Polyurethane urea resin and elastomer composition using same, polyurethane urea resin solution, polyurethane urea resin aqueous dispersion, paint, ink, coating agent and adhesive

Abstract

This polyurethane urea resin (U) has as essential constituent monomers thereof polyol (A), polyisocyanate (B), and a chain extender (C) having a number average molecular weight or chemical formula weight of less than 500. The polyol (A) includes a polyfarnesene polyol (A1) and / or a hydrogenated product (A2) of the polyfarnesene polyol (A1). The chain extender (C) contains at least one type of compound selected from the group consisting of: a diamine (C11) that has a cyclic skeleton other than an aromatic ring; a diamine (C12) that does not have a ring skeleton and does have a chain hydrocarbon group including a heteroatom other than a nitrogen atom in the chain; a diamine (C13) other than the diamines (C11) and (C12), that has a hydroxy group; a triamine (C14) that has a cyclic skeleton other than an aromatic ring; and a triamine (C15) that has a chain hydrocarbon group and does not have a cyclic skeleton; and water. The urea group concentration in the polyurethane urea resin (U) is 0.05–1.5 mmol / g.

Description

[Technical Field]

[0001] The present invention relates to a polyurethane urea resin, and an elastomer composition, a polyurethane urea resin solution, an aqueous polyurethane urea resin dispersion, a paint, an ink, a coating agent, and an adhesive using the same. [Background technology]

[0002] Conventionally, polyurethane resins have been used in fields such as paints, inks, adhesives (binders), coating agents, and elastomers due to their excellent durability, chemical resistance, and abrasion resistance. Due to their excellent adhesion to substrates such as polyester and nylon, in particular, and from the viewpoints of ease of handling and drying, solvent solutions of polyurethane resins are widely used. However, polyurethane resins do not have sufficient adhesive strength to polyolefin substrates such as polyethylene and polypropylene, and chlorinated polyolefin resins are widely used instead for polyolefin substrates. However, chlorinated polyolefin resins do not have sufficient adhesive strength to substrates such as polyester and nylon, which limits the substrates to which they can be applied. In order to improve the adhesive strength of polyester, nylon, and polyolefin substrates and to enable general-purpose use with various plastics, it has been proposed to use a mixture of polyurethane and chlorinated polyolefin (see, for example, Patent Document 1) or a urethane-modified product of oxidized chlorinated polyolefin as a binder (see, for example, Patent Document 2). Also, a method has been proposed in which the surface of the substrate is subjected to a corona treatment or plasma treatment to improve adhesive strength (see, for example, Patent Document 3).

[0003] However, in recent years, there has been growing emphasis on addressing environmental issues, and there is a strong demand for suppressing the generation of hazardous substances in the disposal of used products. The chlorinated polyolefins used in Patent Documents 1 and 2 contain chlorine, and therefore may generate hazardous substances during incineration, which may pollute the environment. Furthermore, in the method of subjecting the surface of the substrate to a corona treatment or plasma treatment, there is a problem in that the adhesiveness decreases with the passage of time after the treatment. Furthermore, toluene is widely used as a solvent for paints, inks, adhesives, and coating agents. However, with the revision of the Industrial Safety and Health Act, environmental concentration regulations for toluene have been strengthened, increasing the demand for toluene-free solvent systems. Furthermore, in recent years, there has been an increasing demand for more environmentally friendly alcohol-solvent and water-based systems. Furthermore, particularly in printing inks, there is a growing need for biomass-based raw materials, and there is an increasing demand for urethane resins with a high biomass concentration as binders. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 10-251594 [Patent Document 2] Japanese Patent Application Publication No. 11-323236 [Patent Document 3] Japanese Patent Application Laid-Open No. 2000-319426 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above-mentioned problems, and has an object to provide a polyurethane urea resin which does not contain harmful substances such as chlorine, has excellent solubility in solvents other than toluene, exhibits particularly excellent adhesion to plastic substrates (polyolefin, polyester, nylon, etc.) that have not been subjected to corona treatment or plasma treatment without impairing mechanical strength, and has excellent solution stability and dispersion stability in aqueous systems, as well as an elastomer composition, polyurethane urea resin solution, polyurethane urea resin aqueous dispersion, paint, ink, coating agent, and adhesive each using the same. [Means for solving the problem]

[0006] The present inventors have conducted extensive research to achieve the above-mentioned object and have arrived at the present invention. Specifically, the present invention relates to a polyurethane urea resin (U) having, as essential constituent monomers, a polyol (A), a polyisocyanate (B), and a chain extender (C) having a number average molecular weight or a chemical formula weight of less than 500, wherein the polyol (A) comprises a polyfarnesene polyol (A1) and / or a hydrogenated product (A2) of the polyfarnesene polyol (A1), and the chain extender (C) is selected from the group consisting of a diamine (C11) having a cyclic skeleton other than an aromatic ring, a diamine (C12) having a chain hydrocarbon group containing a heteroatom other than a nitrogen atom in the middle of the chain and having no cyclic skeleton, a diamine (C13) having a hydroxyl group other than the diamines (C11) and (C12), a triamine having a cyclic skeleton other than an aromatic ring, and a diamine (C14) having a cyclic skeleton other than an aromatic ring. and a polyurethane urea resin (U) containing at least one compound selected from the group consisting of a triamine (C14), a triamine (C15) having a chain hydrocarbon group but not a cyclic skeleton, and water, wherein the polyurethane urea resin (U) has a urea group concentration of 0.05 to 1.5 mmol / g; an elastomer composition containing the polyurethane urea resin; a polyurethane urea resin solution containing the polyurethane urea resin and a solvent (S); an aqueous polyurethane urea resin dispersion containing the polyurethane urea resin and water; and a paint, ink, coating agent, and adhesive containing the polyurethane urea resin solution and / or the aqueous polyurethane urea resin dispersion. [Effects of the Invention]

[0007] The polyurethane urea resin of the present invention does not contain harmful substances such as chlorine, has excellent solubility in solvents other than toluene, and exhibits particularly excellent adhesion to plastic substrates (polyolefin, polyester, nylon, etc.) that have not been subjected to corona treatment or plasma treatment without impairing mechanical strength. It also has the effect of being able to obtain elastomer compositions, polyurethane urea resin solutions, polyurethane urea resin aqueous dispersions, paints, inks, coating agents, and adhesives that are excellent in solution stability and dispersion stability in aqueous systems. DETAILED DESCRIPTION OF THE INVENTION

[0008] <Polyurethane urea resin (U)> The polyurethane urea resin of the present invention is a polyurethane urea resin (U) containing, as essential constituent monomers, a polyol (A), a polyisocyanate (B), and a chain extender (C) having a number average molecular weight or a chemical formula weight of less than 500, wherein the polyol (A) comprises a polyfarnesene polyol (A1) and / or a hydrogenated product (A2) of the polyfarnesene polyol (A1), and the chain extender (C) comprises a diamine (C11) having a cyclic skeleton other than an aromatic ring, a heteroatom other than a nitrogen atom in the middle of the chain, and The polyurethane urea resin (U) contains at least one compound selected from the group consisting of diamine (C12) having a chain hydrocarbon group containing a hydroxyl group but not having a cyclic skeleton, diamine (C13) having a hydroxyl group other than the diamines (C11) and (C12), triamine (C14) having a cyclic skeleton other than an aromatic ring, triamine (C15) having a chain hydrocarbon group but not having a cyclic skeleton, and water, and the polyurethane urea resin (U) has a urea group concentration of 0.05 to 1.5 mmol / g. In the present invention, it has been found that by using a polyol containing a polyfarnesene polyol (A1) and / or a hydrogenated product (A2) of the polyfarnesene polyol (A1) as the polyol (A), a moiety having high affinity for plastics is provided in the molecular structure of the polyurethane urea resin (U), and by setting the urea group concentration of the polyurethane urea resin (U) within the above-mentioned range, it is possible to achieve both adhesiveness to plastics, solution stability when dissolved in a solvent other than toluene, and dispersion stability when formed into an aqueous dispersion, without impairing mechanical strength.

[0009] <Polyol (A)> In the present invention, the polyol (A) comprises a polyfarnesene polyol (A1) and / or a hydrogenated product (A2) of the polyfarnesene polyol (A1). The polyfarnesene polyol (A1) means a polyol obtained by introducing a hydroxyl group into a polymer of a monomer containing farnesene. Farnesene is a sesquiterpene hydrocarbon that is attracting attention not only as a petroleum product but also as a biomaterial obtained from plants. Examples of farnesene include α-farnesene represented by the following chemical formula (1) and β-farnesene represented by the following chemical formula (2). One type of farnesene may be used, or two or more types may be used in combination. [ka]

[0010] The polyfarnesene polyol (A1) includes not only polyols in which hydroxyl groups have been introduced into farnesene homopolymers, but also polyols in which hydroxyl groups have been introduced into polyfarnesene copolymers obtained from farnesene and other vinyl monomers. Examples of other vinyl monomers include aliphatic unsaturated hydrocarbons other than farnesene [olefins having 2 to 36 carbon atoms (e.g., ethylene, propylene, 1-butene, 2-butene, isobutene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, triacosene, hexatriacosene, etc.) and dienes having 4 to 36 carbon atoms (e.g., isoprene, 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene, etc.)], alicyclic unsaturated hydrocarbons [e.g., cyclohexene, , (di)cyclopentadiene, pinene, limonene, indene, vinylcyclohexene, and ethylidenebicycloheptene, etc.], aromatic group-containing unsaturated hydrocarbons (for example, styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, vinylnaphthalene, divinylbenzene, divinyltoluene, divinylxylene, and trivinylbenzene, etc.), and the like. The other vinyl monomers may be used alone or in combination of two or more.

[0011] The content of the farnesene-derived structural unit in the polyfarnesene polyol (A1) is preferably 1 to 100% by weight, more preferably 10 to 100% by weight, even more preferably 30 to 100% by weight, next more preferably 50 to 100% by weight, and particularly preferably 70 to 100% by weight, based on the total weight of the monomers constituting the polyfarnesene polyol (A1), from the viewpoints of adhesiveness and solvent solubility. If farnesene is bio-derived, the amount of other petroleum-derived vinyl monomers used can be reduced, reducing dependency on petroleum.

[0012] Examples of methods for obtaining the polyfarnesene polyol (A1) include a method in which a monomer component containing farnesene and, if necessary, a vinyl monomer other than farnesene is subjected to a radical polymerization reaction to obtain a polyfarnesene (co)polymer, and then hydroxyl groups are introduced into the polyfarnesene (co)polymer. Another method includes a method in which a monomer component containing farnesene and, if necessary, a vinyl monomer other than farnesene is subjected to a living anionic polymerization reaction to obtain a polyfarnesene (co)polymer, and then the living terminals of the living polymer are reacted with an alkylene oxide (e.g., one having 2 to 4 carbon atoms, specifically propylene oxide) and a proton source (e.g., an acid) to obtain a polyol (a diol if the chain is linear, or a polyol with three or more hydroxyl groups if the chain is branched) in which hydroxyl groups have been introduced at each terminal of the polymer chain.

[0013] The number average molecular weight (hereinafter abbreviated as Mn) of the polyfarnesene polyol (A1) is preferably from 500 to 6,000, more preferably from 1,000 to 5,000, from the viewpoints of adhesiveness, mechanical strength, and solvent solubility. The weight average molecular weight (hereinafter abbreviated as Mw) of the polyfarnesene polyol (A1) is preferably from 500 to 10,000, more preferably from 1,000 to 8,000, from the viewpoints of adhesiveness, mechanical strength, and solvent solubility. The molecular weight distribution (Mw / Mn) of the polyfarnesene polyol (A1) is preferably from 1.0 to 1.8, more preferably from 1.0 to 1.5, from the viewpoints of adhesiveness, mechanical strength, and solvent solubility. The Mn, Mw and molecular weight distribution of the polyfarnesene polyol (A1) are measured by GPC (gel permeation chromatography) under the following conditions. Apparatus: High temperature gel permeation chromatograph ["Alliance GPC V2000", Waters, Inc.] Detector: Refractive index detector Solvent: orthodichlorobenzene Reference material: Polystyrene Sample concentration: 3mg / ml Column stationary phase: PLgel 10 μm, MIXED-B, 2 columns in series [Manufactured by Polymer Laboratories, Inc.] Column temperature: 135℃

[0014] The hydroxyl value (mgKOH / g) of the polyfarnesene polyol (A1) is preferably from 18 to 225, more preferably from 22 to 112, from the viewpoints of adhesiveness, mechanical strength, and solvent solubility. In the present invention, the hydroxyl value is a value measured in accordance with JIS K0070-1992. The glass transition temperature of the polyfarnesene polyol (A1) is preferably from -80 to -10°C, more preferably from -70 to -30°C, from the viewpoints of adhesiveness and solvent solubility. In the present invention, the glass transition temperature is a value measured by the method (DSC method) specified in ASTM D3418-82 using, for example, a DSC Q20 manufactured by TA Instruments.

[0015] In the present invention, the hydrogenated product (A2) is obtained by partially or completely hydrogenating the carbon-carbon double bonds of the polyfarnesene polyol (A1). The number of carbon-carbon double bonds per 1,000 carbon atoms in the hydrogenated product (A2) is preferably 0 to 200, and more preferably 0 to 100, from the viewpoint of adhesiveness. The number of double bonds is (A2) 1 It can be determined from a spectrum obtained by H-NMR (nuclear magnetic resonance) spectroscopy. That is, the peaks in the spectrum are assigned, and the relative value between the number of double bonds in (A2) and the number of carbon atoms in (A2) is determined from the integral value derived from the double bonds in (A2) at 4.5 to 6 ppm and the integral value derived from (A2), and the number of double bonds per 1,000 carbon atoms in (A2) is calculated.

[0016] The Mn of the hydrogenated product (A2) is preferably from 500 to 6,000, more preferably from 1,000 to 5,000, from the viewpoints of adhesiveness, mechanical strength, and solvent solubility. The Mw of the hydrogenated product (A2) is preferably from 500 to 10,000, more preferably from 1,000 to 8,000, from the viewpoints of adhesiveness, mechanical strength, and solvent solubility. The molecular weight distribution of the hydrogenated product (A2) is preferably from 1.0 to 1.8, more preferably from 1.0 to 1.5, from the viewpoints of adhesiveness, mechanical strength and solvent solubility. The Mn, Mw and molecular weight distribution of the hydrogenated product (A2) are measured by GPC (gel permeation chromatography) under the same conditions as those for the polyfarnesene polyol (A1). The hydroxyl value (mgKOH / g) of the hydrogenated product (A2) is preferably from 18 to 225, more preferably from 22 to 112, from the viewpoints of adhesiveness, mechanical strength, and solvent solubility. The glass transition temperature of the hydrogenated product (A2) is preferably from -80 to -10°C, more preferably from -70 to -30°C, from the viewpoints of adhesiveness and solvent solubility.

[0017] Known examples of the polyfarnesene polyol (A1) and the hydrogenated product (A2) of (A1) include "KRASOL F 3000 (polyfarnesene diol)" and "KRASOL F 3100 (hydrogenated polyfarnesene diol)" manufactured by Cray Valley Corporation, and are available.

[0018] In the present invention, the polyol (A) may contain, in addition to the polyfarnesene polyol (A1) and the hydrogenated product (A2) of (A1), at least one polyol selected from the group consisting of condensation polyester polyol (A3), polylactone polyol (A4), polycarbonate polyol (A5), polyether polyol (A6), poly(meth)acrylic polyol (A7), (hydrogenated) polybutadiene polyol (A8), castor oil-based polyol (A9), and hydroxyl group-modified polyolefin (A10), and preferably contains at least one polyol selected from the group consisting of condensation polyester polyol (A3), polylactone polyol (A4), polycarbonate polyol (A5), polyether polyol (A6), poly(meth)acrylic polyol (A7), (hydrogenated) polybutadiene polyol (A8), and castor oil-based polyol (A9).

[0019] The hydroxyl value (mgKOH / g) of the polyols (A3) to (A9) is preferably from 22 to 225, and more preferably from 28 to 113, from the viewpoint of solvent solubility.

[0020] From the viewpoint of solvent solubility, Mn of the polyols (A3) to (A10) is preferably from 500 to 5,000, and more preferably from 1,000 to 4,000. The Mn of the polyols (A3) to (A9) in the present invention can be measured by gel permeation chromatography (GPC) under the following conditions, for example: The Mn of the hydroxyl group-modified polyolefin (A10) is measured under the same conditions as those for the polyfarnesene polyol (A1). Apparatus: "Waters Alliance 2695" [Waters] Column: "Guardcolumn Super HL" (1 column), "TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Corporation) connected together" Sample solution: 0.25% by weight tetrahydrofuran solution Solution injection volume: 10μl Flow rate: 0.6ml / min Measurement temperature: 40℃ Detector: Refractive index detector Reference material: Standard polyethylene glycol

[0021] Examples of the condensation type polyester polyol (A3) include those obtained by condensing a diol having an Mn of less than 500 with a dicarboxylic acid or an ester-forming derivative thereof [such as an acid anhydride, a lower (C1 to C4) alkyl ester, or an acid halide].

[0022] Examples of diols having an Mn of less than 500 include aliphatic dihydric alcohols having 2 to 8 carbon atoms [linear diols (ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc.) and diols having branched alkyl chains (1,2-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,2-, 1,3-, or 2,3-butanediol, etc.)]; Examples of suitable diols include alicyclic group-containing dihydric alcohols [1,4-bis(hydroxymethyl)cyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane, etc.]; aromatic ring-containing dihydric alcohols having 8 to 20 carbon atoms [m- or p-xylylene glycol, bis(hydroxyethyl)benzene, bis(hydroxyethoxy)benzene]; AO adducts of bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.), AO adducts of dihydroxynaphthalene, bis(2-hydroxyethyl)terephthalate, etc.]. Diols having an Mn of less than 500 may be used singly or in combination of two or more.

[0023] Examples of dicarboxylic acids or ester-forming derivatives thereof include aliphatic dicarboxylic acids having 2 to 15 carbon atoms [oxalic acid, succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.], aromatic dicarboxylic acids having 8 to 12 carbon atoms [terephthalic acid, isophthalic acid, etc.], and ester-forming derivatives thereof [acid anhydrides, lower alkyl esters (dimethyl esters, diethyl esters, etc.), acid halides (acid chlorides, etc.)]. One type of dicarboxylic acid may be used alone, or two or more types may be used in combination.

[0024] Specific examples of the condensation type polyester polyol (A3) include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, poly(polyoxytetramethylene) adipate diol, poly(3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol, and polyneopentyl terephthalate diol.

[0025] Among the condensation type polyester polyols (A3), from the viewpoint of adhesiveness and solvent solubility, polyester diols having branched alkyl chains are preferred, polyneopentyladipate diol and poly(3-methylpentylene adipate) diol are particularly preferred, and poly(3-methylpentylene adipate) diol is most preferred. The condensation type polyester polyols (A3) may be used alone or in combination of two or more.

[0026] Examples of the polylactone polyol (A4) include those obtained by ring-opening polymerization of lactone monomers (γ-butyrolactone, γ-valerolactone, ε-caprolactone, and mixtures of two or more thereof, etc.) using the above-mentioned diol having an Mn of less than 500 as an initiator. Specific examples of the polylactone polyol (A4) include polybutyrolactone diol, polyvalerolactone diol, and polycaprolactone diol. One type of polylactone polyol (A4) may be used alone, or two or more types may be used in combination.

[0027] Examples of the polycarbonate polyol (A5) include polycarbonate diols produced by condensing the diol having an Mn of less than 500 with a low molecular weight carbonate compound (for example, a dialkyl carbonate having an alkyl group with 1 to 6 carbon atoms, an alkylene carbonate having an alkylene group with 2 to 6 carbon atoms, and a diaryl carbonate having an aryl group with 6 to 9 carbon atoms) while causing a dealcoholization reaction. The polycarbonate polyol (A5) may be used alone or in combination of two or more.

[0028] Specific examples of the polycarbonate polyol (A5) include polyhexamethylene carbonate diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol, and poly(tetramethylene / hexamethylene) carbonate diol (for example, a diol obtained by condensing 1,4-butanediol and 1,6-hexanediol with a dialkyl carbonate while causing a dealcoholization reaction).

[0029] Examples of the polyether polyol (A6) include an adduct of the above-mentioned AO having 2 to 12 carbon atoms with the above-mentioned diol having an Mn of less than 500, and the AO may be used alone or in combination of two or more types as block copolymers or random copolymers.

[0030] Among the polyether polyols (A6), those having branched alkyl chains are preferred from the viewpoint of solvent solubility, i.e., those using as raw materials diols having branched alkyl chains among diols having Mn of less than 500, and those using 1,2-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, 3-methyltetrahydrofuran, etc. as AO in the AO adduct, more preferred are aliphatic polyether diols of dihydric alcohols having branched alkyls, and particularly preferred is polyoxypropylene glycol. The polyether polyols (A6) may be used singly or in combination of two or more.

[0031] Examples of the poly(meth)acrylic polyol (A7) include homopolymers and copolymers of (meth)acrylic acid esters having a hydroxy group. The (meth)acrylic polyol can also be obtained by copolymerizing a compound having a polymerizable unsaturated bond in addition to a (meth)acrylic acid ester having a hydroxy group. In the present invention, "(meth)acrylic" means "methacrylic and / or acrylic".

[0032] The (meth)acrylic acid ester having a hydroxy group includes those having one (meth)acryloyl group, and examples thereof include those having a hydroxyalkyl group having 2 to 20 carbon atoms {for example, hydroxyalkyl (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate}, and (meth)acrylic acid monoesters of trihydric alcohol {for example, (meth)acrylic acid monoester of glycerin, (meth)acrylic acid monoester of trimethylolpropane, etc.}, and the like.

[0033] The compound having a polymerizable unsaturated bond includes compounds having one polymerizable unsaturated bond, and examples thereof include (meth)acrylic acid alkyl esters having 4 to 50 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, lauryl (meth)acrylate, glycidyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; unsaturated carboxylic acids having 3 to 50 carbon atoms, such as (meth)acrylic acid, maleic acid, and itaconic acid; unsaturated amides having 3 to 50 carbon atoms, such as (meth)acrylamide, N-methylol (meth)acrylamide, and diacetone (meth)acrylamide; and other polymerizable monomers, such as styrene, vinyl toluene, vinyl acetate, acrylonitrile, and dibutyl fumarate.

[0034] Examples of the polymerization method for the (meth)acrylic acid ester having a hydroxy group or the compound having a polymerizable unsaturated bond include emulsion polymerization, suspension polymerization, dispersion polymerization, solution polymerization, etc. The emulsion polymerization can also be carried out in stages.

[0035] Specific examples of the commercially available poly(meth)acrylic polyol (A7) include "ARUFON UH-2000, UH-2041, UH-2190, UHE-2012" manufactured by Toagosei Co., Ltd., and "Actflow UT-1001, UMM-1001" manufactured by Soken Chemical & Engineering Co., Ltd.

[0036] Among the poly(meth)acrylic polyols (A7), from the viewpoint of solvent solubility, preferred are poly(meth)acrylic polyols using at least one compound selected from the group consisting of n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, lauryl (meth)acrylate, and 2-ethylhexyl (meth)acrylate as the compound having a polymerizable unsaturated bond, and more preferred are poly(meth)acrylic diols using n-butyl (meth)acrylate and / or 2-ethylhexyl (meth)acrylate. The poly(meth)acrylic polyols (A7) may be used singly or in combination of two or more.

[0037] The (hydrogenated) polybutadiene polyol (A8) includes polybutadiene polyols and hydrogenation reduction products of polybutadiene polyols (hydrogenated polybutadiene polyols). In the present invention, the term "(hydrogenated) polybutadiene polyol" means "polybutadiene polyol and / or hydrogenated polybutadiene polyol." The iodine value of the (hydrogenated) polybutadiene polyol (A8) is preferably in the range of 1 to 1000 g / 100 g, more preferably in the range of 10 to 600 g / 100 g, and even more preferably in the range of 100 to 500 g / 100 g. The iodine value is measured in accordance with JIS K3331 (1995). Commercially available (hydrogenated) polybutadiene polyols (A8) include, for example, the "NISSO-PBG series" (G-1000, G-2000, G-3000, etc.) manufactured by Nippon Soda Co., Ltd., the "Poly Bd (registered trademark) series" (R-45M, R-15HT, R-45HT, CS-15, CN-15, etc.) manufactured by ARCO Corporation of the United States, and KRASOL HLBP-H 1000, HLBP-H 2000, HLBP-H 3000 manufactured by CRAY VALLEY.

[0038] The castor oil-based polyol (A9) is not particularly limited, and examples thereof include castor oil and castor oil derivatives.

[0039] Examples of the castor oil derivatives include castor oil fatty acids, hydrogenated castor oils obtained by hydrogenating castor oil or castor oil fatty acids, transesterification products of castor oil and other fats and oils, reaction products of castor oil and polyhydric alcohols, esterification products of castor oil fatty acids and polyhydric alcohols, and compounds obtained by addition polymerization of these with alkylene oxides. Among the castor oil-based polyols, it is preferable to use castor oil.

[0040] Examples of the hydrogenated castor oil include those disclosed in Japanese Patent Application Laid-Open No. 2-298574. The hydrogenated castor oil is obtained by hydrogenating the above-mentioned castor oil-based polyol.

[0041] Commercially available castor oil polyols (A9) include, for example, castor oil polyol ["H-35" manufactured by Ito Oil Mills, Ltd.] and [KSK polyol manufactured by Toyokuni Oil Mills, Ltd.].

[0042] Examples of the hydroxyl group-modified polyolefin (A10) include those obtained by reacting an acid-modified polyolefin (X) in which a polyolefin (a) having a carbon-carbon double bond is modified with an unsaturated (poly)carboxylic acid (anhydride) (E) with an amino alcohol (G), and those obtained by reacting the acid-modified polyolefin (X) with an alkylene oxide. The polyolefin (a) having a carbon-carbon double bond includes a polyolefin containing an α-olefin having 3 to 8 carbon atoms as a constituent monomer, which has been modified with a hydroxyl group-containing compound, and may contain ethylene as a constituent monomer. Examples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. Two or more α-olefins may be used in combination, but one α-olefin is preferred. Among the above α-olefins, propylene is preferred from the viewpoints of mechanical strength and productivity.

[0043] The weight ratio of ethylene to α-olefin having 3 to 8 carbon atoms (ethylene:α-olefin) in the constituent monomers of polyolefin (a) having a carbon-carbon double bond is preferably 5:95 to 95:5, more preferably 10:90 to 60:40, and even more preferably 15:85 to 40:60. When the weight ratio (ethylene:α-olefin) is 5:95 or more, the adhesiveness to the substrate tends to be good, and when it is 95:5 or less, the mechanical strength tends to be good. The weight ratio (ethylene:α-olefin) is, for example, 1 It can be calculated by H-NMR.

[0044] The polyolefin (a) having a carbon-carbon double bond may contain other monomers as constituent monomers in addition to ethylene and an α-olefin having 3 to 8 carbon atoms. In this case, the weight of the other monomers is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less, based on the weight of all monomers constituting the polyolefin (a) having a carbon-carbon double bond. Examples of the other monomers include α-olefins having 9 to 30 carbon atoms (sometimes abbreviated as C) (1-decene, 1-dodecene, etc.), and unsaturated monomers having 4 to 30 carbon atoms other than α-olefins (for example, olefins such as 2-butene and isobutene, and vinyl monomers such as styrene, acrylonitrile, acrylamide, and vinyl acetate).

[0045] From the viewpoints of adhesiveness, mechanical strength, and solvent solubility, the Mn of the polyolefin (a) having a carbon-carbon double bond is preferably from 800 to 5,800, and more preferably from 800 to 3,800. The Mn of the polyolefin (a) having a carbon-carbon double bond is measured under the same conditions as those for the polyfarnesene polyol (A1).

[0046] The number of double bonds per 1,000 carbon atoms in the polyolefin (a) having a carbon-carbon double bond [the number of carbon-carbon double bonds at the molecular terminals and in the molecular chain of (a)] is preferably 3 to 30, and more preferably 4 to 20, from the viewpoints of reactivity with the unsaturated (poly)carboxylic acid (anhydride) (E) described below and productivity. The number of double bonds is the number of polyolefins (a) having carbon-carbon double bonds. 1 It can be determined from a spectrum obtained by H-NMR (nuclear magnetic resonance) spectroscopy. That is, the peaks in the spectrum are assigned, and the relative value between the number of double bonds in the polyolefin (a) having carbon-carbon double bonds and the number of carbon atoms in the polyolefin (a) having carbon-carbon double bonds is determined from the integrated value derived from the double bonds at 4.5 to 6 ppm of the polyolefin (a) having carbon-carbon double bonds and the integrated value derived from the polyolefin (a) having carbon-carbon double bonds, and the number of double bonds per 1,000 carbon atoms in the polyolefin (a) having carbon-carbon double bonds is calculated. The number of double bonds in the examples described below was determined according to the above method.

[0047] The isotacticity of the α-olefin-derived unit sequences in the polyolefin (a) having carbon-carbon double bonds is preferably 1 to 50%, more preferably 5 to 45%, from the viewpoints of adhesiveness and solvent solubility. The isotacticity of the α-olefin-derived unit sequences in the polyolefin (a) having carbon-carbon double bonds tends to be directly reflected in the isotacticity of the α-olefin-derived unit sequences in the acid-modified polyolefin (X) and hydroxyl-modified polyolefin (A10) described below. The isotacticity of the α-olefin-derived unit sequences in the polyolefin (a) having carbon-carbon double bonds tends to be reflected in the isotacticity of the α-olefin-derived unit sequences in the high-molecular-weight polyolefin (a0) used as a raw material, and can therefore be adjusted by the high-molecular-weight polyolefin (a0) used as a raw material.

[0048] The isotacticity of the unit sequence portion derived from an α-olefin in the present invention is, for example, 13It can be calculated using C-NMR (nuclear magnetic resonance spectroscopy). In general, it is known that a side chain methyl group is affected by the configuration (meso or racemo) of the methyl groups on both sides (triad), on both sides of the triad (pentad), and on both sides of the pentad (heptad), and peaks are observed at different chemical shifts. It is common to evaluate the stereoregularity for the pentad, and the isotacticity in the present invention can also be calculated based on the evaluation of the pentad. That is, when the α-olefin is propylene, 13 Regarding the carbon peaks derived from the side chain methyl groups in propylene obtained by C-NMR, if each pentad peak (H) and the peak derived from the methyl groups in isotactic propylene in which the pentad is formed only of mesostructure (Ha) are used, isotacticity can be calculated using the following formula: Isotacticity (%) = [(Ha) / Σ(H)] × 100 (1) In the formula, Ha is the peak height of the isotactic signal (pentads are formed only from mesostructures), and H is the height of each peak of the pentad.

[0049] In the present invention, the polyolefin (a) having a carbon-carbon double bond can be produced, for example, by thermally degrading a polyolefin (a0) having a high molecular weight (preferably Mn of 60,000 to 400,000, more preferably Mn of 80,000 to 250,000).

[0050] The thermal degradation method includes (1) a method in which the high molecular weight polyolefin (a0) is thermally degraded in the absence of an organic peroxide, for example, at 300 to 450°C for 0.5 to 10 hours, and (2) a method in which the high molecular weight polyolefin (a0) is thermally degraded in the presence of an organic peroxide [for example, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane], for example, at 180 to 300°C for 0.5 to 10 hours. Of these, method (1) is preferred from the industrial viewpoint and from the viewpoint of modification properties, as it is easy to obtain a polymer with a larger number of double bonds at the molecular terminals and / or in the molecular chain.

[0051] The weight ratio [ethylene:α-olefin] of ethylene and α-olefin (having 3 to 8 carbon atoms), which are monomers constituting the polyolefin (a) having the carbon-carbon double bond, tends to be maintained at the same weight ratio [ethylene:α-olefin] of the high molecular weight polyolefin (a0). The higher the thermal degradation temperature and the longer the thermal degradation time, the greater the number of double bonds per 1,000 carbon atoms tends to be. Furthermore, the smaller the Mn of the high molecular weight polyolefin (a0), the higher the thermal degradation temperature, and the longer the thermal degradation time, the smaller the Mn of the polyolefin (a) having a carbon-carbon double bond tends to be.

[0052] Examples of the unsaturated (poly)carboxylic acid (anhydride) (E) in the present invention include C3-30 (poly)carboxylic acid (anhydride) having one polymerizable unsaturated group. In the present invention, the unsaturated (poly)carboxylic acid (anhydride) means an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid and / or an unsaturated polycarboxylic acid anhydride. Examples of unsaturated monocarboxylic acids include aliphatic unsaturated monocarboxylic acids (C3 to C24, for example, acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, isocrotonic acid) and alicyclic-containing unsaturated monocarboxylic acids (C6 to C24, for example, cyclohexenecarboxylic acid). Examples of the unsaturated poly(2 to 3 or more) carboxylic acid (anhydrides) include unsaturated dicarboxylic acid (anhydrides) [aliphatic dicarboxylic acid (anhydrides) (C4 to 24, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and anhydrides thereof) and alicyclic ring-containing dicarboxylic acid (anhydrides) (C8 to 24, for example, cyclohexene dicarboxylic acid, cycloheptene dicarboxylic acid, bicycloheptene dicarboxylic acid, methyltetrahydrophthalic acid, and anhydrides thereof)]. The unsaturated (poly)carboxylic acid (anhydride) (E) may be used alone or in combination of two or more kinds. Among the unsaturated (poly)carboxylic acid (anhydrides) (E), from the viewpoint of reactivity with the polyolefin (a) having a carbon-carbon double bond, unsaturated dicarboxylic acid anhydrides are preferred, and maleic anhydride is more preferred.

[0053] The acid-modified polyolefin (X) contains the polyolefin (a) having a carbon-carbon double bond and the unsaturated (poly)carboxylic acid (anhydride) (E) as constituent monomers. The weight ratio [(a):(E)] of the polyolefin (a) having a carbon-carbon double bond as a constituent monomer to the unsaturated (poly)carboxylic acid (anhydride) (E) in the acid-modified polyolefin (X) is preferably 80:20 to 99.5:0.5, more preferably 90:10 to 99:1, from the viewpoint of the balance between mechanical strength and adhesiveness.

[0054] The acid-modified polyolefin (X) can be preferably produced by reacting a polyolefin (a) having a carbon-carbon double bond and an unsaturated (poly)carboxylic acid (anhydride) (E) in the presence of a radical initiator (F), if necessary, in a suitable organic solvent [C3 to C18, for example, hydrocarbons (hexane, heptane, octane, dodecane, benzene, toluene, xylene, etc.), halogenated hydrocarbons (di-, tri-, or tetrachloroethane, dichlorobutane, etc.), ketones (acetone, methyl ethyl ketone (sometimes abbreviated as MEK), di-t-butyl ketone, etc.), and ethers (ethyl-n-propyl ether, di-n-butyl ether, di-t-butyl ether, dioxane, etc.)]. The radical initiator (F) may be a known initiator, such as an azo initiator (azobisisobutyronitrile, etc.) or a peroxide initiator (dicumyl peroxide, etc.), with the peroxide initiator being preferred.

[0055] The reaction temperature is preferably 100 to 270°C, more preferably 120 to 250°C, and particularly preferably 130 to 240°C, from the viewpoints of the reactivity between the polyolefin (a) having a carbon-carbon double bond and the unsaturated (poly)carboxylic acid (anhydride) (E) and productivity.

[0056] From the viewpoint of the solvent solubility and adhesiveness of the polyurethane urea resin (U), the acid value of the acid-modified polyolefin (X) is preferably 1 to 100 mgKOH / g, more preferably 3 to 75 mgKOH / g, and particularly preferably 5 to 50 mgKOH / g. The acid value here is a value measured in accordance with JIS K0070:1992 by the following procedures (i) to (iii). (i) Dissolve 1 g of (X) in 100 g of xylene adjusted to 100°C. (ii) At the same temperature, titration is carried out with 0.1 mol / L potassium hydroxide ethanol solution (trade name "0.1 mol / L ethanolic potassium hydroxide solution", manufactured by Wako Pure Chemical Industries, Ltd.) using phenolphthalein as an indicator. (iii) Convert the amount of potassium hydroxide required for titration into mg to calculate the acid value (unit: mgKOH / g). In addition, the above measurement results in one acid anhydride group being equivalent to one carboxyl group. The acid value can be adjusted appropriately by the number of double bonds in the polyolefin (a) having a carbon-carbon double bond, the weight of the polyolefin (a) having a carbon-carbon double bond, the type of the unsaturated (poly)carboxylic acid (anhydride) (E), and the weight of the unsaturated (poly)carboxylic acid (anhydride) (E).

[0057] From the viewpoint of the solvent solubility and adhesiveness of the polyurethane urea resin (U), the Mn of the acid-modified polyolefin (X) is preferably 900 to 5,900, more preferably 900 to 5,000, and particularly preferably 900 to 4,000.

[0058] The isotacticity of the α-olefin-derived unit sequence of the acid-modified polyolefin (X) is preferably 1 to 50%, more preferably 5 to 45%, and particularly preferably 10 to 40%, from the viewpoints of the solvent solubility, adhesiveness, and mechanical strength of the polyurethane urea resin (U).

[0059] Examples of the hydroxyl-modified polyolefin (A10) in the present invention include a reaction product of the acid-modified polyolefin (X) with an amino alcohol (G) and a reaction product of the acid-modified polyolefin (X) with an alkylene oxide (hereinafter abbreviated as AO).

[0060] Examples of the amino alcohol (G) include linear alkanolamines, cycloalkanolamines, and alkylalkanolamines having 2 to 12 carbon atoms (for example, 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, diethanolamine, di-n- or isopropanolamine, 3-aminomethyl-3,5,5-trimethylcyclohexanol, methylethanolamine, and ethylethanolamine), and 2-aminoethanol is preferred.

[0061] Examples of AO include AOs having 2 to 12 carbon atoms (ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, styrene oxide, and α-olefin oxide), preferably those having 2 to 4 carbon atoms, and more preferably ethylene oxide and propylene oxide. One type of AO may be used alone, or two or more types may be used in combination. The number of moles of AO added is preferably 1 to 10 moles or more, more preferably 1 to 5 moles, and particularly preferably 1 mole, per carboxyl group of the acid-modified polyolefin (X).

[0062] The modification of the acid-modified polyolefin (X) with the amino alcohol (G) can be carried out by a known method, for example, by adding an excess (for example, 1.1 to 2 times or more moles) of amino alcohol to the carboxyl groups (or carbonyl groups in the case of an anhydride) of the acid-modified polyolefin (X) to react, and then removing the unreacted amino alcohol by a method such as distillation. The reaction can be carried out in the presence or absence of an organic solvent. The reaction temperature is preferably 100 to 220°C, more preferably 120 to 200°C. The modification of the acid-modified polyolefin (X) with AO is carried out by a known method. For example, the reaction temperature when ring-opening addition polymerizing AO is preferably 40 to 200°C, more preferably 70 to 160°C. The reaction pressure is preferably -0.1 to 0.5 MPa. The reaction is carried out in the presence of a catalyst, if necessary.

[0063] The weight ratio of ethylene to an α-olefin having 3 to 8 carbon atoms, which are constituent monomers of the hydroxyl group-modified polyolefin (A10) (ethylene:α-olefin) is preferably 5:95 to 95:5, more preferably 10:90 to 60:40, and even more preferably 15:85 to 40:60. When the weight ratio (ethylene:α-olefin) is 5:95 or more, the adhesiveness tends to be good, and when it is 95:5 or less, the mechanical strength tends to be good. The weight ratio of ethylene and the α-olefin having 3 to 8 carbon atoms, which are constituent monomers of the hydroxyl group-modified polyolefin (A10), can be adjusted appropriately by changing the ratio of ethylene and the α-olefin having 3 to 8 carbon atoms used in the high molecular weight polyolefin (a0).

[0064] The isotacticity of the α-olefin-derived unit chains of the hydroxyl group-modified polyolefin (A10) is preferably 1 to 50%, more preferably 5 to 45%. When the isotacticity is 1% or more, the adhesiveness tends to be good, and when it is 50% or less, the solvent solubility tends to be good. The isotacticity of the α-olefin-derived unit sequence portion of the hydroxyl group-modified polyolefin (A10) can be appropriately adjusted by the isotacticity of the high-molecular-weight polyolefin (a0).

[0065] The Mn of the hydroxyl group-modified polyolefin (A10) is from 1,000 to 6,000, preferably from 1,000 to 4,000, from the viewpoints of adhesiveness and solvent solubility. The Mn of the hydroxyl group-modified polyolefin (A10) can be appropriately adjusted by controlling the Mn of the polyolefin (a) having a carbon-carbon double bond, the type and amount of the unsaturated (poly)carboxylic acid (anhydride) (E) used, and the reaction between the polyolefin (a) having a carbon-carbon double bond and the unsaturated (poly)carboxylic acid (anhydride) (E).

[0066] The hydroxyl value (mgKOH / g) of the hydroxyl group-modified polyolefin (A10) is preferably 14 to 110, preferably 20 to 100, and more preferably 25 to 80. When the hydroxyl value is 14 or more, the solvent solubility of the polyurethane urea resin (U) tends to be improved, and when it is 110 or less, the adhesiveness of the polyurethane urea resin (U) to polyolefin films tends to be improved. The hydroxyl value of the hydroxyl-modified polyolefin (A10) can be appropriately adjusted by the number of double bonds in the polyolefin (a) having a carbon-carbon double bond, the amount of the polyolefin (a) having a carbon-carbon double bond used, and the type and amount of the unsaturated (poly)carboxylic acid (anhydride) (E) used. The acid value (mgKOH / g) of the hydroxyl group-modified polyolefin (A10) is preferably 0-10, more preferably 0-5. The hydroxyl value and acid value of the hydroxyl-modified polyolefin (A10) are values ​​measured in accordance with JIS K0070-1992.

[0067] In the present invention, the number of hydroxyl groups per molecule of the hydroxyl-modified polyolefin (A10) is preferably 1.5 to 2.0, more preferably 1.6 to 2.0, from the viewpoints of the solvent solubility, adhesiveness, and mechanical strength of the polyurethane urea resin (U). The number of hydroxyl groups per molecule of the hydroxyl-modified polyolefin (A10) can be calculated by the following mathematical formula (1): Number of hydroxyl groups per molecule = Mn A ×OHV / 56100 (1) Mn A : Mn of hydroxyl group modified polyolefin (A10) OHV: Hydroxyl value (mgKOH / g) of hydroxyl-modified polyolefin (A10)

[0068] When at least one polyol selected from the group consisting of condensation polyester polyols (A3), polylactone polyols (A4), polycarbonate polyols (A5), polyether polyols (A6), poly(meth)acrylic polyols (A7), (hydrogenated) polybutadiene polyols (A8), castor oil-based polyols (A9) and hydroxyl-modified polyolefins (A10) is used as the polyol (A), the ratio of the total weight of (A3) to (A10) to the total weight of the polyfarnesene polyol (A1) and its hydrogenated product (A2) is preferably 100% by weight or less, more preferably 10 to 90% by weight, from the viewpoints of the solvent solubility and mechanical strength of the polyurethane urea resin (U).

[0069] <Polyisocyanate (B)> Examples of the polyisocyanate (B) in the present invention include chain aliphatic diisocyanates (B1) having 4 to 22 carbon atoms, alicyclic diisocyanates (B2) having 8 to 18 carbon atoms, aromatic diisocyanates (B3) having 8 to 26 carbon atoms, and aromatic aliphatic diisocyanates (B4) having 10 to 18 carbon atoms.

[0070] Examples of the chain aliphatic diisocyanate (B1) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (hereinafter abbreviated as PDI), hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate, and bis(2-isocyanatoethyl) carbonate.

[0071] Examples of the alicyclic diisocyanate (B2) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, and 2,5- or 2,6-norbornane diisocyanate.

[0072] Examples of the aromatic diisocyanate (B3) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter abbreviated as TDI), 4,4'- or 2,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), polyaryl diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, and m- or p-isocyanatophenylsulfonyl isocyanate.

[0073] Examples of the aralkyl diisocyanate (B4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate.

[0074] Among these, the alicyclic diisocyanates (B2) having 8 to 18 carbon atoms are preferred from the viewpoint of adhesiveness, and IPDI is more preferred from the viewpoint of solvent solubility and adhesiveness of the polyurethane urea resin (U). The polyisocyanate (B) may be used alone or in combination of two or more kinds.

[0075] <Chain extender (C)> In the present invention, examples of the chain extender (C) having an Mn or chemical formula weight of less than 500 include polyamine (C1), polyol (C2), water, etc. The chain extender (C) may be used alone or in combination of two or more. The chain extender (C) contains, as an essential component, at least one compound selected from the group consisting of diamines (C11) having a cyclic skeleton other than an aromatic ring, diamines (C12) having a chain hydrocarbon group containing a heteroatom other than a nitrogen atom in the middle of the chain and not having a cyclic skeleton, diamines (C13) having a hydroxyl group other than the diamines (C11) and (C12), triamines (C14) having a cyclic skeleton other than an aromatic ring, triamines (C15) having a chain hydrocarbon group and not having a cyclic skeleton, and water (including ion-exchanged water). The polyamine (C1) means a compound having a total of two or more primary amino groups or secondary amino groups. In addition, in the diamines (C11) to (C13) above, the diamine means a compound having a total of two primary amino groups or two secondary amino groups. In addition, in the above triamines (C14) to (C15), the triamine means a compound having a total of three primary amino groups, secondary amino groups, and tertiary amino groups. It is presumed that a polyurethane urea resin using, for example, at least one compound selected from the group consisting of the above (C11) to (C15) as the chain extender (C) has improved solvent solubility or improved stability of an aqueous polyurethane urea resin dispersion, which will be described later, due to the following mechanism. It is believed that the introduction of a bulky three-dimensional structure by diamine (C11), a heteroatom by diamine (C12), and a hydroxyl group by diamine (C13) into the main chain of the polyurethane urea resin reduces the crystallinity of the polyurethane urea resin, thereby improving the solvent solubility or the stability of the aqueous dispersion. In addition, the triamine (C14) and triamine (C15) give the polyurethane urea resin an appropriate branched structure, which is thought to reduce the crystallinity of the polyurethane urea resin, thereby improving the solvent solubility or the stability of the aqueous dispersion.

[0076] Furthermore, from the viewpoint of solvent solubility or stability of the aqueous dispersion, it is preferable that the chain extender (C) does not contain a chain extender having an aromatic ring skeleton (such as a phenyl group). From the viewpoint of reducing the environmental load, it is preferable that the chain extender (C) does not contain a chain extender having a halogen group. Furthermore, from the viewpoint of solvent solubility or stability of the aqueous dispersion, it is preferable that the chain extender (C) does not contain a chain extender having an acidic group (such as a carboxy group or a sulfo group).

[0077] Examples of diamines (C11) having a cyclic skeleton other than an aromatic ring include isophoronediamine, piperazine, 1,4-bis(3-aminopropyl)piperazine, 1,4-cyclohexanediamine, norbornanediamine, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, and 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane. Of these, isophoronediamine is preferred from the viewpoints of adhesiveness and solvent solubility or stability of aqueous dispersions.

[0078] In the diamine (C12) having a chain hydrocarbon group containing a heteroatom other than a nitrogen atom in the middle of the chain and no cyclic skeleton, an oxygen atom is preferred as the heteroatom. Examples of the diamine (C12) include 2,2'-oxybis(ethylamine), ethylene glycol bis(2-aminoethyl) ether, 1,4-butanediol bis(3-aminopropyl) ether, diethylene glycol bis(3-aminopropyl) ether, bis(2-aminopropyl)polypropylene glycol, etc. Among these, bis(2-aminopropyl)polypropylene glycol is preferred from the viewpoints of adhesiveness and solvent solubility or stability of aqueous dispersion.

[0079] Examples of the diamine (C13) having a hydroxyl group other than the diamines (C11) and (C12) include 2-aminoethylaminopropanol, 3-aminopropylaminoethanol, 2-hydroxy-1,3-diaminopropane, N,N'-bis(2-hydroxyethyl)ethylenediamine, etc. Among these, 2-aminoethylaminopropanol is preferred from the viewpoints of adhesiveness and solvent solubility or stability of aqueous dispersion.

[0080] Examples of triamines (C14) having a cyclic skeleton other than an aromatic ring include N-(2-aminoethyl)piperazine, 1,3,5-triaminocyclohexane, etc. Among these, N-(2-aminoethyl)piperazine is preferred from the viewpoints of adhesiveness, solvent solubility, and stability of aqueous dispersions.

[0081] Examples of triamines (C15) having a chain hydrocarbon group but no cyclic skeleton include diethylenetriamine, dipropylenetriamine, dihexylenetriamine, N-methyl-2,2'-diaminodiethylamine, N-methyl-3,3'-iminobis(propylamine), N,N-bis[2-(methylamino)ethyl]methylamine, 2-[bis(2-aminoethyl)amino]-ethanol, etc. Among these, diethylenetriamine is preferred from the viewpoints of adhesiveness and solvent solubility or stability of aqueous dispersions.

[0082] When the chain extender (C) contains the above-mentioned (C11) to (C15), the total weight proportion of the above-mentioned (C11) to (C15) is preferably 0.1 to 30% by weight, more preferably 0.2 to 20% by weight, based on the weight of the polyurethane urea resin (U), from the viewpoint of solvent solubility or the stability of the aqueous dispersion. When the chain extender (C) contains the above (C11) to (C15) and the polyurethane urea resin (U) is a polyurethane urea resin solution, the total weight proportion of the above (C11) to (C15) is preferably 50 to 100% by weight, and more preferably 60 to 100% by weight, based on the total weight of the chain extender (C) [excluding water] used in the polyurethane urea resin (U), from the viewpoint of solvent solubility or stability of an aqueous dispersion. When the chain extender (C) contains the above-mentioned (C11) to (C15) and the polyurethane urea resin (U) is made into an aqueous polyurethane urea resin dispersion, the total weight proportion of the above-mentioned (C11) to (C15) is preferably 1 to 35% by weight, and more preferably 5 to 30% by weight, based on the total weight of the chain extender (C) [excluding water] used in the polyurethane urea resin (U), from the viewpoint of solvent solubility or stability of the aqueous dispersion. From the viewpoint of solvent solubility or aqueous dispersion stability, the total weight proportion of the (C11) to (C15) is preferably 80 to 100% by weight, and more preferably 90 to 100% by weight, based on the total weight of the polyamine (C1) used in the polyurethane urea resin (U). When the chain extender (C) contains water but does not contain any of the (C11) to (C15), the total weight proportion of the polyamine (C1) is preferably 10% by weight or less, and more preferably 5% by weight or less, based on the total weight of the chain extender (C) [excluding water] used in the polyurethane urea resin (U), from the viewpoint of solvent solubility or stability of the aqueous dispersion.

[0083] Examples of the polyol (C2) include the same as those exemplified above as diols having an Mn of less than 500, and polyols (C22) having an ionic polar group. Of the diols exemplified above having an Mn of less than 500, 1,4-butanediol is preferred from the viewpoints of adhesiveness and solvent solubility.

[0084] The polyol (C22) having an ionic polar group includes a polyol (C221) having an anionic group and a polyol (C222) having a cationic group. One type of (C22) may be used alone, or two or more types may be used in combination.

[0085] The anionic group in the polyol (C221) having an anionic group means an acid group and a neutralized acid anion group. Examples of the polyol (C221) having an anionic group include compounds containing a carboxyl group as the anionic group and having 2 to 10 carbon atoms [dialkylolalkanoic acids (e.g., 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid, and 2,2-dimethyloloctanoic acid), tartaric acid, and amino acids (e.g., glycine, alanine, and valine)], compounds containing a sulfonic acid group as the anionic group and having 2 to 16 carbon atoms [3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid and sulfoisophthalic acid di(ethylene glycol) ester], compounds containing a sulfamic acid group as the anionic group and having 2 to 10 carbon atoms [N,N-bis(2-hydroxyethyl)sulfamic acid, and the like], and salts of these compounds neutralized with a neutralizing agent.

[0086] Examples of the neutralizing agent used for the salt of the polyol (C221) having an anionic group include ammonia, an amine compound having 1 to 20 carbon atoms, and an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.). Examples of the amine compound having 1 to 20 carbon atoms include primary amines such as monomethylamine, monoethylamine, monobutylamine, and monoethanolamine; secondary amines such as dimethylamine, diethylamine, dibutylamine, diethanolamine, diisopropanolamine, and methylpropanolamine; and tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, dimethylmonoethanolamine, and triethanolamine.

[0087] As the neutralizing agent used for the salt of polyol (C221) having an anionic group, a compound having a high vapor pressure at 25° C. is preferred from the viewpoint of the storage stability of the aqueous polyurethane urea resin dispersion described below. From this viewpoint, as the neutralizing agent used for the salt of polyol (C221) having an anionic group, ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, and dimethylethylamine are preferred. From the viewpoint of dispersion stability of the polyurethane urea resin (U) in water, the amount of the neutralizer added is preferably such that the neutralization rate is 50 to 200%, more preferably 60 to 150%, relative to the amount of acidic groups in the polyurethane urea resin (U). When the neutralization rate is 200% or less, the working environment (odor) tends to be good, and when the neutralization rate is 50% or more, the dispersion stability of the polyurethane urea resin (U) in water tends to be good. In the present invention, the neutralization rate refers to the mole % of the neutralizing agent relative to the mole number of anionic groups in the polyol (C221) having an anionic group used in producing the polyurethane urea resin (U).

[0088] Among the polyols (C221) having an anionic group, from the viewpoint of dispersion stability of the aqueous polyurethane urea resin dispersion described below, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and salts thereof are preferred, and neutralized salts of 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid with ammonia or an amine compound having 1 to 20 carbon atoms are more preferred.

[0089] The cationic group in the polyol (C222) having a cationic group means a group in which a proton is added to a tertiary amino group, an unneutralized tertiary amino group, or a quaternary ammonium group.

[0090] The polyol (C222) having a cationic group includes, for example, a polyol having a tertiary amino group as the cationic group, and specific examples thereof include salts obtained by neutralizing compounds such as tertiary amino group-containing diols having 3 to 20 carbon atoms [N-alkyldialkanolamines (e.g., N-methyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, and N-methyldipropanolamine) and N,N-dialkylmonoalkanolamines (e.g., N,N-dimethylethanolamine)] with a neutralizing agent.

[0091] Examples of the neutralizing agent used for the polyol (C222) having a cationic group include monocarboxylic acids having 1 to 10 carbon atoms (such as formic acid, acetic acid, and propanoic acid), carbonic acid, dimethyl carbonate, dimethyl sulfate, methyl chloride, and benzyl chloride.

[0092] The neutralizing agent used for the polyol (C221) having an anionic group and the polyol (C222) having a cationic group may be added at any time before, during, or after the urethanization reaction, or before, during, or after the water-dispersion step, but from the viewpoint of the stability of the polyurethane urea resin (U) and the stability of the polyurethane urea resin aqueous dispersion, it is preferred to add it before or during the water-dispersion step. Furthermore, the neutralizing agent that volatilized during the solvent removal may be added after the solvent removal, and the type of neutralizing agent to be added can be freely selected from those described above.

[0093] In obtaining the polyurethane urea resin (U), in addition to the essential components (A), (B), and (C), a reaction terminator (D) can be used for the purpose of adjusting the molecular weight of the polyurethane urea resin.

[0094] Examples of the reaction terminator (D) include monoalcohols having 1 to 10 carbon atoms (e.g., methanol, propanol, butanol, and 2-ethylhexanol) and monoamines having 2 to 8 carbon atoms (mono- or di-alkylamines having 2 to 8 carbon atoms (e.g., n-butylamine and di-n-butylamine), and mono- or dialkanolamines having 2 to 6 carbon atoms (e.g., monoethanolamine, diethanolamine, and propanolamine)). Among these, mono- or dialkanolamines having 2 to 6 carbon atoms are preferred. One type of reaction terminator (D) may be used alone, or two or more types may be used in combination.

[0095] The amine value of the polyurethane urea resin (U) is preferably 0.1 to 20 mgKOH / g, more preferably 0.1 to 5 mgKOH / g, and particularly preferably 0.2 to 2 mgKOH / g. When the amine value is 0.1 mgKOH / g or more, the adhesiveness is good, and when it is 20 mgKOH / g or less, the viscosity and molecular weight have good stability over time. In the present invention, the amine value is a value measured in accordance with JIS K1557-7.

[0096] The weight ratio [(A):(B):(C)] of the polyol (A), polyisocyanate (B), and chain extender (C) in the polyurethane urea resin (U) is preferably 100:(10-40):(1-20), more preferably 100:(12-35):(2-18), from the viewpoints of the solvent solubility, adhesiveness, and mechanical strength of the polyurethane urea resin (U).

[0097] The method for producing the polyurethane urea resin (U) is not particularly limited, and may be either a one-shot method in which polyol (A), polyisocyanate (B), chain extender (C), and, if necessary, reaction terminator (D) are reacted all at once, or a multi-stage method in which they are reacted in stages [for example, a method in which (A), (B), and, if necessary, (C) are reacted to form an isocyanate-terminated prepolymer, and then (C) and, if necessary, (D) are added and the resulting mixture is further reacted]. However, from the viewpoint of adhesiveness, a preferred method involves forming an isocyanate-terminated prepolymer, and then using a C2-12 diamine as chain extender (C) such that the total number of amino groups in the diamine is in excess relative to the equivalent of the isocyanate groups in the prepolymer, thereby introducing amino groups into the ends of the polyurethane urea molecular chains.

[0098] In producing the polyurethane urea resin (U), the molar ratio of the isocyanate groups of the polyisocyanate (B) to the active hydrogen-containing groups of the polyol (A), the chain extender (C) and the optional reaction terminator (D) (isocyanate groups:active hydrogen-containing groups) is preferably 0.7:1 to 2.5:1, more preferably 0.9:1 to 2:1, in the case of a polyurethane urea resin solution, from the viewpoints of the solvent solubility and mechanical strength of the polyurethane urea resin (U). In the case of an aqueous polyurethane urea resin dispersion, the ratio is preferably 0.7:1 to 1:1, more preferably 0.8:1 to 0.99:1, from the viewpoints of storage stability and mechanical strength. In the case of an elastomer composition, the ratio is preferably 0.7:1 to 2.5:1, more preferably 0.9:1 to 2:1, from the viewpoint of mechanical strength.

[0099] In the present invention, the biomass concentration of the polyurethane urea resin (U) is preferably 5 to 95% by weight, more preferably 40 to 95% by weight, from the viewpoint of reducing carbon dioxide. The biomass concentration means the ratio (percentage) of the weight of the constituent monomers derived from biomass used to the weight of the polyurethane urea resin (U). Furthermore, "biomass-derived constituent monomers" are those obtained from biomass (renewable biological resources) materials, and include those derived from plants (soybeans, corn, cottonseed, rapeseed, rice, etc.).

[0100] In the present invention, the biomass-derived carbon ratio of the polyurethane urea resin (U) is preferably 10% or more, more preferably 40% or more, from the viewpoint of reducing carbon dioxide. The biomass-derived carbon ratio means the ratio of biomass-derived carbon to the total carbon contained in the polyurethane urea resin (U), and can be estimated from the content of carbon isotope with mass number 14 in accordance with ASTM D6886.

[0101] The urea group concentration of the polyurethane urea resin (U) in the present invention is 0.05 to 1.5 mmol / g, and preferably 0.4 to 1.2 mmol / g, based on the weight of the polyurethane urea resin (U). In the present invention, the polyol (A) used contains a polyfarnesene polyol (A1) and / or a hydrogenated product (A2) of the polyfarnesene polyol (A1). If the urea group concentration of the polyurethane urea resin (U) is less than 0.05 mmol / g, the mechanical strength will be poor, and if it exceeds 1.5 mmol / g, the adhesiveness, the solution stability when dissolved in a solvent other than toluene, and the dispersion stability of the aqueous dispersion will be poor. In order to adjust the urea group content in the polyurethane urea resin (U) to fall within a desired range, the amino group content, water content, and isocyanate group content in the raw materials of the polyurethane urea resin (U) may be appropriately adjusted.

[0102] The urethane group concentration of the polyurethane urea resin (U) in the present invention is preferably 0.4 to 1.5 mmol / g, more preferably 0.6 to 1.0 mmol / g, based on the weight of the polyurethane urea resin (U), from the viewpoints of adhesiveness, mechanical strength, and solvent solubility. In the present invention, the total concentration of the urethane group and the urea group in the polyurethane urea resin (U) is preferably 0.7 to 2.2 mmol / g, and more preferably 1.0 to 2.0 mmol / g, based on the weight of the polyurethane urea resin (U), from the viewpoints of adhesiveness, mechanical strength, and solvent solubility. The urethane group concentration and urea group concentration in polyurethane urea resin (U) are determined by the N atom content determined by a nitrogen analyzer. 1 It can be calculated from the ratio of urethane groups to urea groups and the contents of allophanate groups and biuret groups quantified by H-NMR. First, the total amount of N atoms derived from "urethane groups" and "urea groups" is calculated by subtracting the amount of N atoms derived from "allophanate groups" and "biuret groups" from the "N atom content." Next, the amounts of N atoms derived from "urethane groups" and "urea groups" are calculated from the ratio of urethane groups to urea groups. From these values, the urethane group concentration and urea group concentration are calculated.

[0103] Specifically, in the present invention, the urethane group concentration and urea group concentration of the polyurethane urea resin (U) can be measured as follows. (Urethane group concentration and urea group concentration of polyurethane urea resin (U)) The urethane group concentration and urea group concentration of polyurethane urea resin (U) were determined by the N atom content quantified using a nitrogen analyzer [ANTEK7000 (manufactured by Antec)]. 1 It is calculated from the ratio of urethane groups to urea groups determined by H-NMR and the contents of allophanate groups and biuret groups described below. 1 The H-NMR measurement is carried out according to the method described in "Structural Study of Polyurethane Resins by NMR: Takeda Research Institute Bulletin 34(2), 224-323 (1975)". 1When an aliphatic isocyanate is used, the weight ratio of the urea group to the urethane group is determined from the ratio of the integral amount of hydrogen derived from the urea group at a chemical shift of around 6 ppm to the integral amount of hydrogen derived from the urethane group at a chemical shift of around 7 ppm by H-NMR measurement, and the contents of the urethane group and urea group are calculated from this weight ratio, the N atom content, and the allophanate group and biuret group contents. When an aromatic isocyanate is used, the weight ratio of urea groups to urethane groups is calculated from the ratio of the integral amount of hydrogen derived from urea groups at a chemical shift of around 8 ppm to the integral amount of hydrogen derived from urethane groups at a chemical shift of around 9 ppm, and the contents of urethane groups and urea groups are calculated from this weight ratio, the above-mentioned N atom content, and the allophanate group and biuret group contents.

[0104] (Allophanate group and biuret group content) The total content of allophanate and biuret groups in the polyurethane urea resin (U) was calculated using a gas chromatograph (Shimadzu GC-9A, manufactured by Shimadzu Corporation). 50 g of DMF solution containing 0.01 wt. % di-n-butylamine and 0.01 wt. % naphthalene (internal standard) was prepared. The sample was weighed into a stoppered test tube, 2 g of the above DMF solution was added, and the test tube was heated in a constant-temperature water bath at 90°C for 2 hours. After cooling to room temperature, 10 μl of acetic anhydride was added and the mixture was shaken and stirred for 10 minutes. An additional 50 μl of di-n-propylamine was added, and the mixture was shaken for 10 minutes before gas chromatographic measurement. A blank measurement was also performed in parallel, and the amount of amine consumed was calculated from the difference with the test value, and the total content of allophanate and biuret groups was measured. (Gas chromatograph conditions) Equipment: Shimadzu GC-9A Column: 10% PEG-20M on Chromosorb WAW DMLS 60 / 80 mesh glass column, 3 mm diameter x 2 m Column temperature: 160°C, sample inlet temperature: 200°C, carrier gas: nitrogen 40 ml / min Detector: FID, sample injection volume: 2 μl (Calculation formula for the total content of allophanate groups and biuret groups) Total content of allophanate groups and biuret groups = {(BA) / B} × 0.00155 / S A: (peak area of ​​di-n-butylacetamide / peak area of ​​naphthalene) of the sample B: Blank (peak area of ​​di-n-butylacetamide / peak area of ​​naphthalene) S: Polyurethane urea resin (U) collected amount (g)

[0105] When the polyurethane urea resin (U) of the present invention has an aromatic ring moiety that satisfies the following specific conditions, the weight proportion of the aromatic ring moiety is preferably 10% by weight or less, and more preferably 5% by weight or less, based on the weight of the polyurethane urea resin (U), from the viewpoint of solvent solubility or the stability of the aqueous dispersion. <Aromatic ring moiety that meets specific conditions> An aromatic ring moiety to which two or more main chains of the polyurethane urea resin (U) are bonded, and which is symmetrical when the main chain bonded to the aromatic ring is "-R" (for example, the aromatic ring in the moiety derived from the AO adduct of bisphenol A and the aromatic ring in the moiety derived from MDI fall under this category, but the aromatic ring in the moiety derived from TDI does not fall under this category). In addition, the weight of the aromatic ring portion is calculated not including the weight of the elements substituting the aromatic ring (for example, in the case of a disubstituted aromatic ring, the weight of the aromatic ring portion is calculated as 76).

[0106] The reaction between the polyol (A) and the polyisocyanate (B) is carried out at a temperature of preferably 20 to 140°C, more preferably 40 to 120°C. The reaction temperature between the polyisocyanate (B) and the chain extender (C), or the reaction temperature between the isocyanate group-terminated prepolymer obtained by reacting the polyol (A) and the polyisocyanate (B) and the chain extender (C) is preferably 100°C or lower, more preferably 0 to 80°C.

[0107] In order to accelerate the reaction, catalysts generally used in urethane reactions (amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), tin-based catalysts (dibutyltin dilaurate, dioctyltin dilaurate, tin octoate, etc.), titanium-based catalysts (tetrabutyl titanate, etc.) and the like may be used, if necessary. The amount of catalyst used is preferably 0.1% by weight or less based on the polyurethane urea resin.

[0108] The reaction may be carried out in a solvent (S), and the solvent (S) may be added during or after the reaction. Examples of the solvent (S) include ester-based solvents (ethyl acetate, butyl acetate, ethyl cellosolve acetate, etc.), ketone-based solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, etc.), ether-based solvents (dioxane, tetrahydrofuran, propylene glycol monomethyl ether, etc.), aliphatic hydrocarbon-based solvents (n-hexane, n-heptane, cyclohexane, methylcyclohexane, etc.), and alcohol-based solvents (ethanol, methanol, n-propyl alcohol, isopropyl alcohol (also called isopropanol), n-butanol, etc.).

[0109] Among these, from the viewpoint of the solubility of the polyurethane urea resin (U), at least one selected from the group consisting of ethyl acetate, butyl acetate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, n-propyl alcohol, methylcyclohexane, and isopropyl alcohol is preferred, at least one selected from the group consisting of ethyl acetate, propylene glycol monomethyl ether, methyl ethyl ketone, n-propyl alcohol, methylcyclohexane, and isopropyl alcohol is more preferred, and at least one selected from the group consisting of ethyl acetate, methyl ethyl ketone, methylcyclohexane, and isopropyl alcohol is particularly preferred. The solvent (S) may be used alone or in combination of two or more.

[0110] In the present invention, the Mn of the polyurethane urea resin (U) in the case of a polyurethane urea resin solution is preferably 10,000 to 40,000. When the Mn is 10,000 or more, the adhesiveness and mechanical strength are good when used as a one-component, and when the Mn is 40,000 or less, the solubility and workability are good. In the case of an aqueous dispersion of a polyurethane urea resin, the Mn is preferably 5,000 to 100,000, and more preferably 10,000 to 40,000. When Mn is 5,000 or more, the adhesiveness and mechanical strength are good, and when Mn is 100,000 or less, the adhesiveness and storage stability are good. In the case of an elastomer composition, the Mn is preferably at least 10,000, and more preferably at least 20,000. When the Mn is at least 10,000, the mechanical strength is good. The Mn of the polyurethane urea resin (U) is measured under the same conditions as those for the polyfarnesene polyol (A1).

[0111] <Elastomer composition> The elastomer composition of the present invention may contain any of the polyurethane urea resins (U) of the present invention, and may also contain known additives such as plasticizers, antiblocking agents, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, and release agents, as well as pigments, dyes, lubricants, fillers, hydrolysis inhibitors, and flame retardants. The total content of the additives in the elastomer composition is preferably 10% by weight or less, more preferably 0.1 to 5% by weight, based on the weight of the polyurethane urea resin (U), from the viewpoint of adhesiveness.

[0112] The elastomer composition of the present invention may be used as a thermoplastic elastomer. However, when the polyurethane urea resin (U) of the present invention has an isocyanate group at its terminal, it can also be used in combination with, for example, an amine-based or polyol-based curing agent. In this case, examples of the amine-based curing agent include 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), and examples of the polyol-based curing agent include 1,4-butanediol, trimethylolpropane, and various polypropylene glycols. When a curing agent is used, the amount of the curing agent is preferably 0.5 to 30 wt % based on the weight of the polyurethane urea resin (U).

[0113] The elastomer composition of the present invention has excellent mechanical strength and exhibits particularly excellent adhesion to plastic substrates (such as polyolefins, polyesters, and nylons) that have not been subjected to corona treatment or plasma treatment, and therefore can be suitably used as automobile interior and / or exterior parts, shielding materials, laminates of electronic materials, etc.

[0114] <Polyurethane urea resin solution> The polyurethane urea resin solution of the present invention contains the polyurethane urea resin (U) and a solvent (S). Examples of the solvent (S) include those mentioned above, and the preferred examples are also the same. The polyurethane urea resin solution of the present invention may be obtained by producing the polyurethane urea resin (U) in the solvent (S), or by producing the polyurethane urea resin (U) and then dissolving it in the solvent (S).

[0115] The content of the polyurethane urea resin (U) in the polyurethane urea resin solution of the present invention is preferably 10 to 50% by weight, more preferably 20 to 40% by weight, based on the weight of the polyurethane urea resin solution, from the viewpoint of handleability. The polyurethane urea resin (U) in the polyurethane urea resin solution of the present invention has good mechanical strength and excellent adhesion to plastic substrates (polyolefin, polyester, nylon, etc.), and the polyurethane urea resin solution of the present invention has excellent solution stability. Therefore, by using the polyurethane urea resin solution of the present invention, paints, inks, coating agents, and adhesives can be obtained which have good mechanical strength, excellent adhesion to plastic substrates, and excellent solution stability.

[0116] <Polyurethane urea resin aqueous dispersion> The aqueous polyurethane urea resin dispersion of the present invention contains a polyurethane urea resin and water, and is obtained by dispersing the polyurethane urea resin (U) in a medium containing water (aqueous medium).

[0117] The aqueous polyurethane urea resin dispersion can be produced, for example, by the following method. (1) A solution (for example, a solvent solution described below) of a polyurethane prepolymer (P) containing a polyol (A) and a polyisocyanate (B) as constituent monomers and having an isocyanate group at its terminal is prepared. Next, water, the chain extender (C), and, if necessary, a solvent and a neutralizing agent are charged, followed by phase inversion emulsification, and, if necessary, the solvent is distilled off to obtain an aqueous polyurethane urea resin dispersion. (2) A solution (for example, a solvent solution described below) of a polyurethane prepolymer (P) containing polyol (A) and polyisocyanate (B) as constituent monomers and having an isocyanate group at its terminal is prepared. Next, a mixture of water, chain extender (C), and, if necessary, a solvent and a neutralizer is charged and dispersed using a known disperser, and if necessary, the solvent is distilled off to obtain an aqueous polyurethane urea resin dispersion.

[0118] (3) A solution (for example, a solvent solution described below) of a polyurethane prepolymer (P) containing polyol (A) and polyisocyanate (B) as constituent monomers and having an isocyanate group at its terminal is prepared. Next, a mixture containing the solution of (P), water, and the chain extender (C) is dispersed using a known disperser, and then, if necessary, a neutralizing agent and a reaction terminator (D) are added, and if necessary, the solvent is distilled off to obtain an aqueous polyurethane urea resin dispersion. (4) A solvent solution of a polyurethane resin (U) containing a polyol (A) and a polyisocyanate (B) as constituent monomers is prepared. Next, water and the chain extender (C) are added and dispersed, for example, by a disperser, and if necessary, the solvent is distilled off to obtain an aqueous polyurethane urea resin dispersion.

[0119] In addition, in the step of obtaining the polyurethane urea resin aqueous dispersion, in addition to (P), the solvent, the neutralizing agent, the chain extender (C), water, and the reaction terminator (D), a known anionic surfactant, cationic surfactant, amphoteric surfactant, or nonionic surfactant (for example, emulsifier (F) described in JP 2015-131889 A) may be used, if necessary.

[0120] Examples of the solvent include organic solvents such as ketone-based solvents (e.g., acetone and methyl ethyl ketone), ester-based solvents [e.g., ethyl acetate and dibasic acid ester (DBE)], ether-based solvents (e.g., tetrahydrofuran), amide-based solvents (e.g., N,N-dimethylformamide and N-methylpyrrolidone), alcohol-based solvents (e.g., isopropyl alcohol), and aromatic hydrocarbon-based solvents (e.g., toluene).

[0121] The polyurethane urea resin aqueous dispersion is prepared by dispersing the polyurethane urea resin (U) in a water-containing medium, and the medium may contain the above-mentioned solvent. From the viewpoint of the working environment, the content of the solvent in the medium is 30% by weight or less, more preferably 5% by weight or less.

[0122] From the viewpoint of dispersion stability, the volume average particle diameter (Dv) of the polyurethane urea resin (U) particles in the polyurethane urea resin aqueous dispersion of the present invention is preferably 0.01 to 1 μm, more preferably 0.02 to 0.7 μm, and particularly preferably 0.03 to 0.4 μm. When the volume average particle diameter (Dv) is 0.01 μm or more, the viscosity is appropriate and handling is good, and when it is 1 μm or less, dispersion stability is good. The volume average particle diameter (Dv) in the present invention can be measured using a light scattering particle size distribution analyzer [LA950 V2, manufactured by Horiba, Ltd.].

[0123] The volume average particle diameter (Dv) can be controlled by the ionic polar groups in the polyurethane urea resin (U) and the type and operating conditions of the dispersing machine used in the dispersing step. Specifically, the volume average particle diameter can be reduced by increasing the amount of ionic polar groups in the polyurethane urea resin (U), and the volume average particle diameter can be increased by decreasing the amount of ionic polar groups in the polyurethane urea resin (U).

[0124] In the polyurethane urea resin aqueous dispersion, the volume average particle diameter (Dv) of the polyurethane urea resin (U) particles can be adjusted by adjusting the amount of (C22) used so that the content of ionic polar groups in the polyurethane urea resin (U) is preferably 0.5 to 5.0 wt %, more preferably 0.5 to 4.8 wt %, and particularly preferably 0.5 to 4.5 wt %, based on the weight of the polyurethane urea resin (U). In the present invention, the content of ionic polar groups refers to the weight % of unneutralized cationic or anionic groups, and does not include the weight of counterions. For example, the content of ionic polar groups in the polyol (C221) having an anionic group refers to the weight % of carboxyl groups (-COOH) in the case of the triethylamine salt of 2,2-dimethylolpropionic acid, and the weight % of sulfo groups (-SO3H) in the case of the triethylamine salt of 3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid. Furthermore, the content of ionic polar groups in the polyol (C222) having a cationic group refers to the weight % of only the nitrogen atoms in the tertiary amino groups.

[0125] <Paint> The coating material of the present invention contains the polyurethane urea resin solution and / or aqueous polyurethane urea resin dispersion of the present invention. In the coating material of the present invention, the polyurethane urea resin (U) functions as a binder, a pigment dispersing resin, etc. The content of the polyurethane urea resin (U) of the present invention in the coating material of the present invention is preferably 1 to 40% by weight, more preferably 2 to 30% by weight, based on the weight of the coating material, from the viewpoints of adhesiveness, mechanical strength, and handleability.

[0126] The paint of the present invention may contain any additive commonly used in paints. Examples of additives include pigments, curing agents, diluents, leveling agents such as acrylic resins and silicone resins, silicone-based and acrylic-based anti-repellents, anti-skinning agents, thixotropic agents, antifoaming agents, color separation inhibitors, smoothing agents, wetting agents, dispersants, thickeners, anti-settling agents, polymerization inhibitors, structural viscosity imparting agents, electrostatic coating property improvers, anti-sagging agents, curing accelerators, antioxidants, light stabilizers, antifouling agents, flame retardants, coating aids, etc. Preferred examples of light stabilizers and antioxidants include the compounds described in JP-A-2004-117997.

[0127] The coating film formed by the paint can be applied to any thickness depending on the application, but the final coating film thickness is preferably 0.1 to 10,000 μm, more preferably 0.1 to 2,000 μm, even more preferably 1 to 1,000 μm, next more preferably 5 to 1,000 μm, and particularly preferably 5 to 200 μm. These coating materials may be applied by any method, including spraying, dipping, roller coating, flow coating, flow coating, electrodeposition coating, powder flow coating, and brush coating. Drying after application varies depending on the paint components, but can be done by natural drying or heat drying (generally at room temperature to 180°C for about 10 to 90 minutes).

[0128] The viscosity (20° C.) of the coating material of the present invention is preferably 100 to 5,000 mPa·s, more preferably 500 to 3,000 mPa·s, from the viewpoint of ease of handling. The viscosity of the paint can be measured using a B-type viscometer in accordance with JIS-K7117-1.

[0129] The coating material of the present invention can be applied to any substrate, depending on the application, such as metals (steel plates, iron and steel, non-ferrous metals, light metals, etc.), plastics (polyolefins, polyesters, nylons, etc.), wood, glass, concrete, resins, rubber, leather, paper, skin, etc., to form a coating film and produce a desired component, but from the viewpoint of adhesion, plastic substrates are preferred as the substrate. The coating material of the present invention can be used, for example, as an automotive coating material for automobile parts, automobile bumpers and bodies, an electrical appliance coating material, an architectural coating material, an anti-corrosion coating material, etc., and is particularly useful as an automotive coating material.

[0130] <Ink> The ink of the present invention contains the polyurethane urea resin solution and / or aqueous polyurethane urea resin dispersion of the present invention. In the ink of the present invention, the polyurethane urea resin (U) functions as a binder, a pigment dispersing resin, etc. The content of the polyurethane urea resin (U) in the ink of the present invention is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, based on the weight of the ink, from the viewpoints of adhesiveness, mechanical strength and handleability.

[0131] The ink of the present invention may also contain additives such as pigments, dyes, other resins, and pigment dispersants that are generally used preferably in printing inks and textile printing inks, etc. The other resins and additives may each be used alone or in combination of two or more.

[0132] The pigment is not particularly limited, and inorganic pigments and organic pigments used in inks can be preferably used. The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used. Examples of other resins include polyamide resins, nitrocellulose, acrylic resins, vinyl acetate resins, styrene-maleic acid copolymer resins, epoxy resins, and rosin resins. The amount of these other resins used is preferably 30% by weight or less, and more preferably 20% by weight or less, based on the weight of the printing ink.

[0133] There are no particular limitations on the method for producing the ink, and printing ink can be produced by known methods, for example, using general-purpose ink production equipment such as a three-roll mill, a ball mill, and a sand grinder mill.

[0134] An example of the formulation of the ink of the present invention is as follows. Polyurethane urea resin (U): 5 to 40% by weight (preferably 10 to 30% by weight) Pigment: 5 to 40% by weight (preferably 10 to 30% by weight) Other resins: 0 to 30% by weight (preferably 0 to 20% by weight) Medium (aqueous medium, solvent, etc.): 30 to 80% by weight (preferably 40 to 70% by weight)

[0135] Inks made using the polyurethane urea resin solution and / or polyurethane urea resin aqueous dispersion of the present invention may be used as one-component inks, or may be used as two-component inks in combination with, for example, a polyisocyanate-based curing agent. Suitable polyisocyanate-based curing agents in this case include adducts from 1 mole of trimethylolpropane and 3 moles of 1,6-hexamethylene diisocyanate, tolylene diisocyanate, or IPDI; isocyanurate-containing trimers synthesized by cyclotrimerization of the isocyanate groups of 1,6-hexamethylene diisocyanate or IPDI; biuret reaction products of portions derived from 1 mole of water and 3 moles of 1,6-hexamethylene diisocyanate; and mixtures of two or more of these. When used as two-component inks, the amount of polyisocyanate-based curing agent used is preferably 0.5 to 10 wt % based on the weight of the polyurethane urea resin (U).

[0136] Examples of printing methods when the ink of the present invention is used as a printing ink include printing methods conventionally used for printing on plastic films, such as special gravure printing, flexographic printing, inkjet printing, offset printing, and thermal transfer printing. Examples of printing methods when the ink of the present invention is used as a textile printing ink include screen printing and inkjet printing.

[0137] When the ink of the present invention is used as a printing ink, it has particularly excellent adhesion to plastics and can be suitably used for printing on various plastic films such as polyester film, nylon film, polyolefin film (surface-treated or untreated polypropylene film, polyethylene film, etc.), polyvinyl acetal film, acetate film, polyvinyl chloride film, and films obtained by subjecting these films to aluminum vapor deposition. Furthermore, when the ink of the present invention is used as a textile printing ink, it has particularly excellent adhesion to polypropylene-based synthetic fibers and also excellent adhesion to other substrates, so it can be suitably used on various fiber substrates.

[0138] <Coating agent> The coating agent of the present invention contains the polyurethane urea resin solution and / or aqueous polyurethane urea resin dispersion of the present invention. In the coating agent of the present invention, the polyurethane urea resin (U) functions as a binder or the like. The content of the polyurethane urea resin (U) in the coating agent of the present invention is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, based on the weight of the coating agent, from the viewpoints of adhesiveness, mechanical strength, and handleability.

[0139] The coating agent of the present invention may contain other resins in addition to the polyurethane urea resin (U), such as polyurethane resins other than the polyurethane urea resin (U), polyester resins, polyacrylic resins, epoxy resins, etc. From the viewpoint of adhesiveness, the content of other resins is preferably 50% by weight or less, more preferably 30% by weight or less, based on the weight of the polyurethane urea resin (U).

[0140] Any additives commonly used in coating agents may be contained. Examples of additives include stabilizers (antioxidants, ultraviolet absorbers, etc.), fillers, colorants (dyes and pigments), flame retardants (antimony oxide, etc.), dispersants, antifoaming agents, and leveling agents. The content of the additives is preferably 10% by weight or less, more preferably 0.5 to 5% by weight, based on the weight of the polyurethane urea resin (U) in the coating agent. Examples of antioxidants include hindered phenols (e.g., Irganox 1010 (Ciba-Geigy)) and hindered amines (e.g., Sanol LS770 (Ciba-Geigy)). Examples of ultraviolet absorbers include triazoles (e.g., Tinuvin 320 (Ciba-Geigy)) and benzophenones (e.g., Cyasorb UV9 (Cyanamid)). Examples of fillers include clay, calcium carbonate, barium sulfate, alumina, silica, carbon black, zinc oxide, calcium oxide, lead dioxide, titanium oxide, diatomaceous earth, glass fiber and its crushed products (e.g., cut glass, milled glass, glass flakes), talc, and mica.

[0141] The viscosity (20° C.) of the coating agent of the present invention is preferably 100 to 5,000 mPa·s, more preferably 500 to 3,000 mPa·s, from the viewpoint of ease of handling. The viscosity of the coating agent can be measured using a B-type viscometer in accordance with JIS-K7117-1.

[0142] Substrates to which the coating agent of the present invention can be applied include plastic molded bodies [polyolefins (polyethylene, polypropylene, etc.), polystyrene, ABS, polyvinyl chloride, polycarbonate, polyacetal, polyester, nylon, polyamide, polyurethane, modified PPO, polymethyl methacrylate, epoxy resin, phenolic resin, melamine resin, etc.], rubbers [natural rubber, synthetic rubber (chloroprene rubber, isoprene rubber, SBR, NBR, butyl rubber, EP rubber, etc.)], porous materials [wood, paper, cloth (woven or nonwoven fabrics of natural or synthetic fibers), plastic foams (polyolefin foam, polyurethane foam, etc.)], and inorganic materials [metals (iron, tin, galvanized iron, aluminum, galvanized steel sheet, etc.), glass, roofing slate, ceramics, etc.]. Among these, plastics are preferred, and polyolefins, polyesters, and nylons are more preferred.

[0143] The coating agent of the present invention exhibits excellent performance, particularly as a primer for painting polyolefin resin molded articles (such as automobile bumpers) and electrodeposition-coated steel sheets of automobile bodies. When used as a primer for painting, the coating amount (after drying) can be selected depending on the purpose, but is preferably 1 to 50 μm, more preferably 2 to 40 μm. Known application methods such as spray coating, brush coating, roll coating, flow coating, and dipping can be used. The drying (baking) temperature is preferably 40 to 130°C, more preferably 60 to 80°C, and the drying time is preferably 0.5 to 60 minutes, more preferably 3 to 30 minutes.

[0144] As the topcoat, known thermosetting or thermoplastic resin paints such as acrylic enamel, one-component and two-component polyurethane paints, acrylic urethane paints, acrylic melamine paints, and alkyd melamine paints are used. The coating thickness of the topcoat (after drying) is preferably 20 to 80 μm. Methods for applying and drying the topcoat include known methods such as the two-coat one-bake (wet-on-wet coating) method and the two-coat two-bake (dry-on-wet coating) method. The topcoat layer may consist of one layer or two or more layers.

[0145] <Adhesive> The adhesive of the present invention contains the polyurethane urea resin solution and / or aqueous polyurethane urea resin dispersion of the present invention. The content of the polyurethane urea resin (U) in the adhesive of the present invention is preferably 1 to 50% by weight, more preferably 2 to 40% by weight, based on the weight of the adhesive, from the viewpoints of adhesiveness, mechanical strength, and handleability.

[0146] The adhesive of the present invention may further contain various additives in addition to the polyurethane urea resin solution of the present invention, if necessary. The additives include one or more selected from the group consisting of tackifiers, plasticizers, adsorbents, colorants, flame retardants, fillers, lubricants, nucleating agents, antioxidants, mold release agents, light stabilizers, fragrances, and ultraviolet absorbers.

[0147] Examples of tackifiers include terpene resins, terpene phenol resins, phenol resins, aromatic hydrocarbon-modified terpene resins, rosin resins, modified rosin resins, synthetic petroleum resins (aliphatic, aromatic, or alicyclic synthetic petroleum resins, etc.), coumarone-indene resins, xylene resins, styrene-based resins, dicyclopentadiene resins, and hydrogenated products of those of these resins that have hydrogenatable unsaturated double bonds.

[0148] As the plasticizer, various plasticizers [for example, those described in Adhesion Technology Vol. 20, (2), 21 (2000)] can be used, and examples thereof include process oils (paraffin, naphthene, or aromatic compound type); liquid resins (Mn 300 to 6,000, for example, liquid polybutene, liquid polybutadiene, liquid polyisoprene); hydrogenated products of such liquid resins; low molecular weight (Mn 300 to 10,000) polyisobutylene; and mixtures of two or more of these.

[0149] Examples of the adsorbent include alumina, silica gel, and molecular sieves.

[0150] Examples of colorants include inorganic pigments (white pigments, cobalt compounds, iron compounds, sulfides, etc.), organic pigments (azo pigments, polycyclic pigments, etc.), and dyes (azo-based, indigoid-based, sulfide-based, alizarin-based, acridine-based, thiazole-based, nitro-based, aniline-based, etc.).

[0151] Examples of the flame retardant include a halogen-containing flame retardant, a sulfur-containing flame retardant, a phosphorus-containing flame retardant, and a metal hydroxide-containing flame retardant.

[0152] Examples of the filler include inorganic fillers (calcium carbonate, talc, clay, etc.).

[0153] Examples of the lubricant include calcium stearate, butyl stearate, and oleic acid amide.

[0154] Nucleating agents include sorbitol, metal phosphates, metal benzoates, metal phosphates, and the like.

[0155] Examples of antioxidants include phenol compounds [monocyclic phenols (e.g., 2,6-di-t-butyl-p-cresol), bisphenols (e.g., 2,2'-methylenebis(4-methyl-6-t-butylphenol)], polycyclic phenols (e.g., 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene)], sulfur compounds (e.g., dilauryl 3,3'-thiodipropionate), and phosphorus compounds (e.g., triphenyl phosphite).

[0156] Examples of the release agent include carboxy-modified silicone oil and hydroxyl-modified silicone oil.

[0157] Examples of the light stabilizer include hindered amine compounds [(bis-2,2,6,6-tetramethyl-4-piperidyl) sebacate, etc.].

[0158] Fragrances include diterpenes, limonene, and the like.

[0159] Examples of ultraviolet absorbers include benzotriazoles [2-(2'-hydroxy-5'-methylphenyl)benzotriazole, etc.], benzophenones [2-hydroxy-4-methoxybenzophenone, etc.], and salicylates [phenyl salicylate, etc.].

[0160] The total content of the additives is preferably 50% by weight or less, more preferably 0.002 to 40% by weight, and particularly preferably 1 to 30% by weight, based on the total weight of the adhesive, from the viewpoint of the effect of addition and adhesiveness.

[0161] When the additives mentioned above overlap, each additive should not be used in the amount necessary to achieve the corresponding additive effect, but should be adjusted according to the purpose of use, taking into consideration that the effects of other additives can also be obtained at the same time.

[0162] Adhesives made using the polyurethane urea resin solution and / or aqueous polyurethane urea resin dispersion of the present invention may be used as one-component inks. However, when the polyurethane urea resin (U) of the present invention is terminated with an isocyanate group, it can also be used as a two-component adhesive in combination with, for example, an amine-based or polyol-based curing agent. In this case, examples of amine-based curing agents include 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), and examples of polyol-based curing agents include 1,4-butanediol, trimethylolpropane, and various polypropylene glycols. Furthermore, when the polyurethane urea resin (U) of the present invention is terminated with an amino group and a hydroxyl group, it can also be used as a two-component adhesive in combination with, for example, a polyisocyanate-based curing agent. Suitable polyisocyanate curing agents in this case include, for example, an adduct of 1 mole of trimethylolpropane and 3 moles of 1,6-hexamethylene diisocyanate, tolylene diisocyanate, or IPDI; an isocyanurate group-containing trimer synthesized by cyclotrimerization of the isocyanate groups of 1,6-hexamethylene diisocyanate or IPDI; a biuret reaction product of a portion derived from 1 mole of water and 3 moles of 1,6-hexamethylene diisocyanate; and a mixture of two or more of these. When used as a two-component adhesive, the amount of polyisocyanate curing agent used is preferably 0.5 to 10 wt % based on the weight of the polyurethane urea resin (U).

[0163] <Adhesive body> The adhesive of the present invention can be used to bond adherends to obtain an adhered body. Examples of the adherend include various plastics [polyolefins (polyethylene, polypropylene, etc.), polyester, nylon, polystyrene, syndiotactic polystyrene, ABS, polyvinyl chloride, polycarbonate, polyacetal, polyamide, polyimide, polyurethane, modified PPO, polymethyl methacrylate, liquid crystal polymer, epoxy resin, phenolic resin, melamine resin, etc.], rubbers [natural rubber, synthetic rubber (chloroprene rubber, isoprene rubber, SBR, NBR, butyl rubber, EP rubber, etc.)], porous materials [wood, paper, cloth (woven or nonwoven fabrics of natural fibers and synthetic fibers, etc.), plastic foams (polyolefin foam, polyurethane foam, etc.)], and inorganic materials [metals (copper, iron, tin, galvanized iron, aluminum, galvanized steel sheet, etc.), glass, roofing slate, ceramic, etc.]. Among these, from the viewpoint of adhesion, plastic substrates are preferred, and polyolefin, polyester, and nylon are more preferred. At least one of the main surfaces of the adherend is preferably made of a polyolefin substrate.

[0164] The method for applying the adhesive of the present invention to an adherend is not particularly limited, and the adhesive can be applied with a spatula, comb, roller, trowel, rake, etc., or by hand or machine application, such as extrusion or spraying with a sealing gun, to form a coating film of any thickness, film sheet, thick object, or any other shape. A coating film can also be formed by incorporating a compound with anti-sagging properties and applying the coating to vertical surfaces, wall surfaces, curved surfaces, depressions, etc. with a roller, lysine gun, airless gun, etc.

[0165] The adhesive of the present invention can be used as an adhesive for automobile parts using polyolefin parts such as bumpers, for building parts, for optical films, for electronic materials, for battery electrodes, for olefin tapes, for polyolefin-based laminate films, and the like, and is particularly useful as an adhesive for automobile parts and laminate films. [Example]

[0166] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following, "parts" means parts by weight.

[0167] Production Example 1 Production of hydroxyl group-modified polyolefin (A10) A reaction vessel was charged with 1,000 parts of polyolefin (a-1) [trade name "Vistamaxx3980" manufactured by Exxonmobil] composed of 91% by weight propylene and 9% by weight ethylene as constituent monomers. The liquid phase was heated and melted using a mantle heater while nitrogen was purged. Thermal degradation was carried out at 370°C for 90 minutes with stirring to obtain polyolefin (Z1-1). 20 parts of maleic anhydride were then charged to the reaction vessel. After nitrogen substitution, the mixture was heated to 180°C under nitrogen purging to achieve a uniform solution. A solution of 5 parts of radical initiator (dicumyl peroxide, trade name "Percumyl D" manufactured by NOF Corporation) (F-1) dissolved in 50 parts of xylene was added dropwise over 5 minutes, followed by stirring under xylene reflux for 1 hour. Unreacted maleic anhydride was then removed by distillation under reduced pressure (1.5 kPa) to obtain acid-modified polyolefin (X-1). In a similar reaction vessel, 500 parts of acid-modified polyolefin (X-1) and 32 parts of 2-aminoethanol (G-1) were charged and reacted at 180°C for 1 hour under a nitrogen gas atmosphere. Unreacted 2-aminoethanol was then distilled off at 180°C under a reduced pressure of 2.7 kPa to obtain hydroxyl-modified polyolefin (A10). The hydroxyl-modified polyolefin (A10) had a hydroxyl value of 29 mg KOH / g, an acid value of 0.2 mg KOH / g, an Mn of 3,500, and an isotacticity of 43%.

[0168] Example 1 A reactor equipped with a stirrer was charged with 235 parts of polyfarnesene polyol (A1) {Krasol F-3000: Cray Valley, Mn = 3,000}, 3.08 parts of 1,4-butanediol, and 46.6 parts of IPDI. The mixture was reacted at 110°C under a nitrogen atmosphere for 6 hours to produce a urethane prepolymer with an NCO content of 2.52 wt%. After cooling to 40°C, 600 parts of ethyl acetate was added to obtain a homogeneous solution. Next, 100 parts of isopropanol was added and stirred until homogeneous. After that, 13.91 parts of isophoronediamine and 1.72 parts of diethanolamine were added, and the mixture was reacted at 40°C for 1 hour to produce a solution of polyurethaneurea resin (U-1) of the present invention. The viscosity of the polyurethaneurea resin (U-1) solution at 20°C was 800 mPa·s, and the Mn of the polyurethaneurea resin (U-1) was 15,000.

[0169] Examples 2 to 11, Comparative Examples 1 to 4, 6, and 7 Solutions of polyurethane urea resins (U-2) to (U-11), (U'-1) to (U'-4), (U'-6), and (U'-7) were obtained by carrying out the reaction in the same manner as in Example 1, except that the raw materials used were changed to the types and amounts shown in Tables 1 and 2. The results are shown in Tables 1 and 2.

[0170] Example 12 A reactor equipped with a stirrer was charged with 71.0 parts of hydrogenated polyfarnesene polyol (A2) {Krasol F-3100: Cray Valley, Mn = 3,000}, a hydrogenated product of polyfarnesene polyol (A1), 39.5 parts of biomass 1,3-propanediol, 213 parts of Sannix PP-400, 0.35 parts of ion-exchanged water, and 376 parts of TDI. The mixture was reacted at 80°C for 3 hours under a nitrogen atmosphere to produce a urethane prepolymer with an NCO content of 10.3 wt%. After cooling to 40°C, 300 parts of ethyl acetate was added to form a homogeneous solution, yielding a solution of polyurethane urea resin (U-12) of the present invention. The viscosity of the polyurethane urea resin (U-12) solution at 20°C was 500 mPa·s, and the Mn of polyurethane urea resin (U-12) was 700.

[0171] Example 13 A reactor equipped with a stirrer was charged with 731 parts of hydrogenated polyfarnesene polyol (A2), 40.6 parts of 1,6-hexanediol, 40.6 parts of an ethylene oxide 2-mol adduct of bisphenol A, 0.41 parts of ion-exchanged water, and 187 parts of MDI, and the mixture was reacted for 5 hours at 80°C under a nitrogen atmosphere to produce a polyurethane urea resin (U-13) of the present invention. The viscosity of the polyurethane urea resin (U-13) at 20°C was 5,800 mPa s, and the Mn of the polyurethane urea resin (U-13) was 25,000.

[0172] Example 14, Comparative Example 5 Polyurethane urea resins (U-14) and (U'-5) were obtained by carrying out the reaction in the same manner as in Example 13, except that the raw materials used were changed to the types and amounts shown in Tables 1 and 2. The results are shown in Tables 1 and 2.

[0173] [Table 1]

[0174] [Table 2]

[0175] Example 15 (Preparation of urethane prepolymer) A simple pressurized reaction apparatus equipped with a stirrer and a heater was charged with 272 parts of the polyfarnesene polyol (A1), 3.32 parts of 1,4-butanediol, 17.0 parts of 2,2-dimethylolpropionic acid, 82.7 parts of IPDI, and 125 parts of MEK, and the mixture was stirred at 85°C for 10 hours to carry out a urethanization reaction, thereby producing a MEK solution of a urethane prepolymer (P-1). (Production of aqueous polyurethane urea resin dispersion) 500 parts of the obtained MEK solution of urethane prepolymer (P-1) was charged into a simple pressure reaction apparatus equipped with a stirrer and a heating reaction device, and 237 parts of MEK and 12.8 parts of triethylamine (neutralizing agent) were added while stirring at 50°C. The mixture was homogenized at 60 rpm for 30 minutes, and then 581 parts of ion-exchanged water was gradually added while stirring at 500 rpm, maintaining the temperature at 50°C, to emulsify the mixture. 26.0 parts of a 5 wt% aqueous solution of diethylenetriamine was then added, and the MEK was distilled off under reduced pressure at 65°C for 12 hours, yielding an aqueous dispersion of polyurethane urea resin (U-15).

[0176] Examples 16 to 20, Comparative Examples 8 to 10 Aqueous dispersions of polyurethane urea resins (U-16) to (U-20) and (U'-8) to (U'-10) were obtained by carrying out the reaction in the same manner as in Example 15, except that the raw materials used were changed to the types and amounts shown in Table 3. The results are shown in Table 3.

[0177] [Table 3]

[0178] The raw materials for the polyol (A) used in the examples and comparative examples are as follows. <Polyol (A)> Polyfarnesene polyol (A1): Krasol F-3000: CRAY VALLEY, Mn=3,000, Tg=-65°C, hydroxyl value=37.4 Hydrogenated polyfarnesene polyol (A2): Krasol F-3100: CRAY VALLEY, Mn=3,000, Tg=-56°C, hydroxyl value=37.4 Condensation type polyester polyol (A3): Kuraray Polyol P-2010: Poly(3-methyl-1,5-pentanediol, adipic acid polycondensate) with Mn=2,000 [Kuraray Co., Ltd.] Polylactone polyol (A4): PLACCEL 220: Polycaprolactone diol with Mn=2,000 [manufactured by Daicel Corporation] Polycarbonate polyol (A5): Ethanacol UH-200: Polyhexamethylene carbonate diol with Mn=2,000 [manufactured by Ube Industries, Ltd.] Polyether polyol (A6): Sannix PP-3000: Polyoxypropylene glycol with Mn=3,000 [manufactured by Sanyo Chemical Industries, Ltd.] PTMG2000: Polyoxytetramethylene glycol with Mn=2,000 [Mitsubishi Chemical Corporation] Poly(meth)acrylic polyol (A7): Actflow UT-1001: Polyacrylic diol with Mn=2000 [manufactured by Soken Chemical & Engineering Co., Ltd.] (Hydrogenated) polybutadiene polyol (A8): NISSO-PB GI-2000: Hydrogenated polybutadiene diol with Mn=2,000 [manufactured by Nippon Soda Co., Ltd.] Castor oil-based polyol (A9): HS 2G-120: Castor oil diol with Mn=920 [Toyokuni Oil Mills, Ltd.] Hydroxyl-modified polyolefin (A10): Obtained in Manufacturing Example 1

[0179] The raw materials for the diisocyanate (B) and chain extender (C) used in the examples and comparative examples are as follows. <Polyisocyanate (B)> Aliphatic diisocyanates having 4 to 22 carbon atoms (B1): Biomass PDI: Stabio PDI: 1,5-pentamethylene diisocyanate [Mitsui Chemicals, Inc.] HDI Alicyclic diisocyanates having 8 to 18 carbon atoms (B2): IPDI Aromatic diisocyanates having 8 to 26 carbon atoms (B3): TDI MDI <Chain extender (C)> Polyol (C2): 1,4-Butanediol Biomass 1,3-propanediol: Susterra Propanediol [manufactured by DuPont Tate & Lyle Bio Products Company] Biomass neopentyl glycol: Neeture N-40 [Perstorp] 1,6-Hexanediol Ethylene oxide adduct of bisphenol A: Newpol BPE-20T: 2-mol ethylene oxide adduct of bisphenol A [manufactured by Sanyo Chemical Industries, Ltd.] Polyether polyol (molecular weight 500 or less): Sannix PP-400: Polyoxypropylene glycol with Mn=400 [manufactured by Sanyo Chemical Industries, Ltd.] 2,2-Dimethylolpropionic Acid 2,2-dimethylolbutanoic acid Diamines having a cyclic skeleton other than an aromatic ring (C11): Isophoronediamine Diamines (C12) that have a chain hydrocarbon group containing a heteroatom other than a nitrogen atom in the middle of the chain and do not have a cyclic skeleton: Bis(2-aminopropyl)polypropylene glycol: Polyetheramine D230: Bis(2-aminopropyl)polypropylene glycol with Mn=230 [Mitsui Chemicals Fine Co., Ltd.] Diamines (C13) having a hydroxyl group other than the diamines (C11) and (C12): 2-Aminoethylaminopropanol Triamines with a cyclic skeleton other than an aromatic ring (C14): N-(2-aminoethyl)piperazine Triamines (C15) having a chain hydrocarbon group and no cyclic skeleton: Diethylenetriamine (water): Ion-exchanged water others: Ethylenediamine 4,4'-Methylenedianiline

[0180] The raw materials for the reaction terminator (D) and solvent (S) used in the examples and comparative examples are as follows. Reaction stopper (D): Diethanolamine Dibutylamine Solvent(S): Ethyl acetate Methylcyclohexane Isopropanol Methyl ethyl ketone

[0181] The storage stability of the polyurethane urea resin (U) solutions obtained in Examples 1 to 12 and Comparative Examples 1 to 4, 6, and 7, solutions obtained by diluting the polyurethane urea resin (U) obtained in Examples 13 and 14 and Comparative Example 5 with ethyl acetate to a solids concentration of 30% by weight, and aqueous dispersions of the polyurethane urea resin (U) obtained in Examples 15 to 20 and Comparative Examples 8 to 10 at 0°C and 25°C was evaluated by comparing their appearance immediately after production, one day after production, one week after production, and one month after production according to the following criteria. The results are shown in Tables 4 and 5. <Evaluation criteria> ◎: No change in appearance up to one month after production. ○: No change in appearance up to one week after production. Solution separated or gelled one month after production. △: No change in appearance until 1 day after production. Solution separated or gelled 1 week after production. ×: The solution separated or gelled immediately after production.

[0182] Adhesion tests were carried out by the following method using the solutions of polyurethane urea resin (U) obtained in Examples 1 to 12 and Comparative Examples 1 to 4, 6, and 7, the polyurethane urea resin (U) obtained in Examples 13 and 14 and Comparative Example 5, and the aqueous dispersions of polyurethane urea resin (U) obtained in Examples 15 to 20 and Comparative Examples 8 to 10. The results are shown in Tables 4 and 5.

[0183] [Adhesion test method] A polypropylene film (OPP) subjected to a corona treatment as a surface treatment ["Pylen P-2161" (thickness 30 μm) manufactured by Toyobo Co., Ltd.], a polyester film (PET) subjected to a corona treatment as a surface treatment ["Espet E-5102" (thickness 12 μm) manufactured by Toyobo Co., Ltd.], and a nylon film subjected to a corona treatment as a surface treatment ["Harden N-1130" (thickness 15 μm) manufactured by Toyobo Co., Ltd.] were coated with a solution of the polyurethane urea resin (U) obtained in Examples 1 to 12 and Comparative Examples 1 to 4, 6, and 7. Solutions of polyurethane urea resins (U) obtained in Examples 13 and 14 and Comparative Example 5 diluted with ethyl acetate to a solids concentration of 30% by weight, and aqueous dispersions of polyurethane urea resins (U) obtained in Examples 15 to 20 and Comparative Examples 8 to 10 were applied with a bar coater to a film thickness of 10 μm after drying, dried, and aged for 3 days in an atmosphere of 40°C and 50% RH. A cross-cut cellophane tape peel test was then performed at a temperature of 25°C (±2°C) and a relative humidity of 50% (±10%) to determine the percentage of unpeeled area. The untreated side of each film, which had not been subjected to a corona treatment as a surface treatment, was also tested in the same manner. The above-mentioned cross-cut cellophane tape peeling test was carried out under conditions other than temperature and humidity in accordance with JIS K5600-5-6, using Cellophane Tape (registered trademark) (manufactured by Nichiban Co., Ltd.).

[0184] Dry films were produced according to the following recipes using the polyurethane urea resins (U) obtained in Examples 1 to 20 and Comparative Examples 1 to 10, and the physical properties of the films were measured. The results are shown in Tables 4 and 5.

[0185] [Manufacturing of dried film] Examples 21 to 27, 29 to 30, and 33, and Comparative Examples 11 to 13, 16, and 17 A release film was attached to a polypropylene mold, and the polyurethane urea resin (U) or a solution thereof obtained in Examples 1 to 7, 9 to 10, and 13 and Comparative Examples 1 to 3, 6, and 7 was diluted with toluene in advance to a solids concentration of 20% by weight. The polyurethane urea resin solution was gently poured into the mold so that the film would have a thickness of approximately 200 μm after drying. The film was then spread uniformly and allowed to stand at 25°C for 12 hours. The film was then dried at 70°C for 1 hour using a circulating air dryer, and further dried at 105°C under reduced pressure of 1.3 kPa for 1 hour to obtain a dry film.

[0186] Examples 28, 31, 32, 34, Comparative Examples 14 and 15 A release film was attached to a polypropylene mold, and the polyurethane urea resin (U) or its solution obtained in Examples 8, 11, 12, and 14 and Comparative Examples 4 and 5 was mixed with 1,4-butanediol with a hydroxyl group content equivalent to the molar amount of NCO in the polyurethane urea resin (U), and the polyurethane urea resin solution was adjusted to a solids concentration of 20% by weight with toluene. The polyurethane urea resin solution was gently poured into the mold so that the film would have a thickness of approximately 200 μm after drying, spread evenly throughout, and left to stand at 25°C for 12 hours. After drying at 70°C for 1 hour using a circulating air dryer, the film was further dried at 105°C under reduced pressure of 1.3 kPa for 1 hour to obtain a dried film, which was then aged for 3 days in an atmosphere of 40°C and 50% RH.

[0187] Examples 35 to 40, Comparative Examples 18 to 20 A release film was attached to a polypropylene mold, and the aqueous dispersion of polyurethane urea resin (U) obtained in Examples 15 to 20 and Comparative Examples 8 to 10 was mixed with 10% by weight of N-methylpyrrolidone based on the solid content, and the aqueous dispersion of polyurethane urea resin was adjusted to a solid content concentration of 20% by weight with ion-exchanged water. The aqueous dispersion was gently poured into the mold so that the film would have a thickness of approximately 200 μm after drying, spread evenly throughout, and left to stand at 25°C for 12 hours. After that, the film was dried at 105°C for 3 hours using a circulating air dryer, and further dried at 105°C under reduced pressure of 1.3 kPa for 1 hour to obtain a dry film.

[0188] <Coating film properties> [100% modulus, breaking strength and breaking elongation] The dried film obtained above was cut into a dumbbell-shaped No. 3 specimen and measured for 100% modulus, breaking strength, and breaking elongation at a tensile speed of 500 mm / min using an autograph (Shimadzu Corporation, "AGS-500D"). The 100% modulus and breaking strength are indicators of the strength of the coating when applied to the surface of a substrate as a paint, printing ink, or coating agent. A 100% modulus of 1.0 MPa or greater and a breaking strength of 3.0 MPa or greater are considered usable. Furthermore, breaking elongation is an indicator of the conformability to the substrate when used as a paint, printing ink, coating, or adhesive. A breaking elongation of 300% or greater indicates conformability to the substrate and does not deteriorate even when the substrate is deformed.

[0189] [Table 4]

[0190] [Table 5]

[0191] The results in Table 4 show that the polyurethane urea resin of the present invention does not contain harmful substances such as chlorine, has excellent solubility in solvents other than toluene (ethyl acetate), exhibits excellent adhesion to plastic substrates that have been subjected to corona treatment as a surface treatment, and also to plastic substrates that have not been subjected to corona treatment as a surface treatment, has excellent solution stability and dispersion stability in aqueous systems, and also has good mechanical strength. On the other hand, the evaluation results of the comparative examples (Table 5) show that the polyurethane urea resins of Comparative Examples 3 to 5 and 10, which are conventional polyurethane urea resins that do not use the polyfarnesene polyol (A1) or the hydrogenated product (A2), have extremely poor adhesion to polyolefin films (polypropylene films) and polyester and nylon films that have not been subjected to corona treatment as a surface treatment. In particular, a comparison between Example 14, which uses the hydrogenated product (A2), and Comparative Example 5, which uses a polybutadiene polyol, shows that the polyurethane urea resin of Example 14, which uses (A2) containing farnesene as a constituent monomer, has excellent not only adhesion to polyester and nylon films but also elongation at break. Furthermore, the polyurethane urea resins of Comparative Examples 1 and 2, which use polyfarnesene polyol (A1) but have urea group concentrations outside the range specified by the present invention, are inferior in adhesion to polyolefin films (polypropylene films) and polyester and nylon films that have not been subjected to corona treatment as a surface treatment, compared to the polyurethane urea resin of Example 1. In particular, Comparative Example 1, in which the urea group concentration is outside the lower limit range specified by the present invention, has low mechanical strength of the coating film, specifically low 100% modulus and breaking strength, while Comparative Example 2, in which the urea group concentration is outside the upper limit range specified by the present invention, has extremely poor adhesion and poor solution stability. Similarly, the polyurethane urea resins of Comparative Examples 8 and 9, which used polyfarnesene polyol (A1) but had a urea group concentration outside the range specified by the present invention, had inferior adhesion to polyester films and nylon films compared to the polyurethane urea resin of Example 15. Comparative Example 8, in which the urea group concentration was outside the lower limit of the range specified by the present invention, produced coating films with low mechanical strength, specifically low 100% modulus and breaking strength, while Comparative Example 9, in which the urea group concentration was outside the upper limit of the range specified by the present invention, produced extremely poor adhesion, and the aqueous dispersion was so unstable that it was unable to form a film. In Comparative Examples 6 and 7, which do not use any of (C11) to (C15) as chain extenders or ion-exchanged water, the solution stability is extremely poor and the adhesiveness is also poor. [Industrial Applicability]

[0192] The polyurethane urea resins of the present invention, as well as elastomer compositions, polyurethane urea resin solutions, polyurethane urea resin aqueous dispersions, paints, inks, coating agents, and adhesives using the same, are free of harmful substances such as chlorine, have excellent solubility in solvents other than toluene, exhibit excellent adhesion to plastics (such as polyolefins, polyesters, and nylons) that have not been corona-treated or plasma-treated without impairing mechanical strength, and have excellent solution stability and dispersion stability in aqueous systems. Therefore, paints containing the polyurethane urea resin solutions and / or polyurethane urea resin aqueous dispersions of the present invention can be used as automotive paints for automobile parts, automobile bodies, and the like, paints for electrical appliances, architectural paints, and anti-corrosion paints, and are particularly useful as automotive paints. Furthermore, inks containing the polyurethane urea resin solutions and / or polyurethane urea resin aqueous dispersions of the present invention are particularly suitable as printing inks for special gravure printing, flexographic printing, inkjet printing, offset printing, thermal transfer printing, and the like, and further as textile printing inks. Furthermore, the polyurethane urea resin solution and / or polyurethane urea resin of the present invention is useful not only for the above-mentioned applications but also as an adhesive for automobile components using polyolefin components such as bumpers, building components, optical films, electronic materials, battery electrodes, olefin tapes, polyolefin-based laminate films, undercoat coating agents for painting polyolefin resin molded bodies (such as automobile bumpers) and electrodeposition-coated steel sheets of automobile bodies, and elastomers for automobile interior and exterior parts, shielding materials, and laminates of electronic materials.

Claims

1. A polyurethane urea resin (U) containing, as essential constituent monomers, a polyol (A), a polyisocyanate (B), and a chain extender (C) having a number average molecular weight or a chemical formula weight of less than 500, the polyol (A) comprises a polyfarnesene polyol (A1) and / or a hydrogenated product (A2) of the polyfarnesene polyol (A1); the content of the polyfarnesene polyol (A1) and / or the hydrogenated product of the polyfarnesene polyol (A1) (A2) in the polyol (A) is 50% by weight or more; The chain extender (C) is The composition contains at least one compound selected from the group consisting of a diamine (C11) having a cyclic skeleton other than an aromatic ring, a diamine (C12) having a chain hydrocarbon group containing a heteroatom other than a nitrogen atom in the middle of the chain and not having a cyclic skeleton, a diamine (C13) having a hydroxyl group other than the diamines (C11) and (C12), a triamine (C14) having a cyclic skeleton other than an aromatic ring, a triamine (C15) having a chain hydrocarbon group and not having a cyclic skeleton, and water, The polyurethane urea resin (U) has a urea group concentration of 0.05 to 1.5 mmol / g.

2. 2. The polyurethane urea resin according to claim 1, wherein the polyol (A) contains at least one polyol selected from the group consisting of condensation polyester polyols (A3), polylactone polyols (A4), polycarbonate polyols (A5), polyether polyols (A6), poly(meth)acrylic polyols (A7), (hydrogenated) polybutadiene polyols (A8), and castor oil-based polyols (A9).

3. 3. The polyurethane urea resin according to claim 1, wherein the polyurethane urea resin (U) further contains a reaction terminator (D) as a constituent monomer.

4. The polyurethane urea resin according to any one of claims 1 to 3, wherein the ratio of biomass-derived carbon in the polyurethane urea resin (U) is 10% or more.

5. An elastomer composition comprising the polyurethane urea resin according to any one of claims 1 to 4.

6. A polyurethane urea resin solution comprising the polyurethane urea resin according to any one of claims 1 to 4 and a solvent (S).

7. An aqueous polyurethane urea resin dispersion comprising the polyurethane urea resin according to any one of claims 1 to 4 and water.

8. A paint containing the polyurethane urea resin solution according to claim 6 and / or the polyurethane urea resin aqueous dispersion according to claim 7.

9. An ink containing the polyurethane urea resin solution according to claim 6 and / or the polyurethane urea resin aqueous dispersion according to claim 7.

10. A coating agent comprising the polyurethane urea resin solution according to claim 6 and / or the polyurethane urea resin aqueous dispersion according to claim 7.

11. An adhesive comprising the polyurethane urea resin solution according to claim 6 and / or the polyurethane urea resin aqueous dispersion according to claim 7.

Images