Moisture-curable polyurethane resin composition, adhesive, and laminate

Abstract

To provide a moisture-curable polyurethane resin composition having excellent adhesion to a fabric (in particular, a water-repellent fabric), flexibility, compatibility, low-temperature characteristics and mechanical properties.SOLUTION: There is provided a moisture-curable polyurethane hot-melt resin composition which comprises a urethane prepolymer having an isocyanate group (i) and a polyester modifier (ii) represented by the following formula (1) or (2). Further, there is provided an adhesive containing the moisture-curable polyurethane resin composition. Furthermore, there is provided a laminate having at least a fabric and a cured product of the moisture-curable polyurethane resin composition.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Moisture-permeable, waterproof functional clothing, which has both moisture permeability and waterproofness, is a structure in which a moisture-permeable film is bonded to a fabric with an adhesive, and urethane adhesives are commonly used as the adhesive because of their good adhesion to both the moisture-permeable film and the fabric. Furthermore, among these urethane adhesives, the use of solvent-free, moisture-curable polyurethane resin compositions is gradually increasing due to recent global regulations on solvent emissions and residual solvents (see, for example, Patent Document 1).

[0003] On the other hand, the fabrics used are becoming more highly functional, with finer denier and improved water repellency, but this has been pointed out as a problem of poorer adhesion to adhesives. At present, no current moisture-curing polyurethane resin compositions have been found that exhibit particularly high adhesion to ultra-water-repellent fabrics.

[0004] Furthermore, as the recent marine plastic problem has been attracting attention, bio-based resins that aim to move away from petroleum resources are attracting increasing attention day by day, and moisture-curable polyurethane resin compositions are no exception. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2017-202608 Summary of the Invention [Problem to be solved by the invention]

[0006] The problem to be solved by the present invention is to provide a moisture-curable polyurethane resin composition that has excellent adhesion to fabrics (particularly water-repellent fabrics), flexibility, compatibility, low-temperature properties, and mechanical properties. [Means for solving the problem]

[0007] The present invention provides a moisture-curable polyurethane hot-melt resin composition comprising (i) a urethane prepolymer having an isocyanate group and (ii) a polyester modifier represented by the following formula (1) or (2):

[0008] [ka] (In the formulas (1) and (2), B 11 and B 12 each independently represents an aliphatic monocarboxylic acid residue having 7 to 20 carbon atoms. B 21 and B 22 each independently represents an aliphatic monoalcohol residue having 6 to 10 carbon atoms. G represents an alkylene glycol residue having 3 to 10 carbon atoms or an oxyalkylene glycol residue having 3 to 10 carbon atoms. A represents an alkylene dicarboxylic acid residue having 6 to 12 carbon atoms. m and n each represent the number of repeating units enclosed in parentheses, and m and n each independently represent an integer of 1 or more. In each repeating unit enclosed in parentheses, A and G may be the same or different.

[0009] The present invention also provides an adhesive containing the moisture-curable polyurethane resin composition. Furthermore, the present invention also provides a laminate having at least a substrate and a cured product of the moisture-curable polyurethane resin composition. [Effects of the Invention]

[0010] The moisture-curable polyurethane resin composition of the present invention uses biomass raw materials and is an environmentally friendly material. In addition, the moisture-curable polyurethane resin composition of the present invention has excellent adhesion to various fabrics, including water-repellent fabrics. DETAILED DESCRIPTION OF THE INVENTION

[0011] The moisture-curable polyurethane hot-melt resin composition used in the present invention contains a urethane prepolymer (i) having an isocyanate group and a specific polyester modifier (ii).

[0012] The urethane prepolymer (i) has an isocyanate group, and for example, a reaction product of a polyol (A) and a polyisocyanate (B) can be used.

[0013] Examples of the polyol (A) that can be used include polyester polyols, polycarbonate polyols, polyether polyols, polybutadiene polyols, polyacrylic polyols, etc. These polyols may be used alone or in combination of two or more.

[0014] The number average molecular weight of the polyol (A) is, for example, in the range of 500 to 100,000. The number average molecular weight of the other polyols is a value measured by gel permeation chromatography (GPC).

[0015] Among the above-mentioned polyols, polyester polyols are preferred as the polyol (A) since they provide even more excellent adhesiveness, flexibility, compatibility, low-temperature properties, and mechanical properties.

[0016] The polyester polyol may be a biomass-derived polyester polyol (a1), other crystalline polyester polyols, or amorphous polyester polyols. These polyester polyols may be used alone or in combination of two or more. Among these, it is preferable to use a biomass-derived polyester polyol (a1) because it provides even better adhesion, flexibility, compatibility, low-temperature properties, and mechanical properties, and can improve the biomass content.

[0017] As the biomass-derived polyester polyol (a1), for example, a reaction product of a biomass-derived polybasic acid (x) and a biomass-derived glycol (y) can be used.

[0018] Examples of the biomass-derived other basic acid (x) that can be used include sebacic acid, succinic acid, dimer acid, 2,5-furandicarboxylic acid, etc. These compounds may be used alone or in combination of two or more.

[0019] The sebacic acid may be, for example, one obtained by a known cleavage reaction of vegetable oils such as castor oil with caustic alkali. The succinic acid may be, for example, one obtained by fermenting corn, sugarcane, cassava, sago palm, or the like using a known method. The dimer acid may be, for example, one obtained by dimerizing unsaturated fatty acids of natural vegetable oils using a known method. The 2,5-furandicarboxylic acid may be, for example, one obtained from fructose as a raw material; or one obtained by a known method using furancarboxylic acid, a furfural derivative, and carbon dioxide.

[0020] As the biomass-derived other basic acid (x), among the above-mentioned, sebacic acid and / or succinic acid are preferred, and sebacic acid is more preferred, since even more excellent adhesiveness, flexibility, compatibility, low-temperature properties, and mechanical properties can be obtained.

[0021] Examples of the biomass-derived glycol (y) that can be used include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,10-decanediol, dimer diol, isosorbide, etc. These compounds may be used alone or in combination of two or more.

[0022] The ethylene glycol may be, for example, one obtained via ethylene from bioethanol obtained by a known method. The 1,2-propanediol may be, for example, one obtained by fermenting sugars; or one obtained by high-temperature hydrogenation of glycerin produced as a by-product of biodiesel by a known method. The 1,3-propanediol may be, for example, one obtained by producing 3-hydroxypropionaldehyde from glycerol, glucose, or other sugars by a known fermentation method and then converting it into 1,3-propanediol; or one obtained directly from glucose or other sugars by fermentation.

[0023] Examples of the 1,4-butanediol that can be used include those obtained by fermenting glucose using a known method; those obtained from 1,3-butadiene obtained by fermentation; and those obtained by hydrogenating succinic acid using a reduction catalyst. Examples of the 1,10-decanediol include those obtained by hydrogenating sebacic acid directly or after an esterification reaction. Examples of the dimer diol that can be used include those obtained by reducing dimer acid using a known method. Examples of the isosorbide that can be used include those obtained by dehydration condensation using a known method of sorbitol obtained from starch.

[0024] As the biomass-derived glycol (y), among the above-mentioned ones, 1,3-propanediol and / or 1,4-butanediol are preferred, and 1,3-propanediol is more preferred, in that even better adhesiveness, flexibility, heat resistance, low-temperature properties, and mechanical properties can be obtained.

[0025] The polyester polyol (a1) uses the biomass-derived polybasic acid (x) and the biomass-derived glycol (y) as essential raw materials, but may also use other polybasic acids and / or glycols in combination within a range that does not impair the effects of the present invention.

[0026] The number average molecular weight of the polyester polyol (a1) is preferably in the range of 500 to 100,000, more preferably in the range of 700 to 50,000, and even more preferably in the range of 800 to 10,000, from the viewpoint of obtaining even better mechanical strength and adhesiveness to fabrics. The number average molecular weight of the polyester polyol (a1) is a value measured by gel permeation chromatography (GPC).

[0027] The amount of the biomass-derived polyester polyol (a1) used is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 50% by mass or more, of the polyol (A).

[0028] The amount of the biomass-derived polyester polyol (a1) used is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 50% by mass or more, of the polyester polyol.

[0029] It is preferable to further use an amorphous polyester polyol as the polyol (A) in that even better adhesiveness, flexibility, compatibility, low-temperature properties, and mechanical properties can be obtained.

[0030] In the present invention, the term "crystalline" refers to a substance in which a peak of heat of crystallization or heat of fusion can be confirmed in a DSC (differential scanning calorimeter) measurement in accordance with JIS K7121:2012, and the term "amorphous" refers to a substance in which such a peak cannot be confirmed.

[0031] As the amorphous polyester polyol, for example, a reaction product of a compound having two or more hydroxyl groups with a polybasic acid can be used.

[0032] Examples of the compound having a hydroxyl group that can be used include ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, hexanediol, neopentyl glycol, hexamethylene glycol, glycerin, trimethylolpropane, bisphenol A, bisphenol F, and alkylene oxide adducts thereof. Among these, it is preferable to use a linear compound having two hydroxyl groups in combination with a branched compound having two or three hydroxyl groups, in order to obtain even better adhesion, flexibility, compatibility, low-temperature properties, film-forming properties, and mechanical properties.

[0033] Examples of the polybasic acid that can be used include adipic acid, glutaric acid, pimelic acid, suberic acid, dimer acid, sebacic acid, undecanedicarboxylic acid, hexahydroterephthalic acid, phthalic acid, phthalic anhydride, isophthalic acid, and terephthalic acid. Among these, it is preferable to use one or more compounds selected from the group consisting of phthalic acid, phthalic anhydride, isophthalic acid, and terephthalic acid as the polybasic acid, since these provide even better adhesion to the fabric, film strength, and film-forming properties.

[0034] The number average molecular weight of the amorphous polyester polyol is preferably in the range of 500 to 50,000, more preferably in the range of 700 to 10,000, in order to obtain even better adhesiveness, flexibility, compatibility, low-temperature properties, film-forming properties, and mechanical properties.

[0035] When the amorphous polyester polyol is used, the amount used is preferably 10 to 80 mass % of the polyol (A), more preferably 20 to 50 mass %, from the viewpoint of obtaining even better adhesiveness, flexibility, compatibility, low-temperature properties, film-forming properties, and mechanical properties.

[0036] Examples of the polyisocyanate (B) include aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; and aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate. 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, because they offer superior reactivity and adhesion to fabrics.

[0037] The amount of the polyisocyanate (B) used is preferably in the range of 5 to 40 mass %, more preferably in the range of 10 to 30 mass %, based on the total mass of the raw materials constituting the urethane prepolymer (i).

[0038] The hot-melt urethane prepolymer (i) is obtained by reacting the polyol (A) with the polyisocyanate (B), and has an isocyanate group that can react with moisture present in the air or in the substrate to which the moisture-curable polyurethane hot-melt resin composition is applied to form a crosslinked structure.

[0039] The hot-melt urethane prepolymer (i) can be produced, for example, by adding the polyisocyanate (B) to a reaction vessel containing the polyol (A) and reacting them under conditions in which the isocyanate groups of the polyisocyanate (B) are in excess relative to the hydroxyl groups of the polyol (A).

[0040] When producing the hot-melt urethane prepolymer (i), the equivalent ratio (isocyanate groups / hydroxyl groups) of the isocyanate groups in the polyisocyanate (B) to the hydroxyl groups in the polyol (A) is preferably 1.1 to 5, and more preferably 1.3 to 2.5, in order to obtain even better adhesiveness.

[0041] The isocyanate group content (hereinafter abbreviated as "NCO%") of the hot-melt urethane prepolymer (i) obtained by the above method is preferably in the range of 1.1 to 5.0, more preferably 1.5 to 3.5, in order to obtain even better adhesiveness. The NCO% of the hot-melt urethane prepolymer (i) is a value measured by potentiometric titration in accordance with JIS K1603-1:2007.

[0042] Next, the polyester modifier (ii) will be described.

[0043] The polyester modifier (ii) is a polyester represented by the following formula (1) or formula (2), and by adding it to the urethane prepolymer (i), excellent adhesion, flexibility, compatibility (compatibility between the urethane prepolymer (i) and the polyester modifier (ii)), low-temperature properties, and mechanical properties can be obtained.

[0044] [ka] (In the formulas (1) and (2), B 11 represents an aliphatic monocarboxylic acid residue having 7 to 20 carbon atoms. B 12 represents an aliphatic monocarboxylic acid residue having 7 to 20 carbon atoms. B 21 represents an aliphatic monoalcohol residue having 6 to 10 carbon atoms. B 22 represents an aliphatic monoalcohol residue having 6 to 10 carbon atoms. G represents an alkylene glycol residue having 3 to 10 carbon atoms or an oxyalkylene glycol residue having 3 to 10 carbon atoms. A represents an alkylene dicarboxylic acid residue having 6 to 12 carbon atoms. m and n each represent the number of repeating units enclosed in parentheses, and m and n each independently represent an integer of 1 or more. In each repeating unit enclosed in parentheses, A and G may be the same or different.

[0045] In the present invention, the term "carboxylic acid residue" refers to the organic group remaining after removing the carboxyl group from the carboxylic acid. The number of carbon atoms in the "carboxylic acid residue" does not include the carbon atoms in the carboxy group. In the present invention, the term "alcohol residue" refers to the organic group remaining after removing the hydroxyl group from an alcohol. In the present invention, the term "glycol residue" refers to the organic group remaining after removing the hydroxyl group from glycol.

[0046] B 11 and B 12 Examples of the aliphatic monocarboxylic acid residue having 7 to 20 carbon atoms include caprylic acid residue, capric acid residue, lauric acid residue, myristic acid residue, pentadecylic acid residue, palmitic acid residue, margaric acid residue, stearic acid residue, and arachidic acid residue. B 11 and B 12 The aliphatic monocarboxylic acid residue having 7 to 20 carbon atoms may have a secondary hydroxyl group and / or a tertiary hydroxyl group in the fatty chain, and includes a 12-hydroxystearic acid residue, etc.

[0047] B 11 and B 12 is preferably an aliphatic monocarboxylic acid residue having 11 to 17 carbon atoms, more preferably a lauric acid residue, a myristic acid residue, a palmitic acid residue or a stearic acid residue.

[0048] B of polyester represented by formula (1) 11 and B12 When at least one of them is an aliphatic monocarboxylic acid residue having 11 to 17 carbon atoms, the compound can exhibit even more excellent effects as a modifier.

[0049] B 21 and B 22 Examples of the aliphatic monoalcohol residue having 6 to 10 carbon atoms include normal octanol, 2-ethylhexanol, and isononyl alcohol.

[0050] B 21 and B 22 is preferably an aliphatic monoalcohol residue having 7 to 10 carbon atoms, more preferably an aliphatic monoalcohol residue having 8 or 9 carbon atoms.

[0051] Examples of the alkylene dicarboxylic acid residue having 6 to 12 carbon atoms for A include an azelaic acid residue, a sebacic acid residue, a dodecanedicarboxylic acid residue, a cyclohexanedicarboxylic acid residue, and a hexahydrophthalic acid residue.

[0052] The alkylene dicarboxylic acid residue of A having 6 to 12 carbon atoms is preferably an alkylene dicarboxylic acid residue having 7 to 10 carbon atoms, more preferably an azelaic acid residue, a sebacic acid residue, or a dodecanedioic acid residue, and even more preferably a sebacic acid residue.

[0053] Examples of the alkylene glycol residue having 3 to 10 carbon atoms for G include 1,2-propylene glycol residue, 1,3-propylene glycol residue, 1,2-butanediol residue, 1,3-butanediol residue, 2-methyl-1,3-propanediol residue, 1,4-butanediol residue, 1,5-pentanediol residue, 2,2-dimethyl-1,3-propanediol (neopentyl glycol) residue, and 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane). residues, 2-n-butyl-2-ethyl-1,3 propanediol (3,3-dimethylolheptane) residues, 3-methyl-1,5-pentanediol residues, 1,6-hexanediol residues, cyclohexanedimethanol residues, 2,2,4-trimethyl-1,3-pentanediol residues, 2-ethyl-1,3-hexanediol residues, 2-methyl-1,8-octanediol residues, 1,9-nonanediol residues, 1,10-decanediol residues, and diethylene glycol residues.

[0054] The alkylene glycol residue having 3 to 10 carbon atoms for G is preferably an alkylene glycol residue having 3 to 6 carbon atoms, and more preferably a 1,2-propanediol residue, a 1,3-butanediol residue, a 1,4-butanediol residue, a neopentyl glycol residue, a 2-methyl-1,3-propanediol residue, a 3-methyl-1,5-pentanediol residue, a 1,6-hexanediol residue, or a diethylene glycol residue.

[0055] The oxyalkylene glycol residue of G having 3 to 10 carbon atoms is, for example, one of the carbon atoms of the alkylene glycol residue having 3 to 10 carbon atoms replaced with an oxygen atom, and examples thereof include a diethylene glycol residue, a triethylene glycol residue, a tetraethylene glycol residue, a dipropylene glycol residue, and a tripropylene glycol residue. The oxyalkylene glycol residue of G having 3 to 10 carbon atoms is preferably an oxyalkylene glycol residue having 4 to 6 carbon atoms, more preferably a diethylene glycol residue or a triethylene glycol residue.

[0056] The upper limit of each of m and n is not particularly limited, but is 15, for example. The polyester modifier (ii) used in the present invention may be, for example, a mixture of polyester resins in which m in the formula (1) is different from each other and / or a mixture of polyester resins in which n in the formula (2) is different from each other, where the average value of m is, for example, in the range of 1 to 9, and the average value of n is, for example, in the range of 1 to 9. The average values ​​of m and n can be confirmed from the number average molecular weight of the polyester.

[0057] The number average molecular weight (Mn) of the polyester modifier (ii) is, for example, 500 to 5,000, preferably 1,000 to 3,500, more preferably 1,200 to 2,800, and even more preferably 1,600 to 2,400. The number-average molecular weight (Mn) of the polyester of the present invention within the above range can provide even better adhesiveness, flexibility, compatibility, low-temperature properties, and mechanical properties. The number-average molecular weight (Mn) is a value calculated in terms of polystyrene based on gel permeation chromatography (GPC) measurements, and is measured by the method described in the Examples.

[0058] The polyester modifier (ii) preferably has an acid value of 2.0 or less, more preferably 1.0 or less, and the polyester modifier (ii) preferably has a hydroxyl value of 15 or less, more preferably 10 or less.

[0059] The viscosity of the polyester modifier (ii) is preferably 7000 mPa·s or less, more preferably 5000 mPa·s or less. The acid value, hydroxyl value, and viscosity of the polyester modifier (ii) are confirmed by the methods described in the examples.

[0060] The properties of the polyester modifier (ii) vary depending on the number average molecular weight, composition, etc., but are usually liquid, solid, paste, etc. at room temperature.

[0061] The polyester modifier (ii) is obtained using a reaction raw material containing at least one selected from, for example, a monocarboxylic acid, a monoalcohol, a glycol, and a dicarboxylic acid. Here, the reaction raw material means a raw material that constitutes the polyester of the present invention, and does not include a solvent or a catalyst that do not constitute the polyester.

[0062] The method for producing the polyester modifier (ii) is not particularly limited, and it can be produced by a known method, such as the following production method.

[0063] The polyester modifier (ii) may contain one or more selected from monocarboxylic acids, monoalcohols, glycols, and dicarboxylic acids, and may also contain other raw materials. The reactive raw materials for the polyester of the present invention preferably comprise one or more selected from monocarboxylic acids, monoalcohols, glycols, and dicarboxylic acids in an amount of 90 mass% or more based on the total amount of the reactive raw materials, and more preferably consist of only one or more selected from monocarboxylic acids, monoalcohols, glycols, and dicarboxylic acids.

[0064] The monocarboxylic acid used to produce the polyester modifier (ii) is B 11 and B 12 The monocarboxylic acid used may be one kind or two or more kinds in combination. The monoalcohol used to produce the polyester modifier (ii) is B 21 and B 22 The monoalcohol to be used may be one type or two or more types in combination. The glycol used in producing the polyester modifier (ii) is a glycol corresponding to the alkylene glycol residue having 3 to 10 carbon atoms or the oxyalkylene glycol residue having 3 to 10 carbon atoms of G, and the glycols used may be one type or two or more types may be used in combination. The dicarboxylic acid used in producing the polyester modifier (ii) is a dicarboxylic acid corresponding to the alkylene dicarboxylic acid residue of A having 6 to 12 carbon atoms, and the dicarboxylic acid used may be one type or two or more types may be used in combination.

[0065] The polyester represented by the formula (1) in which m is 1 or more can be obtained, for example, by the method shown below. Method 1: A method in which the monocarboxylic acid, dicarboxylic acid and glycol constituting the respective residues of the polyester represented by formula (1) are charged all at once and reacted. Method 2: Dicarboxylic acids and glycols constituting each residue of the polyester represented by formula (1) are reacted under conditions in which the equivalent of the hydroxyl group is greater than the equivalent of the carboxyl group to obtain a polyester having a hydroxyl group at the end of the main chain, and then the obtained polyester resin and B 11 and B 12 A method of reacting a monocarboxylic acid with a monocarboxylic acid.

[0066] The polyester represented by the formula (2) in which n is 1 or more can be obtained, for example, by the method shown below. Method 3: A method in which the monoalcohol, dicarboxylic acid and glycol constituting the respective residues of the polyester represented by formula (2) are charged all at once and reacted. Method 4: Dicarboxylic acids and glycols constituting each residue of the polyester represented by formula (2) are reacted under conditions in which the equivalent of the carboxyl group is greater than the equivalent of the hydroxyl group to obtain a polyester having a carboxyl group at the end of the main chain, and then the obtained polyester is mixed with B 21 and B 22 A method of reacting a monoalcohol comprising the above.

[0067] Hydrogenated vegetable oil fatty acids may be used as the aliphatic monocarboxylic acid used in producing the polyester modifier (ii) represented by formula (1). Examples of such hydrogenated vegetable oil fatty acids include hydrogenated coconut oil fatty acids, hydrogenated palm kernel oil fatty acids, hydrogenated palm oil fatty acids, hydrogenated olive oil fatty acids, hydrogenated castor oil fatty acids, and hydrogenated rapeseed oil fatty acids. These fatty acids are obtained by hydrolyzing and hydrogenating oils obtained from coconut, palm kernel, palm, olive, castor, and rapeseed, respectively, and are all mixtures of two or more long-chain aliphatic monocarboxylic acids containing an aliphatic monocarboxylic acid having 8 to 21 carbon atoms. The aliphatic monocarboxylic acid used in producing the polyester modifier (ii) represented by the formula (1) may be the above-mentioned vegetable oil fatty acid that has not been hydrogenated, provided that the effects of the present invention are not impaired. Also, the vegetable oil fatty acid is not limited to the above.

[0068] When the above-mentioned hydrogenated vegetable oil fatty acid is used as the aliphatic monocarboxylic acid used in producing the polyester modifier (ii) represented by the formula (1), the resulting polyester is a mixture of two or more polyesters represented by the formula (1).

[0069] The polyester modifier (ii) is preferably a polyester obtained by reacting alkylene glycol having 3 to 10 carbon atoms, alkylene dicarboxylic acid having 8 to 14 carbon atoms, and hydrogenated vegetable oil fatty acid as reaction raw materials. Regarding the polyester modifier (ii), when the aliphatic monocarboxylic acid is a hydrogenated vegetable oil fatty acid, the alkylene dicarboxylic acid is sebacic acid, and the alkylene glycol is one or more selected from the group consisting of 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and diethylene glycol, all of the reaction raw materials can be biomass-derived raw materials.

[0070] In the production of the polyester modifier (ii), the reaction of the raw materials may be carried out as an esterification reaction, for example, in the presence of an esterification catalyst at a temperature of 180 to 250°C for 10 to 25 hours. The conditions of the esterification reaction, such as temperature and time, are not particularly limited and may be set appropriately.

[0071] Examples of the esterification catalyst include titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate; tin-based catalysts such as dibutyltin oxide; and organic sulfonic acid-based catalysts such as p-toluenesulfonic acid.

[0072] The amount of the esterification catalyst used may be set appropriately, but is usually in the range of 0.001 to 0.1 part by mass per 100 parts by mass of the total amount of the reaction raw materials.

[0073] The amount of the polyester modifier (ii) used is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the urethane prepolymer (i), in order to obtain even better adhesion, flexibility, compatibility, low-temperature properties, and mechanical properties.

[0074] The moisture-curable polyurethane hot-melt resin composition of the present invention contains the urethane prepolymer (i) and the polyester modifier (ii) as essential components, but other additives may also be used as needed.

[0075] Examples of the other additives that can be used include light resistance stabilizers, curing catalysts, tackifiers, plasticizers, stabilizers, fillers, dyes, pigments, fluorescent brighteners, silane coupling agents, waxes, thermoplastic resins, etc. These additives may be used alone or in combination of two or more.

[0076] The moisture-curable polyurethane resin composition of the present invention preferably has a biomass degree of 40% or more, more preferably 50% or more. The biomass degree of the moisture-curable polyurethane hot-melt resin composition indicates the total weight ratio of biomass-derived raw materials used in producing the moisture-curable polyurethane hot-melt resin composition to the total weight of the moisture-curable polyurethane hot-melt resin composition.

[0077] As described above, the moisture-curable polyurethane hot-melt resin composition of the present invention uses biomass raw materials and is an environmentally friendly material. Furthermore, the moisture-curable polyurethane resin composition of the present invention has excellent adhesion to various fabrics, including water-repellent fabrics. Therefore, the moisture-curable polyurethane hot-melt resin composition of the present invention can be particularly suitably used as an adhesive when producing moisture-permeable, waterproof functional clothing.

[0078] Next, the laminate of the present invention will be described.

[0079] The laminate of the present invention comprises at least a substrate (i) and a cured product of the moisture-curable polyurethane hot-melt resin composition.

[0080] Examples of the fabric (i) that can be used include fiber substrates such as nonwoven fabrics, woven fabrics, and knitted fabrics made from polyester fibers, polyethylene fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, polylactic acid fibers, cotton, hemp, silk, wool, glass fibers, carbon fibers, and blends thereof; nonwoven fabrics impregnated with resins such as polyurethane resins; nonwoven fabrics further provided with a porous layer; and resin substrates.

[0081] Furthermore, in the present invention, the fabric (i) is the one that has been subjected to a water-repellent treatment (hereinafter abbreviated as "water-repellent fabric") and still exhibits excellent adhesiveness. Note that, in the present invention, the "water-repellent" of the water-repellent fabric means that the surface free energy obtained by the following calculation is 50 mJ / m 2 Show that:

[0082] The contact angles of the test liquids (water and diiodomethane) on the 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 the fabric (i) was calculated using the following formula (1). (1+cosA)·γL / 2=(γsd·γLd)1 / 2+(γsp·γLp)1 / 2

[0083] A: Contact angle of the test liquid on the fabric (i) γL: Surface tension of the liquid to be measured γLd: Dispersion force component of the surface free energy of the liquid to be measured γLp: Polar component of the surface free energy of the liquid to be measured γsd: Dispersion force component of the surface free energy of fabric (i) γsp; polar component of the surface free energy of substrate (i)

[0084] Examples of methods for applying the moisture-curable polyurethane hot-melt resin composition include methods using a roll coater, knife coater, spray coater, gravure roll coater, comma coater, T-die coater, applicator, dispenser, etc.

[0085] After the moisture-curable polyurethane hot-melt resin composition is applied, it can be dried and cured by a known method.

[0086] The thickness of the cured product of the moisture-curable urethane hot-melt resin composition is, for example, in the range of 5 to 300 μm.

[0087] When the moisture-curable polyurethane hot-melt resin composition of the present invention is used as an adhesive for moisture-permeable, waterproof functional clothing, the moisture-curable polyurethane hot-melt resin composition is preferably applied intermittently using a gravure roll coater or a dispenser, and then the fabric (i) is bonded to a known moisture-permeable film. In such a case, the thickness of the cured product of the moisture-curable polyurethane hot-melt resin composition is, for example, in the range of 5 to 50 μm. [Example]

[0088] The present invention will be described in more detail below using examples.

[0089] [Synthesis Example 1] Synthesis of urethane prepolymer (i-1) A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser was charged with 247 parts by mass of biomass polyester polyol (a reaction product of sebacic acid ("Sebacic Acid" manufactured by Toyokuni Oil Mills Co., Ltd.) and 1,3-propanediol ("SUSTERRA Propanediol" manufactured by DuPont), number average molecular weight: 2,000, hereinafter abbreviated as "BioPEs (1)") and 133 parts by mass of amorphous polyester polyol (a reaction product of neopentyl glycol and orthophthalic acid, number average molecular weight: 1,000), mixed, and heated under reduced pressure at 100°C to dehydrate the flask until the water content was 0.05% by mass or less. Next, the flask was cooled to 90°C, and 115.8 parts by mass of 4,4'-diphenylmethane diisocyanate melted at 70°C was added. The mixture was reacted at 110°C for approximately 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, thereby obtaining a urethane prepolymer (i-1) with an NCO% of 3.4% by mass.

[0090] [Synthesis Example 2] Synthesis of urethane prepolymer (i-2) A urethane prepolymer (i-2) having an isocyanate group was obtained in the same manner as in Example 1, except that a biomass polyester polyol (a reaction product of sebacic acid ("Sebacic Acid" manufactured by Toyokuni Oil Mills Co., Ltd.) and 1,4-butanediol ("Bio-BDO" manufactured by Genomatica), number average molecular weight: 2,000, hereinafter abbreviated as "BioPEs (2)") was used instead of the BioPEs (1).

[0091] [Synthesis Example 3] Synthesis of urethane prepolymer (i-3) A urethane prepolymer (i-3) having an isocyanate group was obtained in the same manner as in Example 1, except that a biomass polyester polyol (a reaction product of succinic acid (SUCCINITY's "Succinic Acid") and 1,3-propanediol (DUPONT's "SUSTERRA Propanediol"), number average molecular weight: 2,000, hereinafter abbreviated as "BioPEs (3)") was used instead of the BioPEs (1).

[0092] [Synthesis Example 4] Synthesis of polyester modifier (ii-1) A 2-L four-neck flask equipped with a thermometer, stirrer, and reflux condenser was charged with 1,010 g (5.0 mol) of sebacic acid, 152 g (2.0 mol) of 1,2-propanediol, and 180 g (2.0 mol) of 1,3-butanediol. The mixture was heated in stages to 220 °C while stirring under a nitrogen stream. Next, 410 g (2.0 mol) of hydrogenated coconut oil fatty acid and 0.1 g of tetraisopropoxytitanium as an esterification catalyst were added, and the resulting water was continuously removed. After the reaction, the mixture was evaporated under reduced pressure at the same temperature to yield polyester modifier (ii-1) (number average molecular weight 1,860, viscosity 680 mPa s, acid value 0.8, hydroxyl value 6.0).

[0093] [Synthesis Example 5] Synthesis of polyester modifier (ii-2) A 2-L four-neck flask equipped with a thermometer, stirrer, and reflux condenser was charged with 808 g (4.0 mol) of sebacic acid and 380 g (5.0 mol) of 1,2-propanediol. The mixture was heated in stages to 220 °C while stirring under a nitrogen stream. Next, 410 g (2.0 mol) of hydrogenated coconut oil fatty acid and 0.1 g of tetraisopropoxytitanium as an esterification catalyst were added, and the resulting water was continuously removed. After the reaction, the mixture was evaporated under reduced pressure at the same temperature to yield polyester modifier (ii-2) (number average molecular weight 1,800, viscosity 700 mPa·s, acid value 0.4, hydroxyl value 7.0).

[0094] [Comparative Synthesis Example 1] Synthesis of other ester modifiers (iiR-1) A 2-L four-neck flask equipped with a thermometer, stirrer, and reflux condenser was charged with 327 g (2.24 mol) of adipic acid (Asahi Kasei Chemicals), 401 g (5.28 mol) of 1,2-propylene glycol (Asahi Glass Co., Ltd.), 545 g (4.47 mol) of benzoic acid (Kalama), and 0.120 g of tetraisopropyl titanate as an esterification catalyst. The mixture was heated stepwise to 230 °C with stirring under a nitrogen stream. The mixture was heated at 230 °C until the acid value reached 5 or less, and the resulting water was continuously removed. After the reaction, unreacted 1,2-propylene glycol was removed under reduced pressure at 230 to 200 °C to obtain 988 g of ester modifier (iiR-1) (acid value 0.5, viscosity 672 mPa·s at 25 °C).

[0095] [Example 1] A moisture-curable polyurethane hot-melt resin composition was obtained by mixing 277.9 parts by mass of the urethane prepolymer (i-1) obtained in Synthesis Example 1 and 41.7 parts by mass of the polyester modifier (ii-1) obtained in Synthesis Example 4.

[0096] [Example 2] A moisture-curable polyurethane hot-melt resin composition was obtained by mixing 602.7 parts by mass of the urethane prepolymer (i-1) obtained in Synthesis Example 1 and 156.7 parts by mass of the polyester modifier (ii-2) obtained in Synthesis Example 5.

[0097] [Example 3] A moisture-curable polyurethane hot-melt resin composition was obtained by mixing 409.8 parts by mass of the urethane prepolymer (i-2) obtained in Synthesis Example 1 and 41.0 parts by mass of the polyester modifier (ii-1) obtained in Synthesis Example 4.

[0098] [Example 4] A moisture-curable polyurethane hot-melt resin composition was obtained by mixing 420.1 parts by mass of the urethane prepolymer (i-3) obtained in Synthesis Example 1 and 88.2 parts by mass of the polyester modifier (ii-1) obtained in Synthesis Example 4.

[0099] [Comparative Example 1] A moisture-curable polyurethane hot-melt resin composition was obtained in the same manner as in Example 1, except that the amount of polyester modifier (ii-1) was changed from 41.7 parts by mass to 0 parts by mass.

[0100] Comparative Example 2 A moisture-curable polyurethane hot-melt resin composition was obtained in the same manner as in Example 1, except that 4.17 parts by mass of polyester modifier (ii-1) was changed to 97.3 parts by mass of other ester modifier (iiR-1) obtained in Comparative Synthesis Example 1.

[0101] In the examples of the present application, the acid value, hydroxyl value and viscosity of the polyester modifier (ii) were evaluated by the following methods. <Acid value measurement method> Measurement was carried out according to the method of JIS K0070-1992. <Method for measuring hydroxyl value> Measurement was carried out according to the method of JIS K0070-1992. <Viscosity measurement method> Measurement was carried out according to the method of JIS K6901-1986.

[0102] In the examples of the present application, the number average molecular weight of the polyester modifier (ii) is a value calculated in terms of polystyrene based on GPC measurement, and the measurement conditions are as follows. [GPC measurement conditions] Measurement equipment: Tosoh Corporation's high-speed GPC equipment "HLC-8320GPC" Column: Tosoh Corporation "TSK GURDCOLUMN SuperHZ-L" + Tosoh Corporation "TSK gel SuperHZM-M" + Tosoh Corporation "TSK gel SuperHZM-M" + Tosoh Corporation "TSK gel SuperHZ-2000" + Tosoh Corporation "TSK gel SuperHZ-2000" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "EcoSEC Data Analysis Version 1.07" Column temperature: 40℃ Developing solvent: tetrahydrofuran Flow rate: 0.35mL / min Measurement sample: 7.5 mg of the sample was dissolved in 10 ml of tetrahydrofuran, and the resulting solution was filtered through a microfilter to prepare a measurement sample. Sample injection volume: 20 μl Standard sample: In accordance with the measurement manual for the above-mentioned "HLC-8320GPC," the following monodisperse polystyrene with known molecular weight was used.

[0103] (monodisperse polystyrene) Tosoh Corporation "A-300" Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation Tosoh Corporation "F-80" Tosoh Corporation "F-128" Tosoh Corporation "F-288"

[0104] [Method for measuring number average molecular weight] The number average molecular weights of the polyols used in the examples and comparative examples are values ​​measured by gel permeation chromatography (GPC) under the following conditions.

[0105] Measurement equipment: High-speed GPC equipment (Tosoh Corporation "HLC-8220GPC") Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "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 (sample concentration 0.4% by mass in tetrahydrofuran solution) Standard sample: A calibration curve was prepared using the following standard polystyrene.

[0106] (standard polystyrene) Tosoh Corporation's "TSKgel Standard Polystyrene A-500" Tosoh Corporation's "TSKgel Standard Polystyrene A-1000" Tosoh Corporation's "TSKgel Standard Polystyrene A-2500" Tosoh Corporation's "TSKgel Standard Polystyrene A-5000" "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation Tosoh Corporation's "TSKgel Standard Polystyrene F-2" Tosoh Corporation's "TSKgel Standard Polystyrene F-4" Tosoh Corporation's "TSKgel Standard Polystyrene F-10" Tosoh Corporation's "TSKgel Standard Polystyrene F-20" Tosoh Corporation's "TSKgel Standard Polystyrene F-40" Tosoh Corporation's "TSKgel Standard Polystyrene F-80" Tosoh Corporation's "TSKgel Standard Polystyrene F-128" Tosoh Corporation's "TSKgel Standard Polystyrene F-288" Tosoh Corporation's "TSKgel Standard Polystyrene F-550"

[0107] [Mechanical property evaluation method] The moisture-curable polyurethane hot-melt resin compositions obtained in the examples and comparative examples were melted at 100°C, coated to a thickness of 100 μm using a roll coater, and left to stand for 2 days in an atmosphere of 23°C and 50% humidity to obtain a film. The obtained film was cut into strips 5 mm wide and 50 mm long and subjected to tension testing at a crosshead speed of 10 mm / sec using an Autograph AG-I tensile tester (Shimadzu Corporation) in an atmosphere of 23°C to measure the breaking strength (MPa) and evaluate it as follows: "Good": Tensile strength is 20 MPa or more. "X": The tensile strength is less than 20 MPa.

[0108] [Compatibility evaluation method] The film obtained in the same manner as in the above [Method for evaluating mechanical properties] was cut into a piece of 5 cm wide x 5 cm long and left to stand at a temperature of 70°C and a humidity of 95% for 7 days, after which the condition of the film surface was evaluated according to the following criteria. "Good": No powdery or viscous foreign matter (bleed) was found by visual observation of the film surface, and no bleeding was found by touching the sheet surface with a finger. "X": Powdery or viscous foreign matter (bleed) can be confirmed by visually observing the film surface, or bleeding can be confirmed by touching the sheet surface with a finger.

[0109] [Low temperature characteristic evaluation] The processed fabrics using the moisture-curable polyurethane hot-melt resin compositions obtained in the Examples and Comparative Examples were left in a freezer at -10°C for 3 hours. After that, the texture of the processed fabrics immediately after being taken out of the freezer was evaluated according to the following criteria. "◯": Not stiff and has a soft feel. "X": Rough or hard to the touch.

[0110] [Method for evaluating adhesion to fabric] The moisture-curable 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 (40 L / inch, 130 depth, coating amount: 10 g / m 2) was applied to a moisture-permeable film ("VENTEX" manufactured by Kahei Co., Ltd.) and a super water-repellent fabric (surface free energy: 10 mJ / m 2 The resulting treated fabric was then left for 2 days in an atmosphere at a temperature of 23°C and a humidity of 50%, yielding a treated fabric. The treated fabric was cut into 1-inch widths, and the peel strength (N / inch) between the moisture-permeable film and the fabric was measured using an Autograph AG-1 manufactured by Shimadzu Corporation, and evaluated as follows: "〇"; 6.0 (N / inch) or more "×": Less than 6.0 (N / inch)

[0111] [Flexibility evaluation method] The processed fabric (water-repellent fabric) obtained in the "Method for evaluating adhesion to fabric" was left in a constant temperature and humidity room at 23°C and 50% RH for 24 hours, and then the softness was measured three times using a softness tester (leather softness measuring device ST300: manufactured by MSA Engineering Systems, UK) with a measuring ring of 25 mm diameter attached, in accordance with ISO 17235:2015 (IULTCS / IUP 36). The average value was used as the softness. The higher the measurement value, the softer the texture. "Yes": The number is 3 or more. "×": The value is less than 3.

[0112] [Table 1]

[0113] It has been found that the moisture-curable polyurethane hot-melt resin composition of the present invention has a high biomass content and exhibits excellent adhesion to water-repellent fabrics, flexibility, compatibility, low-temperature properties, and mechanical properties.

[0114] On the other hand, Comparative Example 1, which is an embodiment in which the polyester modifier (ii) was not used, had poor low-temperature properties and flexibility.

[0115] Comparative Example 2 is an embodiment in which another modifier was used in place of the polyester modifier (ii), but the compatibility with the urethane prepolymer was poor.

Claims

1. A moisture-curable polyurethane hot-melt resin composition comprising (i) a urethane prepolymer having an isocyanate group and (ii) a polyester modifier represented by the following formula (1) or (2): 【Chemical 1】 (In the formulas (1) and (2), B １１ and B １２ each independently represents an aliphatic monocarboxylic acid residue having 7 to 20 carbon atoms. B ２１ and B ２２ each independently represents an aliphatic monoalcohol residue having 6 to 10 carbon atoms. G represents an alkylene glycol residue having 3 to 10 carbon atoms or an oxyalkylene glycol residue having 3 to 10 carbon atoms. A represents an alkylene dicarboxylic acid residue having 6 to 12 carbon atoms. m and n each represent the number of repeating units enclosed in parentheses, and m and n each independently represent an integer of 1 or more. A and G in each repeating unit enclosed in parentheses may be the same or different.

2. 2. The moisture-curable polyurethane hot-melt resin composition according to claim 1, wherein A is a sebacic acid residue.

3. The moisture-curable polyurethane hot-melt resin composition according to claim 1 or 2, wherein G is a 1,2-propanediol residue, a 1,3-butanediol residue, a 1,4-butanediol residue, a neopentyl glycol residue, a 2-methyl-1,3-propanediol residue, a 3-methyl-1,5-pentanediol residue, a 1,6-hexanediol residue, or a diethylene glycol residue.

4. The moisture-curable polyurethane hot-melt resin composition according to any one of claims 1 to 3, wherein the polyester modifier (ii) is a polyester obtained by reacting an alkylene glycol having 3 to 10 carbon atoms, an alkylene dicarboxylic acid having 8 to 14 carbon atoms, and a hydrogenated vegetable oil fatty acid as reaction raw materials.

5. 5. The moisture-curable polyurethane hot-melt resin composition according to claim 4, wherein the hydrogenated vegetable oil fatty acid is at least one selected from the group consisting of hydrogenated coconut oil fatty acid, hydrogenated palm kernel oil fatty acid, hydrogenated palm oil fatty acid, hydrogenated olive oil fatty acid, hydrogenated castor oil fatty acid, and hydrogenated rapeseed oil fatty acid.

6. The plasticizer for vinyl chloride resin according to any one of claims 1 to 5, wherein the polyester modifier (ii) has a number average molecular weight of 500 to 5,000.

7. The moisture-curable polyurethane hot-melt resin composition according to any one of claims 1 to 6, wherein the urethane prepolymer (i) is a reaction product of a polyol (A) containing a polyester polyol (a1) made from a biomass-derived polybasic acid (x) and a biomass-derived glycol (y), and a polyisocyanate (B).

8. 8. The moisture-curable polyurethane hot-melt resin composition according to claim 7, wherein the biomass-derived polybasic acid (x) is sebacic acid and / or succinic acid.

9. The moisture-curable polyurethane resin composition according to claim 7 or 8, wherein the biomass-derived glycol (y) is 1,3-propanediol and / or 1,4-butanediol.

10. The moisture-curable polyurethane resin composition according to any one of claims 7 to 9, wherein the polyol (A) further contains an amorphous polyester polyol.

11. An adhesive comprising the moisture-curable polyurethane hot-melt resin composition according to any one of claims 1 to 10.

12. A laminate comprising at least a fabric and a cured product of the moisture-curable polyurethane hot melt resin composition according to any one of claims 1 to 10.

13. The laminate according to claim 12, wherein the fabric is a water-repellent fabric.

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