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

Abstract

The object of the present invention is to provide a moisture-curing polyurethane hot-melt resin composition that exhibits excellent adhesion to water-repellent fabrics and the like, and also has a superior texture. [Solution] The present invention provides a moisture-curing polyurethane hot melt resin composition comprising a urethane prepolymer (X) having an isocyanate group, wherein the urethane prepolymer (X) is produced from a compound (A) having a hydroxyl group, produced from a five-membered ring cyclic carbonate compound (a1) and a monoamine compound (a2), a polyol (B), and a polyisocyanate (C). The present invention also provides an adhesive comprising the moisture-curing polyurethane hot melt resin composition. Furthermore, 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.

Description

Technical Field

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

Background Art

[0002] A moisture-permeable and waterproof functional clothing having both moisture permeability and waterproofness is a structure in which a moisture-permeable film is bonded to a fabric with an adhesive. As the adhesive, a urethane-based adhesive is generally used because of its good adhesion to both the moisture-permeable film and the fabric. Among the urethane-based adhesives, the amount of use of a solvent-free moisture-curable polyurethane hot melt resin composition is gradually increasing due to recent global solvent emission regulations and residual solvent regulations (for example, see Patent Document 1).

[0003] On the other hand, the fabrics used have become finer in denier and have improved water repellency due to weight reduction and high functionality, and there is a problem that the adhesion between the pre-water-repellent treated fabric and the adhesive decreases. Among the current moisture-curable polyurethane hot melt resin compositions, those that exhibit high adhesion particularly to pre-water-repellent treated fabrics have not been found.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The problem to be solved by the present invention is to provide a moisture-curable polyurethane hot melt resin composition having excellent adhesion to a pre-water-repellent treated fabric or the like and excellent texture.

Means for Solving the Problems

[0006] The present invention provides a moisture-curing polyurethane hot-melt resin composition comprising a urethane prepolymer (X) having an isocyanate group, wherein the urethane prepolymer (X) is produced from a compound (A) having a hydroxyl group, which is produced from a five-membered ring cyclic carbonate compound (a1) and a monoamine compound (a2), a polyol (B), and a polyisocyanate (C).

[0007] Furthermore, the present invention provides an adhesive characterized by containing the moisture-curing polyurethane hot-melt resin composition. Moreover, the present invention provides a laminate characterized by having at least a fabric (i) and a cured product of the moisture-curing polyurethane hot-melt resin composition. [Effects of the Invention]

[0008] The moisture-curing polyurethane hot-melt resin composition of the present invention is solvent-free and is an environmentally friendly material. Furthermore, the moisture-curing polyurethane hot-melt resin composition of the present invention exhibits excellent adhesion to various fabrics, including excellent adhesion to pre-treated water-repellent fabrics, and also boasts superior texture and strength. [Modes for carrying out the invention]

[0009] The moisture-curing polyurethane hot-melt resin composition used in the present invention contains a urethane prepolymer (X) having an isocyanate group, which is derived from a specific compound (A) having a hydroxyl group, a polyol (B), and a polyisocyanate (C).

[0010] Compound (A) is derived from a five-membered ring carbonate compound (a1) and a monoamine compound (a2) and has a hydroxyl group. By using the above raw materials, compound (A) can be given hydrophobicity and strength, thus ensuring excellent adhesion and texture, especially to pre-treated water-repellent fabrics.

[0011] Examples of the five-membered ring carbonate compound include the reaction product of a bifunctional epoxy compound and carbon dioxide, and the compound represented by the following formula (1). These compounds may be used individually or in combination of two or more.

[0012] [ka] (In formula (1), R 1 and R 2 Each of these independently represents a hydrogen atom, an alkyl group with 1 to 22 carbon atoms, and a hydroxyalkyl group with 1 to 22 carbon atoms.

[0013] Examples of the aforementioned bifunctional epoxy compounds include 1,4-bis(ethylene oxide-2-ylmethoxy)butane, bisphenol A-type glycidyl ether, bisphenol F-type glycidyl ether, bisphenol S-type glycidyl ether, bisphenol AD-type glycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, hydroquinone diglycidyl ether, 4,4'-dihydroxybiphenyl-type diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, etc. These compounds may be used individually or in combination of two or more. Among these, 1,4-bis(ethylene oxide-2-ylmethoxy)butane, bisphenol A-type glycidyl ether, and propanetriol 1,2-carbonate are preferred because they provide even better hydrophobicity and strength.

[0014] For the reaction between the bifunctional epoxy compound and carbon dioxide, known methods can be used, and reference can be made to Japanese Patent Publication No. 2020-117565, Japanese Patent Publication No. Hei 8-169976, etc.

[0015] Specific examples of reaction products between the aforementioned bifunctional epoxy compound and carbon dioxide include, for example, the compounds shown in the following formulas (2) to (16). In formulas (2) to (16), R independently represents either a hydrogen atom or a methyl group.

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[0027] [ka]

[0028] [ka]

[0029] [ka]

[0030] [ka]

[0031] A preferred example of the five-membered ring carbonate compound (a1) is the compound represented by formula (10), which is a reaction product of 1,4-bis(ethylene oxide-2-ylmethoxy)butane and carbon dioxide, where R in formula (1) 1 R represents a hydrogen atom, 2 Preferably, the element is a hydroxyalkyl group having 1 to 22 carbon atoms.

[0032] The monoamine compound (a2) is a compound having one amino group, and for example, monoamines having a linear and / or branched chain with an alkyl group having 8 to 22 carbon atoms, saturated cyclic monoamines having the above structure, saturated heterocyclic monoamines, etc., can be used. These compounds may be used alone or in combination of two or more. Among these, those having a linear and / or branched chain with an alkyl group having 12 to 18 carbon atoms are preferred because they improve affinity with the pre-treated water-repellent fabric, thereby improving penetration into the fabric and obtaining even better adhesion.

[0033] A known method can be used for the reaction between the five-membered ring carbonate compound (a1) and the monoamine compound (a2).

[0034] The number-average molecular weight of the resulting compound (A) having a hydroxyl group is preferably 200 to 5,000, and more preferably 300 to 3,000. The number-average molecular weight of compound (A) is the value measured by gel permeation chromatography (GPC).

[0035] The amount of compound (A) used is preferably 0.5 to 20.0% by mass, and more preferably 1.0 to 15.0% by mass, of the total mass of the raw materials constituting the urethane prepolymer (X).

[0036] As the polyol (B), for example, polyester polyol, polycaprolactone polyol, polyether polyol, polycarbonate polyol, polyacrylic polyol, polybutadiene polyol, etc., can be used. These polyols may be used individually or in combination of two or more. Among these, one or more polyols selected from the group consisting of polyester polyol, polyether polyol, polycaprolactone polyol, and polycarbonate polyol are preferred because they provide even better mechanical strength and adhesion.

[0037] The number-average molecular weight of the polyol (B) is preferably 500 to 10,000, and more preferably 700 to 5,000, from the viewpoint of obtaining even better mechanical strength and adhesive properties. The number-average molecular weight of the polyol is the value measured by gel permeation chromatography (GPC).

[0038] The polyol (B) may, if necessary, be used in combination with a chain extension agent having a molecular weight of less than 500, such as a compound having two or more hydroxyl groups or a compound having two or more amino groups.

[0039] The amount of polyol (B) used is preferably 80 to 99.5% by mass, and more preferably 85 to 99% by mass, of the total mass of the raw materials constituting the urethane prepolymer (X).

[0040] As the polyisocyanate (C), aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate can be used; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred, in that they provide even better reactivity and adhesion to the fabric.

[0041] The amount of polyisocyanate (C) used is preferably 10.0 to 50.0% by mass, and more preferably 15.0 to 30.0% by mass, of the total mass of the raw materials constituting the urethane prepolymer (X).

[0042] The hot melt urethane prepolymer (X) is obtained by reacting (A) to (C) above and has isocyanate groups that can react with moisture present in the air or in the substrate to which the moisture-curing polyurethane hot melt resin composition is applied to form a crosslinked structure.

[0043] As an example of a method for producing the urethane prepolymer (X), the polyisocyanate (C) is placed in a reaction vessel containing the compound (A) and the polyol (B), and the reaction is carried out under conditions in which the isocyanate groups of the polyisocyanate (C) are in excess of the hydroxyl groups of the compound (A) and the polyol (B).

[0044] When producing the urethane prepolymer (X), the equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate group of the polyisocyanate (C) and the hydroxyl group of the compound (A) and the polyol (B) is preferably 1.1 to 5.0, and more preferably 1.5 to 3.0, in order to obtain even better adhesion to the fabric.

[0045] 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, from which even better adhesion can be obtained. The NCO% of the hot melt urethane prepolymer (X) is the value measured by potentiometric titration in accordance with JIS K1603-1:2007.

[0046] The moisture-curing polyurethane hot-melt resin composition used in the present invention contains the urethane prepolymer (X) as an essential component, but other additives may be used as needed.

[0047] Other additives that can be used include, for example, light stabilizers, curing catalysts, tackifiers, plasticizers, stabilizers, fillers, dyes, pigments, fluorescent whitening agents, silane coupling agents, waxes, thermoplastic resins, and the like. These additives may be used individually or in combination of two or more.

[0048] As described above, the moisture-curing polyurethane hot-melt resin composition of the present invention is solvent-free and is an environmentally friendly material. Furthermore, the moisture-curing polyurethane hot-melt resin composition of the present invention exhibits excellent adhesion to various fabrics, including excellent adhesion to pre-treated water-repellent fabrics, and also boasts superior texture and strength.

[0049] Next, the laminate of the present invention will be described.

[0050] The laminate of the present invention comprises at least a fabric (i) and a cured product of the moisture-curing polyurethane hot-melt resin composition.

[0051] The fabric (i) can be, for example, a fiber base material such as 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, linen, silk, wool, fiberglass, carbon fiber, or blends thereof; a nonwoven fabric impregnated with a resin such as polyurethane resin; a nonwoven fabric further provided with a porous layer; or a resin base material.

[0052] Furthermore, the present invention also exhibits excellent adhesion even when the fabric (i) is the same as described above but has been treated with a water-repellent finish (hereinafter abbreviated as "water-repellent fabric"). In this invention, "water-repellent" of the water-repellent fabric means that the surface free energy obtained by the following calculation is 50 mJ / m 2 The following applies. In this specification, "pre-treated water-repellent fabric" refers to fabric that has been treated with a water-repellent finish before the adhesive is applied.

[0053] The contact angles of the measurement liquids (water and diiodomethane) on the aforementioned fabric (i) were measured using a contact angle meter (DM500, manufactured by Kyowa Interface Science Co., Ltd.). Based on these results, the surface free energy of fabric (i) was calculated using the following equation (1). (1+cosA)·γL / 2=(γsd·γLd)1 / 2+(γsp·γLp)1 / 2

[0054] A; Contact angle of the measuring liquid on the fabric (i) γL; Surface tension of the measuring solution γLd; Dispersion force component of the surface free energy of the measurement solution. γLp; Polar force component of the surface free energy of the measurement solution. γsd; Dispersion force component of the surface free energy of fabric (i) γsp; Polar force component of the surface free energy of fabric (i)

[0055] Methods for applying the moisture-curing polyurethane hot-melt resin composition include, for example, using a roll coater, knife coater, spray coater, gravure roll coater, comma coater, T-die coater, applicator, dispenser, etc.

[0056] After coating, the moisture-curing polyurethane hot-melt resin composition can be dried and cured by known methods.

[0057] The thickness of the cured product of the moisture-curing urethane hot-melt resin composition is, for example, in the range of 5 to 300 μm.

[0058] Furthermore, when the moisture-curing polyurethane hot melt resin composition of the present invention is used as an adhesive for breathable waterproof functional clothing, it is preferable to intermittently coat the moisture-curing polyurethane hot melt resin composition using a gravure roll coater or dispenser to bond the fabric (i) to a known breathable film. In such cases, the thickness of the cured product of the moisture-curing polyurethane hot melt resin composition is, for example, in the range of 5 to 50 μm.

[0059] A mesh fabric may be further bonded to the aforementioned moisture-permeable film by intermittently applying a moisture-curing polyurethane hot-melt resin composition. [Examples]

[0060] The present invention will be described in more detail below using examples.

[0061] [Synthesis Example 1] Preparation of a five-membered ring carbonate compound (a1-1) 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 refluxer. Next, the carbon dioxide pressure in the reaction vessel was increased from atmospheric pressure to 2.0 MPa at a temperature of 120°C, and carbon dioxide was intermittently blown in while stirring, maintaining the pressure at 2 MPa, and the reaction was carried out for 24 hours to obtain the five-membered ring carbonate compound (a1-1). The five-membered ring carbonate compound (a1-1) was a yellowish solid at room temperature, and analysis by 1H-NMR (400M, JEOL) showed that the cyclic carbonate equivalent of the obtained five-membered ring carbonate compound (a1-1) was 235.7 in 1H-NMR with DMF as the internal standard. In the quantitative carbon spectrum, the absorption originating from the epoxy group of the raw material around 50 ppm disappeared, and the carbonyl group of the carbonate group of the obtained substance appeared around 155 ppm. The reaction can be described using equation (2) below.

[0062] [ka] (17)

[0063] [Synthesis Example 2] Preparation of Compound (A-1) Having a Hydroxyl Group 0.1 moles of the five-membered ring 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 valve with an atmospheric outlet. The compounds were then reacted in a liquid state at a temperature of 80°C under a nitrogen atmosphere, and stirred for 8 hours to obtain compound (A-1) having a hydroxyl group. The resulting product was a white to yellowish solid at room temperature. Analysis by 13C-NMR (400M, JEOL) revealed that the characteristic peak of the cyclic carbon in the cyclic carbonate of the resulting compound (A-1) had disappeared. Furthermore, the ratio of primary hydroxyl groups (62.9 ppm):secondary hydroxyl groups (69.3 ppm) was 0.25:0.75, and titration of the hydroxyl value determined that the hydroxyl value of the obtained substance was 155 mgKOH / g. The reaction can be described by formula (3) below.

[0064] [ka] (18)

[0065] [Synthesis Example 3] Preparation of Compound (A-2) Having a Hydroxyl Group 0.1 mole of propanetriol 1,2-carbonate and 0.1 mole of octadecyl primary monoamine were charged into a reaction vessel equipped with a stirrer and a reflux valve with an atmospheric outlet. The reaction was then carried out under a nitrogen atmosphere at a temperature of 80°C with ODA in a liquid state, and stirred for 8 hours to obtain compound (A-2). The obtained compound (A-2) was a white to yellowish solid at room temperature, and its hydroxyl value was 293.0 mgKOH / g. For this reaction, refer to formula (4) below.

[0066] [ka] (19)

[0067] [Example 1] 2.0 parts by mass of the compound (A-1) obtained in Synthesis Example 2, 90 parts by mass of polyester polyol 1 (a reaction of 1,6-hexanediol, 2-methyl-1,3-propanediol, and adipic acid, number average molecular weight: 2,000), 135 parts by mass of polyester polyol 2 (a reaction of 1,6-hexanediol and adipic acid, number average molecular weight: 2,000), and 20 parts by mass of polyether polyol 1 (polypropylene glycol, number average molecular weight: 1,000) were charged into a reaction vessel equipped with a stirrer and a reflux valve with an atmospheric outlet. Vacuum dehydration was carried out for 1 hour at 110°C under a nitrogen stream while mixing and stirring. Next, the mixture was cooled to 80°C, and 80.0 parts by mass of diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") was added. The temperature was then slowly raised to 110°C and the reaction was carried out for 3 hours to obtain a urethane prepolymer (X-1) having isocyanate groups. The NCO% of (X-1) was 4.75% by mass, and the melt viscosity at 120°C, as measured by a cone-plate viscometer, was 1,300 mPa·s.

[0068] [Example 2] 10 parts by mass of 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 valve with an atmospheric outlet. Vacuum dehydration was carried out for 1 hour at 110°C under a nitrogen stream while mixing and stirring. Then, the mixture was cooled to 80°C, 83.5 parts by mass of MDI were added, and the temperature was slowly raised to 110°C for 3 hours to obtain a urethane prepolymer (X-2) having isocyanate groups. The NCO% of (X-2) was 4.68% by mass, and the melt viscosity at 100°C measured with a cone plate viscometer was 1,500 mPa·s.

[0069] [Example 3] 35 parts by mass of 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 valve with an atmospheric outlet. Vacuum dehydration was carried out for 1 hour at 110°C under a nitrogen stream while mixing and stirring. Then, the mixture was cooled to 80°C, 97.7 parts by mass of MDI were added, and the temperature was slowly raised to 110°C for 3 hours to obtain a urethane prepolymer (X-3) having isocyanate groups. The NCO% of (X-3) was 4.75% by mass, and the melt viscosity at 100°C measured with a cone plate viscometer was 2,000 mPa·s.

[0070] [Example 4] 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 valve with an atmospheric outlet. Vacuum dehydration was carried out for 1 hour at 110°C under a nitrogen stream while mixing and stirring. Then, the mixture was cooled to 80°C, 80.7 parts by mass of MDI were added, and the temperature was slowly raised to 110°C for 3 hours to obtain a urethane prepolymer (X-4) having isocyanate groups. The NCO% of (X-4) was 4.75% by mass, and the melt viscosity at 100°C measured with a cone plate viscometer was 1,350 mPa·s.

[0071] [Example 5] 10 parts by mass of 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 valve with an atmospheric outlet. Vacuum dehydration was carried out for 1 hour at 110°C under a nitrogen stream while mixing and stirring. Then, the mixture was cooled to 80°C, 87 parts by mass of MDI were added, and the temperature was slowly raised to 110°C for 3 hours to obtain a urethane prepolymer (X-5) having isocyanate groups. The NCO% of (X-5) was 4.66% by mass, and the melt viscosity at 100°C measured with a cone plate viscometer was 1,600 mPa·s.

[0072] [Example 6] 10 parts by mass of 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 valve with an atmospheric outlet. Vacuum dehydration was carried out for 1 hour at 110°C under a nitrogen atmosphere while mixing and stirring. Then, the mixture was cooled to 80°C, 83.5 parts by mass of MDI were added, and the temperature was slowly raised to 110°C for 3 hours to obtain a urethane prepolymer (X-6) having isocyanate groups. The NCO% of (X-6) was 4.68% by mass, and the melt viscosity at 100°C measured with a cone plate viscometer was 1,750 mPa·s.

[0073] [Example 7] In Synthesis Example 2, 10 parts by mass of compound (A-1), 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 (Ethanacol UH-100, manufactured by Ube Industries, Ltd., number average molecular weight: 2,000) were charged into a reaction vessel equipped with a stirrer and a reflux valve with an atmospheric outlet. Under a nitrogen atmosphere, the mixture was vacuum dehydrated for 1 hour at 110°C while mixing and stirring. The mixture was then cooled to 80°C, 75.6 parts by mass of MDI were added, and the temperature was slowly raised to 110°C for 3 hours to obtain a urethane prepolymer (X-7) having isocyanate groups. The NCO% of (X-7) was 4.82% by mass, and the melt viscosity at 100°C measured with a cone plate viscometer was 2,200 mPa·s.

[0074] [Example 8] 10 parts by mass of compound (A-1) obtained in Synthesis Example 2, 125 parts by mass of polyester polyol 3 (reaction product of neopentyl glycol and orthophthalic 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 valve with an atmospheric outlet. Vacuum dehydration was carried out for 1 hour at 110°C under a nitrogen atmosphere while mixing and stirring. Then, the mixture was cooled to 80°C, 80 parts by mass of MDI were added, and the temperature was slowly raised to 110°C for 3 hours to obtain a urethane prepolymer (X-8) having isocyanate groups. The NCO% of (X-8) was 4.5% by mass, and the melt viscosity at 100°C measured with a cone plate viscometer was 1,600 mPa·s.

[0075] [Comparative Example 1] 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 valve with an atmospheric outlet. Under a nitrogen atmosphere, vacuum dehydration was carried out for 1 hour while mixing and stirring at 110°C. Then, the mixture was cooled to 80°C, 75.6 parts by mass of MDI were added, and the temperature was slowly raised to 110°C for 3 hours to obtain a urethane prepolymer (XR-1) having isocyanate groups. The NCO% of (XR-1) was 4.45% by mass, and the melt viscosity at 100°C measured with a cone plate viscometer was 1,200 mPa·s.

[0076] [Comparative 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 were charged into a reaction vessel equipped with a stirrer and a reflux valve with an atmospheric outlet. Under a nitrogen atmosphere, vacuum dehydration was carried out for 1 hour while mixing and stirring at 110°C. Then, the mixture was cooled to 80°C, 78 parts by mass of MDI were added, and the temperature was slowly raised to 110°C for 3 hours to obtain a urethane prepolymer (XR-2) having isocyanate groups. The NCO% of (XR-2) was 4.67% by mass, and the melt viscosity at 100°C measured with a cone plate viscometer was 1,600 mPa·s.

[0077] [Comparative Example 3] 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 charged into a reaction vessel equipped with a stirrer and a reflux valve with an atmospheric outlet. Under a nitrogen atmosphere, the mixture was vacuum dehydrated for 1 hour while being mixed and stirred at 110°C. Then, it was cooled to 80°C, 75.6 parts by mass of MDI was added, and the temperature was slowly raised to 110°C for 3 hours to obtain a urethane prepolymer (XR-3) having isocyanate groups. The NCO% of (XR-3) was 4.12% by mass, and the melt viscosity at 100°C measured with a cone plate viscometer was 1,550 mPa·s.

[0078] [Comparative Example 4] 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 valve with an atmospheric outlet. Under a nitrogen atmosphere, vacuum dehydration was carried out for 1 hour while mixing and stirring at 110°C. Then, the mixture was cooled to 80°C, 75.8 parts by mass of MDI were added, and the temperature was slowly raised to 110°C for 3 hours to obtain a urethane prepolymer (XR-4) having isocyanate groups. The NCO% of (XR-4) was 4.59% by mass, and the melt viscosity at 100°C measured with a cone plate viscometer was 2,000 mPa·s.

[0079] [Method for measuring number-average molecular weight] The number-average molecular weights of the polyols used in the synthesis examples are shown as values ​​measured by gel permeation chromatography (GPC) under the following conditions.

[0080] Measurement device: High-speed GPC device (HLC-8220GPC manufactured by Tosoh Corporation) Columns: 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" (7.8mmI.D. x 30cm) x 1 Detector: RI (Differential Refractometer) Column temperature: 40℃ Eluent: Tetrahydrofuran (THF) Flow rate: 1.0mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard samples: Calibration curves were prepared using the following standard polystyrene samples.

[0081] (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.

[0082] [Method 1 for evaluating adhesion to fabric] The moisture-curing polyurethane hot-melt resin compositions obtained in the examples and comparative examples were melted at 100°C, and then coated with a gravure roll coater (coating amount: 17.5±5 g / m²). 2 Using ) intermittently coating a breathable film (DIC Corporation's "Crisbon S-517" processed into a 15μm film), water-repellent fabric 1 (polyester fabric (manufactured by the Japanese Standards Association, warp / weft: 75D / 36f-FDY, basis weight: 71.8g / m²) is applied, and water-repellent fabric 1 is applied intermittently. 2 Fabric 1 is a fabric treated with a water-repellent agent ("Neoseed NR-8800" manufactured by Nikka Chemical Co., Ltd.) and has a water-repellent rating of 5. (Hereinafter abbreviated as "Fabric 1.") and Water-repellent Fabric 2 is a polyester fabric (manufactured by the Japan Standards Association, warp / weft: 75D / 36f-FDY, basis weight: 71.8g / m²). 2The fabric was treated with a water-repellent agent (NeoSeed "NR-7080" manufactured by Nikka Chemical Co., Ltd.) and given a water-repellent rating of 5. Hereinafter referred to as "Fabric 2". The fabrics were bonded together and left for 24 hours in an atmosphere of 23°C and 50% humidity to obtain processed fabrics. Each of the obtained processed fabrics was cut to a width of 1 inch, and the peel strength was measured using a Tensilon (Tensilon universal machine "RTC-1210A" manufactured by Orientec Co., Ltd.) at a crosshead speed of 200 mm / min, and evaluated as follows. "T": 0.6 N / inch or higher. "F": Less than 0.6 N / inch.

[0083] [Method 2 for evaluating adhesion to fabric] Each resulting laminate was subjected to 20 water washes in accordance with JIS L1089-1970, and its appearance after washing was evaluated. The appearance was evaluated visually according to the following criteria. "T"; Visually, there was no peeling at all. "F"; Visually, more than half of the adhesive surface area had peeled off.

[0084] [Method for evaluating texture] Each laminate obtained in the above [Method for Evaluating Adhesion to Fabric] was cut to a width of 1 inch and a length of 8 cm. Using a precision universal testing machine (Shimadzu Corporation's "AutoFluff AG-1"), the test piece was folded in half, and the folded portion was attached to the top of the clamping jig so that a 5 cm length was rounded. The stress at a displacement of 5 mm was measured when a flat indenter was pressed in at a test speed of 10 mm / min and evaluated as follows. "T"; 100mN or less. "F"; exceeds 100mN.

[0085] [Table 1]

[0086] [Table 2]

[0087] [Table 3]

[0088] The moisture-curing polyurethane hot-melt resin composition of the present invention has been found to have excellent adhesion to pre-treated water-repellent fabrics and a good texture.

[0089] On the other hand, Comparative Examples 1 to 4, which did not use compound (A), exhibited poor adhesion to water-repellent fabrics.

Claims

1. It contains a urethane prepolymer (X) having an isocyanate group, The aforementioned urethane prepolymer (X) is made from the following raw materials: Compound (A) having a hydroxyl group, manufactured using a five-membered ring cyclic carbonate compound (a1) and a monoamine compound (a2) as raw materials. Polyol (B), and Polyisocyanate (C) A moisture-curable polyurethane hot-melt resin composition manufactured using [a specific method / tool].

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

3. The moisture-curing polyurethane hot-melt resin composition according to claim 1, wherein the five-membered ring carbonate compound (a1) is a reaction product of a bifunctional epoxy compound and carbon dioxide, and / or a compound represented by the following formula (1). 【Chemistry 1】 (In formula (1), R １ and R ２ Each of these independently represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, and a hydroxyalkyl group having 1 to 22 carbon atoms.

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

5. An adhesive characterized by containing the moisture-curing polyurethane hot-melt resin composition described in claim 1.

6. A laminate characterized by comprising at least a fabric (i) and a cured product of the moisture-curing polyurethane hot-melt resin composition described in claim 1.

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