＥｓ－２を１８質量部入れ、混合し、１００℃で減圧加熱することにより、フラスコ内の水分が０．０５質量％以下となるまで脱水した。次いで、フラスコ内を９０℃に冷却し、７０℃で溶融したＭＤＩを２７質量部加え、窒素雰囲気下でイソシアネート基含有量が一定となるまで１１０℃で約３時間反応させ、ホットメルトウレタンプレポリマーを得た。このホットメルトウレタンプレポリマー１００質量部に対し、難燃剤（Ｂ１）２５質量部を配合し、湿気硬化型ポリウレタンホットメルト樹脂組成物（２）を得た。 [Example 2]
In a four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 74 parts by mass of PEt-1, 31 parts by mass of PEs-1, and 18 parts by mass of PEs-2 were added, mixed, and heated under reduced pressure at 100 ° C., and the moisture in the flask was dehydrated until it was 0.05% by mass or less. Next, the flask was cooled to 90 ° C., 27 parts by mass of MDI melted at 70 ° C. was added, and the mixture was reacted at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot melt urethane prepolymer. 25 parts by mass of flame retardant (B1) was blended with 100 parts by mass of this hot melt urethane prepolymer to obtain a moisture-curable polyurethane hot melt resin composition (2).
［実施例３］
　温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四ツ口フラスコに、ポリプロピレングリコール（数平均分子量；２、０００、以下「ＰＥｔ－２」と略記する。）を４８質量部、ＰＥｓ－１を１７質量部、ポリエステルポリオール（エチレングリコール、ネオペンチルグリコール、１６－ヘキサンジオール、及び、アジピン酸を反応させたもの、数平均分子量；５，５００、以下「ＰＥｓ－３」と略記する。）を２２質量部入れ、混合し、１００℃で減圧加熱することにより、フラスコ内の水分が０．０５質量％以下となるまで脱水した。次いで、フラスコ内を９０℃に冷却し、７０℃で溶融したＭＤＩを１８質量部加え、窒素雰囲気下でイソシアネート基含有量が一定となるまで１１０℃で約３時間反応させ、ホットメルトウレタンプレポリマーを得た。このホットメルトウレタンプレポリマー１００質量部に対し、難燃剤（Ｂ１）３５質量部を配合し、湿気硬化型ポリウレタンホットメルト樹脂組成物（３）を得た。 [Example 3]
In a four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 48 parts by mass of polypropylene glycol (number average molecular weight: 2,000, hereinafter abbreviated as "PEt-2"), 17 parts by mass of PEs-1, and 22 parts by mass of polyester polyol (ethylene glycol, neopentyl glycol, 16-hexanediol, and adipic acid reacted, number average molecular weight: 5,500, hereinafter abbreviated as "PEs-3") were placed, mixed, and heated under reduced pressure at 100 ° C. to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90 ° C., 18 parts by mass of MDI melted at 70 ° C. was added, and the mixture was reacted at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot melt urethane prepolymer. 35 parts by mass of a flame retardant (B1) was added to 100 parts by mass of this hot-melt urethane prepolymer to obtain a moisture-curable polyurethane hot-melt resin composition (3).
［実施例４］
　温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四ツ口フラスコに、ＰＥｔ－１を１３３質量部、ＰＥｓ－１を５６質量部、ＰＥｓ－２を３３質量部入れ、混合し、１００℃で減圧加熱することにより、フラスコ内の水分が０．０５質量％以下となるまで脱水した。次いで、フラスコ内を９０℃に冷却し、７０℃で溶融したＭＤＩを４９質量部加え、窒素雰囲気下でイソシアネート基含有量が一定となるまで１１０℃で約３時間反応させ、ホットメルトウレタンプレポリマーを得た。このホットメルトウレタンプレポリマー１００質量部に対し、難燃剤（Ｂ１）３０質量部を配合し、湿気硬化型ポリウレタンホットメルト樹脂組成物（４）を得た。 [Example 4]
A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 133 parts by mass of PEt-1, 56 parts by mass of PEs-1, and 33 parts by mass of PEs-2, mixed, and heated under reduced pressure at 100 ° C. to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90 ° C., 49 parts by mass of MDI melted at 70 ° C. was added, and the mixture was reacted at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot melt urethane prepolymer. 30 parts by mass of flame retardant (B1) was blended with 100 parts by mass of this hot melt urethane prepolymer to obtain a moisture-curable polyurethane hot melt resin composition (4).
［実施例５］
　温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四ツ口フラスコに、ＰＥｔ－２を１３９質量部、ＰＥｓ－１を３２質量部、ＰＥｓ－３を４３質量部入れ、混合し、１００℃で減圧加熱することにより、フラスコ内の水分が０．０５質量％以下となるまで脱水した。次いで、フラスコ内を９０℃に冷却し、７０℃で溶融したＭＤＩを４７質量部加え、窒素雰囲気下でイソシアネート基含有量が一定となるまで１１０℃で約３時間反応させ、ホットメルトウレタンプレポリマーを得た。このホットメルトウレタンプレポリマー１００質量部に対し、難燃剤（Ｂ１）３５質量部を配合し、湿気硬化型ポリウレタンホットメルト樹脂組成物（５）を得た。 [Example 5]
A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 139 parts by mass of PEt-2, 32 parts by mass of PEs-1, and 43 parts by mass of PEs-3, mixed, and heated under reduced pressure at 100 ° C. to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90 ° C., 47 parts by mass of MDI melted at 70 ° C. was added, and the mixture was reacted at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot melt urethane prepolymer. 35 parts by mass of flame retardant (B1) was blended with 100 parts by mass of this hot melt urethane prepolymer to obtain a moisture-curable polyurethane hot melt resin composition (5).
［実施例６］
　温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四ツ口フラスコに、ＰＥｔ－１を８３質量部、ＰＥｓ－１を１９質量部、ＰＥｓ－３を２６質量部入れ、混合し、１００℃で減圧加熱することにより、フラスコ内の水分が０．０５質量％以下となるまで脱水した。次いで、フラスコ内を９０℃に冷却し、７０℃で溶融したＭＤＩを２６質量部加え、窒素雰囲気下でイソシアネート基含有量が一定となるまで１１０℃で約３時間反応させ、ホットメルトウレタンプレポリマーを得た。このホットメルトウレタンプレポリマー１００質量部に対し、難燃剤（Ｂ１）４０質量部を配合し、湿気硬化型ポリウレタンホットメルト樹脂組成物（６）を得た。 [Example 6]
In a four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 83 parts by mass of PEt-1, 19 parts by mass of PEs-1, and 26 parts by mass of PEs-3 were added, mixed, and heated under reduced pressure at 100 ° C. to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90 ° C., 26 parts by mass of MDI melted at 70 ° C. was added, and the mixture was reacted at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot melt urethane prepolymer. 40 parts by mass of flame retardant (B1) was blended with 100 parts by mass of this hot melt urethane prepolymer to obtain a moisture-curable polyurethane hot melt resin composition (6).
［実施例７］
　温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四ツ口フラスコに、ＰＥｔ－１を１２１質量部、ＰＥｔ－２を１２１質量部、ＰＥｓ－１を８１質量部、ＰＥｓ－２を８１質量部入れ、混合し、１００℃で減圧加熱することにより、フラスコ内の水分が０．０５質量％以下となるまで脱水した。次いで、フラスコ内を９０℃に冷却し、７０℃で溶融したＭＤＩを８７質量部加え、窒素雰囲気下でイソシアネート基含有量が一定となるまで１１０℃で約３時間反応させ、ホットメルトウレタンプレポリマーを得た。このホットメルトウレタンプレポリマー１００質量部に対し、難燃剤（Ｂ１）３０質量部を配合し、湿気硬化型ポリウレタンホットメルト樹脂組成物（７）を得た。 [Example 7]
A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 121 parts by mass of PEt-1, 121 parts by mass of PEt-2, 81 parts by mass of PEs-1, and 81 parts by mass of PEs-2, mixed, and heated under reduced pressure at 100 ° C. to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90 ° C., 87 parts by mass of MDI melted at 70 ° C. was added, and the mixture was reacted at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot melt urethane prepolymer. 30 parts by mass of flame retardant (B1) was blended with 100 parts by mass of this hot melt urethane prepolymer to obtain a moisture-curable polyurethane hot melt resin composition (7).
［実施例８］
　ＰＥｔ－１をバイオマスポリテトラメチレングリコール（三菱ケミカル株式会社製「Ｂｉｏ　ＰＴＭＧ」、数平均分子量；２，０００）に種類を変更した以外は実施例１と同様にして湿気硬化型ポリウレタンホットメルト樹脂組成物（８）を得た。 [Example 8]
A moisture-curable polyurethane hot melt resin composition (8) was obtained in the same manner as in Example 1, except that PEt-1 was replaced with biomass polytetramethylene glycol ("Bio PTMG" manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000).
［比較例１］
　温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四ツ口フラスコに、ＰＥｔ－１を９２質量部、ＰＥｓ－１を３３質量部、ＰＥｓ－２を２５質量部入れ、混合し、１００℃で減圧加熱することにより、フラスコ内の水分が０．０５質量％以下となるまで脱水した。次いで、フラスコ内を９０℃に冷却し、７０℃で溶融したＭＤＩを３３質量部加え、窒素雰囲気下でイソシアネート基含有量が一定となるまで１１０℃で約３時間反応させ、ホットメルトウレタンプレポリマーを得た。このホットメルトウレタンプレポリマー１００質量部に対し、難燃剤（Ｂ１）１０質量部を配合し、湿気硬化型ポリウレタンホットメルト樹脂組成物（Ｒ１）を得た。 [Comparative Example 1]
A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 92 parts by mass of PEt-1, 33 parts by mass of PEs-1, and 25 parts by mass of PEs-2, mixed, and heated under reduced pressure at 100 ° C. to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90 ° C., 33 parts by mass of MDI melted at 70 ° C. was added, and the mixture was reacted at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot melt urethane prepolymer. 100 parts by mass of this hot melt urethane prepolymer was mixed with 10 parts by mass of flame retardant (B1) to obtain a moisture-curable polyurethane hot melt resin composition (R1).
［比較例２］
　温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四ツ口フラスコに、ＰＥｔ－２を１０９質量部、ＰＥｓ－１を４５質量部、ＰＥｓ－２を２７質量部入れ、混合し、１００℃で減圧加熱することにより、フラスコ内の水分が０．０５質量％以下となるまで脱水した。次いで、フラスコ内を９０℃に冷却し、７０℃で溶融したＭＤＩを４０質量部加え、窒素雰囲気下でイソシアネート基含有量が一定となるまで１１０℃で約３時間反応させ、ホットメルトウレタンプレポリマーを得、湿気硬化型ポリウレタンホットメルト樹脂組成物（Ｒ２）を得た。 [Comparative Example 2]
In a four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 109 parts by mass of PEt-2, 45 parts by mass of PEs-1, and 27 parts by mass of PEs-2 were placed, mixed, and heated under reduced pressure at 100 ° C. to dehydrate the water content in the flask to 0.05% by mass or less. Next, the flask was cooled to 90 ° C., 40 parts by mass of MDI melted at 70 ° C. was added, and the mixture was reacted at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot melt urethane prepolymer, and a moisture-curable polyurethane hot melt resin composition (R2) was obtained.
［比較例３］
　温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四ツ口フラスコに、ＰＥｔ－１を１１１質量部、ＰＥｓ－１を７７質量部、ＰＥｓ－３を６６質量部入れ、混合し、１００℃で減圧加熱することにより、フラスコ内の水分が０．０５質量％以下となるまで脱水した。次いで、フラスコ内を９０℃に冷却し、７０℃で溶融したＭＤＩを５０質量部加え、窒素雰囲気下でイソシアネート基含有量が一定となるまで１１０℃で約３時間反応させ、ホットメルトウレタンプレポリマーを得た。このホットメルトウレタンプレポリマー１００質量部に対し、難燃剤（Ｂ１）６５質量部を配合し、湿気硬化型ポリウレタンホットメルト樹脂組成物（Ｒ３）を得た。 [Comparative Example 3]
In a four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 111 parts by mass of PEt-1, 77 parts by mass of PEs-1, and 66 parts by mass of PEs-3 were added, mixed, and heated under reduced pressure at 100 ° C., and the moisture in the flask was dehydrated until it was 0.05% by mass or less. Next, the flask was cooled to 90 ° C., 50 parts by mass of MDI melted at 70 ° C. was added, and the mixture was reacted at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot melt urethane prepolymer. 65 parts by mass of flame retardant (B1) was blended with 100 parts by mass of this hot melt urethane prepolymer to obtain a moisture-curable polyurethane hot melt resin composition (R3).
［比較例４］
　温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四ツ口フラスコに、ＰＥｔ－１を２７質量部、ＰＥｓ－１を４１質量部、ＰＥｓ－３を２３質量部入れ、混合し、１００℃で減圧加熱することにより、フラスコ内の水分が０．０５質量％以下となるまで脱水した。次いで、フラスコ内を９０℃に冷却し、７０℃で溶融したＭＤＩを１８質量部加え、窒素雰囲気下でイソシアネート基含有量が一定となるまで１１０℃で約３時間反応させ、ホットメルトウレタンプレポリマーを得た。このホットメルトウレタンプレポリマー１００質量部に対し、難燃剤（Ｂ１）４０質量部を配合し、湿気硬化型ポリウレタンホットメルト樹脂組成物（Ｒ４）を得た。 [Comparative Example 4]
In a four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 27 parts by mass of PEt-1, 41 parts by mass of PEs-1, and 23 parts by mass of PEs-3 were added, mixed, and heated under reduced pressure at 100 ° C., and the moisture in the flask was dehydrated until it was 0.05% by mass or less. Next, the flask was cooled to 90 ° C., 18 parts by mass of MDI melted at 70 ° C. was added, and the mixture was reacted at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, to obtain a hot melt urethane prepolymer. 40 parts by mass of flame retardant (B1) was blended with 100 parts by mass of this hot melt urethane prepolymer to obtain a moisture-curable polyurethane hot melt resin composition (R4).
［数平均分子量、重量平均分子量の測定方法］
実施例および比較例で用いたポリオールの数平均分子量は、ゲル・パーミエーション・カラムクロマトグラフィー（ＧＰＣ）法により、下記の条件で測定し得られた値を示す。 [Method of measuring number average molecular weight and weight average molecular weight]
The number average molecular weights of the polyols used in the examples and comparative examples are values measured by gel permeation column chromatography (GPC) under the following conditions.
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
　「ＴＳＫｇｅｌ　Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成した。 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. x 30cm) x 1 Detector: RI (differential refractometer)
Column temperature: 40°C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min Injection volume: 100 μL (sample concentration 0.4% by mass in tetrahydrofuran solution)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
（標準ポリスチレン）
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－１０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－２５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－８０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１２８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２８８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－５５０」 (Standard polystyrene)
"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation
［合成皮革の作製方法］
　温度２３℃、湿度５０±５％に調整された恒温恒湿室にて、ポリ塩化ビニルシートにグラビアコーターを用いて、実施例及び比較例で得られた湿気硬化型ポリウレタンホットメルト樹脂組成物を４０±５ｇ／ｍ２となるように間欠塗布し、ポリエステル系生地と貼り合わせしたものを温度２３℃、湿度５０±５％の条件で２４時間熟成させることで合成皮革を得た。 [Method of producing synthetic leather]
In a constant temperature and humidity chamber adjusted to a temperature of 23°C and a humidity of 50±5%, a polyvinyl chloride sheet was intermittently coated with a gravure coater to give a coating of 40±5 g/ m2 of the moisture-curable polyurethane hot-melt resin composition obtained in the Examples and Comparative Examples. The sheet was then laminated with a polyester fabric and aged for 24 hours at a temperature of 23°C and a humidity of 50±5%, to obtain synthetic leather.
［接着性の評価方法］
　得られたそれぞれの合成皮革に対して、テンシロン（オリエンテック株式会社製テンシロン万能試験機「ＲＴＣ－１２１０Ａ」）を使用して、クロスヘッド測度；２００ｍｍ／分の条件で剥離強度を測定し、６Ｎ／ｃｍ以上を「○」、６Ｎ／ｃｍ未満を「×」と評価した。 [Method for evaluating adhesiveness]
For each of the obtained synthetic leathers, the peel strength was measured using a Tensilon (Tensilon universal testing machine "RTC-1210A" manufactured by Orientec Co., Ltd.) under the condition of a crosshead measurement of 200 mm/min, and a value of 6 N/cm or more was evaluated as "○", and a value of less than 6 N/cm was evaluated as "×".
［低温屈曲性の評価方法］
　得られたそれぞれの合成皮革をフレキソメーターでの屈曲性試験（－１０℃、１００回／毎分）を行い、合成皮革の表面に割れが生じるまでの回数を測定し、２０，０００回以上を「○」、２０，０００回未満を「×」と評価した。 [Method for evaluating low-temperature flexibility]
Each of the obtained synthetic leathers was subjected to a bending test using a flexometer (−10° C., 100 times/min) to measure the number of times until cracks appeared on the surface of the synthetic leather. 20,000 times or more was evaluated as "○", and less than 20,000 times was evaluated as "×".
［難燃性の評価方法］
　実施例及び比較例で得られた湿気硬化型ポリウレタンホットメルト樹脂組成物をロールコーターにて厚さ３００ミクロンになるように塗布し、その後、温度２３℃、湿度５０±５％の条件で７２時間以上熟成させて皮膜を作製した。次いで、得られた皮膜を幅１０２ｍｍ、長さ３５６ｍｍの長方形に裁断し、燃焼性試験（ＦＭＶＳＳ３０２）を実施した。試験片に着火しない又はＡ標線手前で自消するもの、燃焼距離５１ｍｍ以内(且つ６０秒以内)で自消するもの、燃焼速度が１０２ｍｍ／分以下のものを「○」、それ以外のものを「×」とした。 [Flame retardancy evaluation method]
The moisture-curable polyurethane hot melt resin composition obtained in the examples and comparative examples was applied to a thickness of 300 microns using a roll coater, and then aged for 72 hours or more under conditions of a temperature of 23°C and a humidity of 50±5% to produce a film. The obtained film was then cut into a rectangle with a width of 102 mm and a length of 356 mm, and a flammability test (FMVSS302) was performed. Test pieces that did not ignite or self-extinguished before the A-marked line, those that self-extinguished within a burning distance of 51 mm (and within 60 seconds), and those with a burning rate of 102 mm/min or less were marked as "○", and those that did not were marked as "×".
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　本発明の湿気硬化型ポリウレタンホットメルト樹脂組成物である実施例１～８は、接着性、低温屈曲性、及び、難燃性に優れることが分かった。 　It was found that Examples 1 to 8, which are moisture-curable polyurethane hot melt resin compositions of the present invention, have excellent adhesion, low-temperature flexibility, and flame retardancy.
　一方、比較例１は、難燃剤（Ｂ）の含有量が、本発明で規定する範囲を下回る態様であるが、難燃性が不良であった。 On the other hand, in Comparative Example 1, the content of flame retardant (B) was below the range specified in the present invention, but the flame retardancy was poor.
　比較例２は、難燃剤（Ｂ）を用いない態様であるが、難燃性が不良であった。 Comparative Example 2 is an embodiment in which flame retardant (B) is not used, but the flame retardancy was poor.
　比較例３及び４は、ポリエーテルポリオール（ａ１）の使用量が、本発明で規定する範囲を下回る態様であるが、低温屈曲性等が不良であった。 Comparative examples 3 and 4 are examples in which the amount of polyether polyol (a1) used is below the range specified in the present invention, but the low-temperature flexibility and other properties were poor.

Claims (4)

  1. イソシアネート基を有するホットメルトウレタンプレポリマー（Ａ）、及び、難燃剤（Ｂ）を含有する湿気硬化型ポリウレタンホットメルト樹脂組成物であって、
    前記ホットメルトプレポリマー（Ａ）が、ポリエーテルポリオール（ａ１）を５０質量％以上含むポリオール（ａ）を原料とするものであり、
    前記難燃剤（Ｂ）の含有量が、前記ホットメルトウレタンプレポリマー（Ａ）１００質量部に対して、１５質量部を超えるものであることを特徴とする湿気硬化型ポリウレタンホットメルト樹脂組成物。     A moisture-curable polyurethane hot-melt resin composition comprising a hot-melt urethane prepolymer (A) having an isocyanate group and a flame retardant (B),
    The hot melt prepolymer (A) is made from a polyol (a) containing 50% by mass or more of a polyether polyol (a1),
    A moisture-curable polyurethane hot-melt resin composition, characterized in that the content of the flame retardant (B) is more than 15 parts by mass per 100 parts by mass of the hot-melt urethane prepolymer (A).
  2. 前記難燃剤（Ｂ）が、芳香環を３つ以上有するリン酸エステルである請求項１記載の湿気硬化型ポリウレタンホットメルト樹脂組成物。 The moisture-curable polyurethane hot melt resin composition according to claim 1, wherein the flame retardant (B) is a phosphoric acid ester having three or more aromatic rings.
  3. 請求項１記載の湿気硬化型ポリウレタンホットメルト樹脂組成物を含有することを特徴とする接着剤。 An adhesive comprising the moisture-curable polyurethane hot melt resin composition according to claim 1.
  4. 少なくとも、熱可塑性樹脂層、及び、請求項３記載の接着剤層とを有することを特徴とする合成皮革。 Synthetic leather characterized by having at least a thermoplastic resin layer and the adhesive layer described in claim 3.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003049147A (en) * 2001-08-08 2003-02-21 Dainippon Ink & Chem Inc Nonsolvent-type hot-melt urethane resin adhesive curable by moisture for synthetic leather, and synthetic leather structure using the same
JP2005206828A (en) * 2003-12-25 2005-08-04 Dainippon Ink & Chem Inc Moisture-curing polyurethane hot melt resin composition
CN104099055A (en) * 2013-04-07 2014-10-15 广东国望精细化学品有限公司 Halogenn-free flame retardant polyurethane sealant and preparation method thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003049147A (en) * 2001-08-08 2003-02-21 Dainippon Ink & Chem Inc Nonsolvent-type hot-melt urethane resin adhesive curable by moisture for synthetic leather, and synthetic leather structure using the same
JP2005206828A (en) * 2003-12-25 2005-08-04 Dainippon Ink & Chem Inc Moisture-curing polyurethane hot melt resin composition
CN104099055A (en) * 2013-04-07 2014-10-15 广东国望精细化学品有限公司 Halogenn-free flame retardant polyurethane sealant and preparation method thereof
JP2020002262A (en) * 2018-06-28 2020-01-09 Dic株式会社 Moisture-curable polyurethane hot-melt resin composition

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HIDEO SASAKI: "Flame Retardants", NEW REVISED EDITION: PLASTIC COMPOUNDING AGENTS - FUNDAMENTALS AND APPLICATIONS. K.K. TAISEISHA, 1996, pages 139 *
IMAMURA, TAKEO: "Flame Retardants", PLASTIC DATA BOOK. KOGYO CHOSAKAI PUBLISHING CO., LTD., 1 December 1999 (1999-12-01), pages 1003 *

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