Moisture-cured polyurethane hot melt resin composition, adhesive and laminate

Abstract

The object of this invention is to provide a moisture-curing polyurethane resin composition that exhibits excellent adhesion and superior texture to waterproof fabrics and the like. This invention provides a moisture-curing polyurethane hot-melt resin composition comprising a urethane prepolymer (X) having isocyanate groups, said urethane prepolymer (X) being produced using the following materials as raw materials: a compound (A) having hydroxyl groups, said compound (A) being produced using a five-membered cyclic carbonate compound (a1) and a monoamine compound (a2); a polyol (B); and a polyisocyanate (C). Furthermore, this invention provides an adhesive comprising a moisture-curing polyurethane hot-melt resin composition. Furthermore, this invention provides a laminate comprising at least: a fabric (i); and a cured product of the moisture-curing polyurethane hot-melt resin composition.

Description

Technical Field

[0001] This invention relates to a moisture-curing polyurethane hot melt resin composition, adhesive, and laminate. Background Technology

[0002] Breathable and waterproof functional garments are constructed by bonding a breathable membrane to a fabric using an adhesive. As an adhesive, urethane adhesives are widely used due to their excellent adhesion to both the breathable membrane and the fabric. Among urethane adhesives, solvent-free, moisture-curing polyurethane hot-melt resin compositions are increasingly being used due to recent global solvent emission and residual solvent regulations (see, for example, patent literature (PTL) 1).

[0003] On the other hand, the fabrics to be used have become finer and more waterproof due to their lighter weight and higher functionality, which has led to a problem of reduced adhesion between the waterproofed fabric and the adhesive. Among existing wet-curing polyurethane hot melt resin compositions, no wet-curing polyurethane hot melt resin composition has been found that has particularly high adhesion to waterproofed fabrics.

[0004] Citation List

[0005] Patent documents

[0006] PTL 1: Japanese Unexamined Patent Application Publication No. 2017-202608. Summary of the Invention

[0007] Technical issues

[0008] The purpose of this invention is to provide a wet-curing polyurethane hot melt resin composition that has excellent adhesion to waterproof fabrics and the like and has excellent texture.

[0009] Problem Solution

[0010] The present invention provides a moisture-curing polyurethane hot melt resin composition comprising a urethane prepolymer (X) having isocyanate groups, the urethane prepolymer (X) being produced using the following materials as raw materials: a compound (A) having hydroxyl groups, the compound (A) being produced using a five-membered cyclic carbonate compound (a1) and a monoamine compound (a2) as raw materials; a polyol (B); and a polyisocyanate (C).

[0011] Furthermore, the present invention provides an adhesive comprising the moisture-curing polyurethane hot melt resin composition. Additionally, the present invention provides a laminate comprising at least: a fabric (i); and a cured product of the moisture-curing polyurethane hot melt resin composition.

[0012] Advantages of the invention

[0013] The moisture-curing polyurethane hot melt resin composition according to the present invention does not contain solvents, and therefore is an environmentally responsive material. Furthermore, the moisture-curing polyurethane hot melt resin composition according to the present invention exhibits excellent adhesion to various fabrics (even waterproof fabrics), and possesses excellent texture and high strength. Detailed Implementation

[0014] The wet-curing polyurethane hot melt resin composition used in this invention comprises a urethane prepolymer (X) having isocyanate groups, said urethane prepolymer (X) being produced using the following materials as raw materials: a specific compound having hydroxyl groups; a polyol (B); and a polyisocyanate (C).

[0015] Compound (A) is produced using a five-membered cyclic carbonate compound (a1) and a monoamine compound (a2) as raw materials and has hydroxyl groups. The raw materials using compound (A) provide hydrophobicity and strength, thereby ensuring excellent adhesion and texture, especially to waterproof fabrics.

[0016] Examples of five-membered cyclic carbonate compounds include reaction products of bifunctional epoxides with carbon dioxide and compounds represented by formula (1). These compounds may be used alone or in combination of two or more.

[0017] [Chemical Formula 1]

[0018] .

[0019] In equation (1), R 1 and R 2 Each can be independently represented as a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a hydroxyalkyl group having 1 to 22 carbon atoms.

[0020] Examples of usable bifunctional epoxy compounds include 1,4-bis(ethylene oxide-2-ylmethoxy)butane, bisphenol A glycidyl ether, bisphenol F glycidyl ether, bisphenol S glycidyl ether, bisphenol AD ​​glycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, hydroquinone diglycidyl ether, 4,4'-dihydroxybiphenyl diglycidyl ether, neopentyl glycol diglycidyl ether, and resorcinol diglycidyl ether. These compounds can be used alone or in combination of two or more. Among these compounds, 1,4-bis(ethylene oxide-2-ylmethoxy)butane, bisphenol A glycidyl ether, and glycerol 1,2-carbonate are preferred from the perspective of achieving better hydrophobicity and higher strength.

[0021] For the reaction of bifunctional epoxides with carbon dioxide, known methods can be used. For example, see Japanese Unexamined Patent Application Publication No. 2020-117565 and Japanese Unexamined Patent Application Publication No. H8-169976.

[0022] Specific examples of the reaction products of bifunctional epoxy compounds with carbon dioxide include compounds represented by formulas (2) to (16). In formulas (2) to (16), R independently represents a hydrogen atom or a methyl group.

[0023] [Chemical Formula 2]

[0024]

[0025] [Chemical Formula 3]

[0026]

[0027] [Chemical Formula 4]

[0028]

[0029] [Chemical Formula 5]

[0030]

[0031] [Chemical Formula 6]

[0032]

[0033] [Chemical Formula 7]

[0034]

[0035] [Chemical Formula 8]

[0036]

[0037] [Chemical Formula 9]

[0038]

[0039] [Chemical Formula 10]

[0040]

[0041] [Chemical Formula 11]

[0042]

[0043] [Chemical Formula 12]

[0044]

[0045] [Chemical Formula 13]

[0046]

[0047] [Chemical Formula 14]

[0048]

[0049] [Chemical Formula 15]

[0050]

[0051] [Chemical Formula 16]

[0052]

[0053] The five-membered cyclic carbonate compound (a1) is preferably the product of the reaction of 1,4-bis(ethylene oxide-2-ylmethoxy)butane with carbon dioxide and is represented by formula (10), such that R in formula (1) 1 It is a hydrogen atom and R 2 It is a hydroxyalkyl compound having 1 to 22 carbon atoms.

[0054] The monoamine compound (a2) is a compound having one amino group, and examples of usable monoamine compounds (a2) include straight-chain and / or branched monoamines containing alkyl groups having 8 to 22 carbon atoms, saturated cyclic monoamines having the above-described structure, and saturated heterocyclic monoamines having the above-described structure. These compounds can be used alone or in combination of two or more. Among these compounds, straight-chain and / or branched monoamines having alkyl groups having 12 to 18 carbon atoms are preferred from the viewpoint of improving affinity with waterproof fabrics and thereby improving the permeability of the fabric and thus achieving better adhesion.

[0055] For the reaction of a five-membered cyclic carbonate compound (a1) with a monoamine compound (a2), known methods can be used.

[0056] The number-average molecular weight of the obtained compound (A) having hydroxyl groups is preferably in the range of 200 to 5,000, and more preferably in the range of 300 to 3,000. Note that the number-average molecular weight of compound (A) is a value determined by gel permeation chromatography (GPC).

[0057] The amount of compound (A) used is preferably in the range of 0.5% by mass to 20.0% by mass, and more preferably in the range of 1.0% by mass to 15.0% by mass, based on the total mass of the raw materials constituting the urethane prepolymer (X).

[0058] Examples of usable polyols (B) include polyester polyols, polycaprolactone polyols, polyether polyols, polycarbonate polyols, polyacrylic acid polyols, and polybutadiene polyols. These polyols can be used alone or in combination of two or more. Among these polyols, from the viewpoint of achieving superior mechanical strength, adhesiveness, etc., it is preferable to use at least one polyol selected from the group consisting of polyester polyols, polyether polyols, polycaprolactone polyols, and polycarbonate polyols.

[0059] From the perspective of achieving superior mechanical strength, adhesiveness, etc., the number average molecular weight of the polyol (B) is preferably in the range of 500 to 10,000, and more preferably in the range of 700 to 5,000. Note that the number average molecular weight of the polyol is a value determined by gel permeation chromatography (GPC).

[0060] For polyols (B), if necessary, chain extenders with a molecular weight of less than 500 may be used, such as compounds with two or more hydroxyl groups or compounds with two or more amino groups.

[0061] The amount of polyol (B) is preferably in the range of 80% to 99.5% by mass, and more preferably in the range of 85% to 99% by mass, based on the total mass of the raw materials constituting the urethane prepolymer (X).

[0062] Examples of usable polyisocyanates (C) include: aromatic polyisocyanates, such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane isocyanate, xylene diisocyanate, phenylene diisocyanate, methylphenylene diisocyanate, and naphthalene diisocyanate; and 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 polyisocyanates, aromatic polyisocyanates are preferred from the viewpoint of achieving better reactivity and adhesion to fabrics, and diphenylmethane diisocyanate is more preferred.

[0063] The amount of polyisocyanate (C) is preferably in the range of 10.0% by mass to 50.0% by mass, and more preferably in the range of 15.0% by mass to 30.0% by mass, based on the total mass of the raw materials constituting the urethane prepolymer (X).

[0064] The hot melt urethane prepolymer (X) is obtained by reacting the above raw materials (A) to raw material (C) with each other, and has isocyanate groups that can form a cross-linked structure by reacting with moisture present in the air or in the substrate on which the wet-curing polyurethane hot melt resin composition is applied.

[0065] The urethane prepolymer (X) can be produced, for example, by filling a reaction vessel containing a compound (A) and a polyol (B) with polyisocyanate (C) and reacting the compound (A) and the polyol (B) with the polyisocyanate (C) under conditions where the isocyanate groups of the polyisocyanate (C) exceed the hydroxyl groups of the polyol (B).

[0066] In the production of urethane prepolymer (X), from the perspective of achieving better adhesion to fabrics, the equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate group of polyisocyanate (C) to the hydroxyl group of compound (A) and polyol (B) is preferably in the range of 1.1 to 5.0, and more preferably in the range of 1.5 to 3.0.

[0067] From the perspective of achieving superior adhesion, the isocyanate group content (hereinafter abbreviated as "NCO%)" of the urethane prepolymer (X) obtained by the above method is preferably in the range of 1.7 to 6.0, and more preferably in the range of 1.8 to 5.0. The NCO% of the hot melt urethane prepolymer (X) is a value measured by potentiometric titration according to Japanese Industrial Standards (JIS) K1603-1:2007.

[0068] The wet-curing polyurethane hot melt resin composition used in this invention contains urethane prepolymer (X) as the main component and may contain other additives as needed.

[0069] Examples of other additives that may be used include light stabilizers, curing catalysts, tackifiers, plasticizers, stabilizers, fillers, dyes, pigments, optical brighteners, silane coupling agents, waxes, and thermoplastic resins. These additives may be used alone or in combination of both or more.

[0070] As described above, the moisture-curing polyurethane hot melt resin composition according to the present invention does not contain solvents, and therefore is an environmentally responsive material. Furthermore, the moisture-curing polyurethane hot melt resin composition according to the present invention exhibits excellent adhesion to various fabrics (even waterproof fabrics), and possesses excellent texture and high strength.

[0071] The laminate according to the present invention will be described next.

[0072] The laminate according to the invention comprises at least a fabric (i) and a cured product of a wet-curing polyurethane hot melt resin composition.

[0073] Examples of usable fabrics (i) include: fiber substrates, such as nonwoven fabrics, woven fabrics, and knitted fabrics, said fiber substrates being made of polyester fibers, polyethylene fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, polylactic acid fibers, cotton, linen, silk, wool, glass fibers, carbon fibers, or fiber mixtures thereof; substrates obtained by impregnating nonwoven fabrics with resins such as polyurethane resins; substrates obtained by providing a porous layer to nonwoven fabrics; and resin substrates.

[0074] This invention also exhibits excellent adhesion to fabrics intended for use as fabric (i): fabrics obtained by applying a water-repellent treatment to any of the fabrics listed above (hereinafter abbreviated as "water-repellent fabric"). Note that in this invention, the "water-repellency" of a water-repellent fabric means a surface free energy of 50 mJ / m² or less, determined by the following calculations. In this specification, a water-repellent fabric is a fabric that has undergone a water-repellent treatment before the use of an adhesive.

[0075] The contact angles of the measurement liquids (water and diiodomethane) on fabric (i) were measured using a contact angle meter (“DM500”, manufactured by Kyowa Interface Science Co., Ltd.). Based on the measurement results, the surface free energy of fabric (i) was calculated using the following equation (1).

[0076]

[0077] A: Measure the contact angle of the liquid on the fabric (i).

[0078] γL: Measure the surface tension of a liquid

[0079] γLd: The dispersion force component of the surface free energy of a liquid.

[0080] γLp: Polar force component for measuring the surface free energy of a liquid

[0081] γsd: Dispersion force component of the surface free energy of fabric (i)

[0082] γsp: Polar force component of the surface free energy of fabric (i)

[0083] Examples of methods for applying wet-curing polyurethane hot melt resin compositions include methods using a roll coater, knife coater, spray coater, gravure roll coater, comma coater, T-die coater, applicator, or dispenser.

[0084] After application, the wet-curing polyurethane hot melt resin composition can be dried and cured by known methods.

[0085] The thickness of the cured product of the wet-curing urethane hot melt resin composition is, for example, in the range of 5 micrometers to 300 micrometers.

[0086] Note that when the moisture-curing polyurethane hot melt resin composition according to the invention is used as an adhesive for breathable and waterproof functional clothing, it is preferable to apply the moisture-curing polyurethane hot melt resin composition intermittently using a gravure roller coater or dispenser to bond the fabric (i) to a known breathable membrane. In this case, the thickness of the cured product of the moisture-curing polyurethane hot melt resin composition is, for example, in the range of 5 micrometers to 50 micrometers.

[0087] In addition, mesh fabric can be laminated onto a moisture-permeable membrane by intermittently applying a wet-curing polyurethane hot melt resin composition.

[0088] [Example]

[0089] The invention will be described in more detail below through examples.

[0090] [Synthetic Example 1] Preparation of a five-membered cyclic carbonate compound (a1-1)

[0091] One mole of 1,4-bis(ethylene oxide-2-ylmethoxy)butane with a molecular weight of 202 and 1.25% molar equivalent of tetrabutylammonium iodide (TBAI) were charged into a reaction vessel equipped with a stirrer and an atmospheric pressure reflux device. Subsequently, the pressure of carbon dioxide in the reaction vessel was increased from atmospheric pressure to 2.0 MPa at 120 °C, and carbon dioxide was intermittently purged while stirring to maintain the carbon dioxide pressure at 2 MPa for 24 hours, thereby obtaining a five-membered cyclic carbonate compound (a1-1). The five-membered cyclic carbonate compound (a1-1) is a pale yellow solid at room temperature and was analyzed by 1H nuclear magnetic resonance (NMR) (400 M, Japan Electron Optics Laboratory, JEOL). As a result, in 1H-NMR using N,N-dimethylformamide (DMF) as an internal standard, the cyclic carbonate equivalent of the obtained five-membered cyclic carbonate compound (a1-1) was 235.7. In quantitative carbon spectroscopy, the absorption of the epoxy groups of the starting material disappeared at around 50 ppm, while the carbonyl group of the carbonate group of the obtained substance appeared at around 155 ppm. The above reaction can be referred to in equation (17).

[0092] [Chemical Formula 17]

[0093] (17)

[0095] [Synthetic Example 2] Preparation of a compound (A-1) having a hydroxyl group

[0096] 0.1 moles of the five-membered cyclic carbonate compound (a1-1) obtained in Synthesis Example 1 and 0.2 moles of octadecyl primary (mono)amine (hereinafter abbreviated as ODA) were charged into a reaction vessel equipped with a stirrer and a reflux device with an atmospheric pressure vent. The resulting mixture, in which the above compounds were in a liquid state, was then reacted under a nitrogen stream at 80°C with stirring for 8 hours, thereby obtaining a compound with hydroxyl groups (A-1).

[0097] The obtained product was a white to pale yellow solid at room temperature and was analyzed by 13C-NMR (400M, JEOL). The analysis showed that the characteristic peak of the cyclic carbon in the cyclic carbonate of the obtained compound (A-1) had disappeared, and the ratio of primary hydroxyl (62.9 ppm) to secondary hydroxyl (69.3 ppm) was 0.25:0.75. Hydroxyl value titration showed that the obtained compound had a hydroxyl value of 155 mg KOH / g. The above reaction can be referred to in equation (18).

[0098] [Chemical Formula 18]

[0099] (18)

[0101] [Synthetic Example 3] Preparation of a compound (A-2) containing a hydroxyl group

[0102] 0.1 mol of glycerol 1,2-carbonate and 0.1 mol of octadecyl monoamine were charged into a reaction vessel equipped with a stirrer and a reflux device with an atmospheric pressure vent. The resulting mixture, in which ODA was in a liquid state, was then reacted under a nitrogen stream at 80°C with stirring for 8 hours to obtain compound (A-2). The obtained compound (A-2) is a white to pale yellow solid at room temperature and has a hydroxyl value of 293.0 mg KOH / g. The above reaction can be described with reference to the following formula (19).

[0103] [Chemical Formula 19]

[0104] (19)

[0106] [Example 1]

[0107] A reaction vessel equipped with a stirrer and a reflux device with an atmospheric pressure vent was filled with 2.0 parts by weight of the compound (A-1) obtained in Synthesis Example 2, 90 parts by weight of polyester polyol 1 (produced by reacting 1,6-hexanediol, 2-methyl-1,3-propanediol with adipic acid, number average molecular weight: 2,000), 135 parts by weight of polyester polyol 2 (produced by reacting 1,6-hexanediol with adipic acid, number average molecular weight: 2,000), and 20 parts by weight of polyether polyol 1 (polypropylene glycol, number average molecular weight: 1,000). The mixture was stirred under a nitrogen atmosphere at 110°C and then dehydrated under vacuum for 1 hour. Subsequently, after cooling the mixture to 80°C, 80.0 parts by weight of diphenylmethane diisocyanate (hereinafter abbreviated as MDI) was added. The resulting mixture was heated to 110°C and reacted for 3 hours until the isocyanate group content became constant, thereby obtaining the urethane prepolymer (X-1). The NCO% of the urethane prepolymer (X-1) was 4.75% by mass, and the melt viscosity of the urethane prepolymer (X-1) at 120°C, measured by a cone-plate viscometer, was 1,300 mPa·s (mPa). s).

[0108] [Example 2]

[0109] Ten parts by mass of the compound (A-1) obtained in Synthesis Example 2, 90 parts by mass of polyester polyol 1, 135 parts by mass of polyester polyol 2, and 20 parts by mass of polyether polyol 1 were charged into a reaction vessel equipped with a stirrer and a reflux device with an atmospheric pressure vent. The mixture was stirred under a nitrogen atmosphere at 110°C and dehydrated under vacuum for 1 hour. The resulting product was then cooled to 80°C and 83.5 parts by mass of MDI were added. The resulting mixture was slowly heated to 110°C and reacted for 3 hours, thereby obtaining a urethane prepolymer (X-2) with isocyanate groups. The NCO% of the urethane prepolymer (X-2) was 4.68% by mass, and the melt viscosity of the urethane prepolymer (X-2) at 100°C, as measured by a cone-plate viscometer, was 1,500 mPa·s.

[0110] [Example 3]

[0111] 35 parts by mass of the compound (A-1) obtained in Synthesis Example 2, 90 parts by mass of polyester polyol 1, 135 parts by mass of polyester polyol 2, and 20 parts by mass of polyether polyol 1 were packed into a reaction vessel equipped with a stirrer and a reflux device with an atmospheric pressure vent. The mixture was stirred under a nitrogen atmosphere at 110°C and dehydrated under vacuum for 1 hour. The resulting product was then cooled to 80°C and 97.7 parts by mass of MDI were added. The resulting mixture was slowly heated to 110°C and reacted for 3 hours, thereby obtaining a urethane prepolymer (X-3) with isocyanate groups. The NCO% of the urethane prepolymer (X-3) was 4.75% by mass, and the melt viscosity of the urethane prepolymer (X-3) at 100°C, as measured by a cone-plate viscometer, was 2,000 mPa·s.

[0112] [Example 4]

[0113] Two parts by mass of the compound (A-2) obtained in Synthesis Example 3, 90 parts by mass of polyester polyol 1, 135 parts by mass of polyester polyol 2, and 20 parts by mass of polyether polyol 1 were charged into a reaction vessel equipped with a stirrer and a reflux device with an atmospheric pressure vent. The mixture was stirred under a nitrogen atmosphere at 110°C and dehydrated under vacuum for 1 hour. The resulting product was then cooled to 80°C and 80.7 parts by mass of MDI were added. The resulting mixture was slowly heated to 110°C and reacted for 3 hours, thereby obtaining a urethane prepolymer (X-4) with isocyanate groups. The NCO% of the urethane prepolymer (X-4) was 4.75% by mass, and the melt viscosity of the urethane prepolymer (X-4) at 100°C, measured by a cone-plate viscometer, was 1,350 mPa·s.

[0114] [Example 5]

[0115] Ten parts by mass of the compound (A-2) obtained in Synthesis Example 3, 90 parts by mass of polyester polyol 1, 135 parts by mass of polyester polyol 2, and 20 parts by mass of polyether polyol 1 were charged into a reaction vessel equipped with a stirrer and a reflux device with an atmospheric pressure vent. The mixture was stirred under a nitrogen atmosphere at 110°C and dehydrated under vacuum for 1 hour. The resulting product was then cooled to 80°C and 87 parts by mass of MDI were added. The resulting mixture was slowly heated to 110°C and reacted for 3 hours, thereby obtaining a urethane prepolymer (X-5) with isocyanate groups. The NCO% of the urethane prepolymer (X-5) was 4.66% by mass, and the melt viscosity of the urethane prepolymer (X-5) at 100°C, measured by a cone-plate viscometer, was 1,600 mPa·s.

[0116] [Example 6]

[0117] Ten parts by mass of the compound (A-1) obtained in Synthesis Example 2, 90 parts by mass of polyester polyol 1, 135 parts by mass of polyester polyol 2, and 20 parts by mass of polyether polyol 2 (polytetramethylene glycol, number average molecular weight: 1,000) were charged into a reaction vessel equipped with a stirrer and a reflux device with an atmospheric pressure vent. The mixture was stirred under a nitrogen atmosphere at 110°C and dehydrated under vacuum for 1 hour. The resulting product was then cooled to 80°C and 83.5 parts by mass of MDI were added. The resulting mixture was slowly heated to 110°C and reacted for 3 hours, thereby obtaining a urethane prepolymer (X-6) with isocyanate groups. The NCO% of the urethane prepolymer (X-6) was 4.68% by mass, and the melt viscosity of the urethane prepolymer (X-6) at 100°C, measured by a cone-plate viscometer, was 1,750 mPa·s.

[0118] [Example 7]

[0119] Ten parts by mass of the compound (A-1) obtained in Synthesis Example 2, 90 parts by mass of polyester polyol 1, 135 parts by mass of polyester polyol 2, and 20 parts by mass of polycarbonate polyol 1 (“ETERNACOLL UH-100”, manufactured by UBE Corporation, number average molecular weight: 2,000) were packed into a reaction vessel equipped with a stirrer and a reflux device with an atmospheric pressure vent. The mixture was stirred under a nitrogen atmosphere at 110°C and dehydrated under vacuum for 1 hour. The resulting product was then cooled to 80°C and 75.6 parts by mass of MDI were added. The resulting mixture was slowly heated to 110°C and reacted for 3 hours, thereby obtaining a urethane prepolymer (X-7) with isocyanate groups. The NCO% of the urethane prepolymer (X-7) is 4.82% by mass, and the melt viscosity of the urethane prepolymer (X-7) at 100°C, as measured by a cone-plate viscometer, is 2,200 mPa·s.

[0120] [Example 8]

[0121] Ten parts by mass of the compound (A-1) obtained in Synthesis Example 2, 125 parts by mass of polyester polyol 3 (the reaction product of neopentyl glycol and phthalic acid, number average molecular weight: 2,000), and 125 parts by mass of polycaprolactone polyol 1 (number average molecular weight: 2,000) were charged into a reaction vessel equipped with a stirrer and a reflux device with an atmospheric pressure vent. The mixture was stirred under a nitrogen atmosphere at 110°C and dehydrated under vacuum for 1 hour. The resulting product was then cooled to 80°C and 80 parts by mass of MDI were added. The resulting mixture was slowly heated to 110°C and reacted for 3 hours, thereby obtaining a urethane prepolymer (X-8) with isocyanate groups. The NCO% of the urethane prepolymer (X-8) was 4.5% by mass, and the melt viscosity of the urethane prepolymer (X-8) at 100°C, as measured by a cone-plate viscometer, was 1,600 mPa·s.

[0122] [Comparative Example 1]

[0123] 90 parts by mass of polyester polyol 1, 135 parts by mass of polyester polyol 2, and 20 parts by mass of polyether polyol 1 were packed into a reaction vessel equipped with a stirrer and a reflux device with an atmospheric pressure vent. The mixture was stirred under a nitrogen atmosphere at 110°C and then dehydrated under vacuum for 1 hour. Subsequently, the resulting product was cooled to 80°C and 75.6 parts by mass of MDI were added. The resulting mixture was slowly heated to 110°C and reacted for 3 hours, thereby obtaining a urethane prepolymer (XR-1) with isocyanate groups. The NCO% of the urethane prepolymer (XR-1) was 4.45% by mass, and the melt viscosity of the urethane prepolymer (XR-1) at 100°C, measured by a cone-plate viscometer, was 1200 mPa·s.

[0124] [Comparative Example 2]

[0125] 90 parts by mass of polyester polyol 1, 135 parts by mass of polyester polyol 2, and 20 parts by mass of polyether polyol 2 were packed into a reaction vessel equipped with a stirrer and a reflux device with an atmospheric pressure vent. The mixture was stirred under a nitrogen atmosphere at 110°C and then dehydrated under vacuum for 1 hour. The resulting product was then cooled to 80°C, and 78 parts by mass of MDI were added. The resulting mixture was slowly heated to 110°C and reacted for 3 hours, thereby obtaining a urethane prepolymer (XR-2) with isocyanate groups. The NCO% of the urethane prepolymer (XR-2) was 4.67% by mass, and the melt viscosity of the urethane prepolymer (XR-2) at 100°C, measured by a cone-plate viscometer, was 1,600 mPa·s.

[0126] [Comparative Example 3]

[0127] 90 parts by mass of polyester polyol 1, 135 parts by mass of polyester polyol 2, and 20 parts by mass of polycarbonate polyol 1 were packed into a reaction vessel equipped with a stirrer and a reflux device with an atmospheric pressure vent. The mixture was stirred under a nitrogen atmosphere at 110°C and dehydrated under vacuum for 1 hour. Subsequently, the resulting product was cooled to 80°C and 75.6 parts by mass of MDI were added. The resulting mixture was slowly heated to 110°C and reacted for 3 hours, thereby obtaining a urethane prepolymer (XR-3) with isocyanate groups. The NCO% of the urethane prepolymer (XR-3) was 4.12% by mass, and the melt viscosity of the urethane prepolymer (XR-3) at 100°C, measured by a cone-plate viscometer, was 1,550 mPa·s.

[0128] [Comparative Example 4]

[0129] 125 parts by mass of polyester polyol 3 and 125 parts by mass of polycaprolactone polyol 1 were charged into a reaction vessel equipped with a stirrer and a reflux device with an atmospheric pressure vent. The mixture was stirred under a nitrogen atmosphere at 110°C and dehydrated under vacuum for 1 hour. Subsequently, the resulting product was cooled to 80°C and 75.8 parts by mass of MDI were added. The resulting mixture was slowly heated to 110°C and reacted for 3 hours, thereby obtaining a urethane prepolymer (XR-4) with isocyanate groups. The NCO% of the urethane prepolymer (XR-4) was 4.59% by mass, and the melt viscosity of the urethane prepolymer (XR-4) at 100°C, measured by a cone-plate viscometer, was 2,000 mPa·s.

[0130] [Method for measuring number-average molecular weight]

[0131] The average molecular weight of each of the polyols used in the synthesis examples was determined by gel permeation chromatography (GPC) under the following conditions.

[0132] Measurement device: High-performance GPC ("HLC-8220GPC", manufactured by Tosoh Corporation)

[0133] Tube Strings: The following tube strings, manufactured by Tosoh Corporation, are connected in series and used.

[0134] “TSKgel G5000” (7.8 mm inner diameter (ID) × 30 cm) × 1

[0135] “TSKgel G4000” (7.8 mm inner diameter × 30 cm) × 1

[0136] “TSKgel G3000” (7.8 mm inner diameter × 30 cm) × 1

[0137] “TSKgel G2000” (7.8 mm inner diameter × 30 cm) × 1

[0138] Detector: Differential refractometer (RI)

[0139] Column temperature: 40℃

[0140] Eluent: Tetrahydrofuran (THF)

[0141] Flow rate: 1.0 ml / min

[0142] Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)

[0143] Standard samples: Use the following types of standard polystyrene to generate calibration curves.

[0144] (Standard polystyrene)

[0145] "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation

[0146] "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation

[0147] "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation

[0148] "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation

[0149] "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation

[0150] "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation

[0151] "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation

[0152] "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation

[0153] "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation

[0154] "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation

[0155] "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation

[0156] "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation

[0157] "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation

[0158] "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[0159] [Method 1 for evaluating the adhesive strength to fabrics]

[0160] Each of the wet-curing polyurethane hot melt resin compositions obtained in the examples and comparative examples was melted at 100°C and then intermittently applied to a moisture-permeable membrane (obtained by applying "Crisbon S-517" manufactured by DIC to a 15-micron membrane) using a gravure roller coater (coating amount: 17.5 ± 5 g / m²). The resulting membrane is bonded to either waterproof fabric 1 (polyester fabric manufactured by the Japanese Standards Association, warp and weft: 75 denier (D) / 36 filament-fully drawn yarn (f-FDY), weight: 71.8 g / m²), which is treated with a waterproofing agent (“NEOSEED NR-8800”, manufactured by NICCA CHEMICAL CO., LTD.) and has a waterproof rating of 5, hereinafter referred to as “Fabric 1”) or waterproof fabric 2 (polyester fabric manufactured by the Japanese Standards Association, warp and weft: 75 D / 36 f-FDY, weight: 71.8 g / m²), which is treated with a waterproofing agent (“NEOSEED NR-7080”, manufactured by NICCA CHEMICAL CO., LTD.) and has a waterproof rating of 5, hereinafter referred to as “Fabric 2”). The resulting material was left to stand for 24 hours at a temperature of 23°C and a humidity of 50% to obtain the treated fabric. Each of the obtained treated fabrics was cut into samples with a width of 1 inch, and the peel strength of the samples was measured using a TENSILON (TENSILON multi-testing machine, “RTC-1210A”, manufactured by Orientec Co., Ltd) at a crosshead speed of 200 mm / min, and evaluated as follows.

[0161] T: 0.6 N / inch or greater than 0.6 N / inch

[0162] F: less than 0.6 N / inch

[0163] [Method 2 for evaluating the adhesive strength to fabrics]

[0164] Each of the obtained laminates was washed 20 times with water according to JIS L1089-1970, and the appearance after washing was evaluated. Note that the appearance was visually evaluated according to the following criteria.

[0165] T: No peeling was observed in appearance.

[0166] F: Delamination is observed in more than half of the adhesive area of ​​the laminate.

[0167] [Methods for evaluating texture]

[0168] Each of the laminates obtained by the above-described "Method for Evaluating Adhesion to Fabrics" was cut into samples with a width of 1 inch and a length of 8 cm. The samples were folded in half using a precision multi-instrument ("AUTOGRAPH AG-1", manufactured by Shimadzu Corporation), and a 5 cm section of the folded sample was attached to the upper part of the clamping fixture so that the section protruded while being rounded. The stress at a 5 mm displacement was measured when a flat indenter was pressed in at a test speed of 10 mm / min, and the following evaluation was performed.

[0169] T: 100 millinewtons or less

[0170] F: Greater than 100 millinewtons

[0171] [Table 1]

[0172]

[0173] [Table 2]

[0174]

[0175] [Table 3]

[0176]

[0177] It has been found that the wet-curing polyurethane hot melt resin composition according to the present invention has excellent adhesion to waterproof fabrics and excellent texture.

[0178] In contrast, Comparative Examples 1 to 4, which do not contain compound (A), exhibit poor adhesion to waterproof fabrics.

Claims

1. A moisture-curing polyurethane hot melt resin composition, comprising... Carbamate prepolymer (X), having isocyanate groups, The urethane prepolymer (X) is produced using the following materials as raw materials: A compound (A) having a hydroxyl group, said compound (A) being produced using a five-membered cyclic carbonate compound (a1) and a monoamine compound (a2) as raw materials; Polyols (B); and Polyisocyanate (C).

2. The wet-curing polyurethane hot melt resin composition according to claim 1, wherein the monoamine compound (a2) contains an alkyl group having 8 to 22 carbon atoms.

3. The wet-curing polyurethane hot-melt resin composition according to claim 1, wherein the five-membered cyclic carbonate compound (a1) is a reaction product of a bifunctional epoxy compound and carbon dioxide and / or a compound represented by formula (1). [Chemical Formula 1] Where R 1 and R 2 Each can be independently represented as a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a hydroxyalkyl group having 1 to 22 carbon atoms.

4. The wet-curing polyurethane hot melt resin composition according to claim 1, wherein the polyol (B) is selected from at least one of the group consisting of polyester polyols, polyether polyols, polycaprolactone polyols and polycarbonate polyols.

5. An adhesive comprising the wet-curing polyurethane hot melt resin composition as described in claim 1.

6. A laminate comprising at least: Fabric (i); and The cured product of the wet-curing polyurethane hot melt resin composition as described in claim 1.

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