Aqueous urethane resin composition, coating agent, and article

Abstract

To provide an aqueous urethane resin composition capable of forming a coating film having excellent compounding stability, corrosion resistance, and chemical resistance (alkali resistance).SOLUTION: The aqueous urethane resin composition is used which contains a cationic urethane resin (A) and an aqueous medium (B). The cationic urethane resin (A) has a structural unit represented by general formula (1) in one molecule. The cationic urethane resin (A) contains a polyol compound (a1), a polyisocyanate compound (a2), and a nonionic group-containing compound (a3) as essential raw materials. The polyol compound (a1) contains a tertiary amino group-containing polyol compound. The nonionic group-containing compound (a3) is a compound having one functional group capable of reacting with an isocyanate group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an aqueous urethane resin composition, a coating agent, and an article. [Background technology]

[0002] Aqueous urethane resin compositions generally have good adhesion to substrates and form flexible coating films. Because it can be formed into a thin film, it is used in a variety of applications, including as a coating agent or adhesive. do.

[0003] Among these, cationic urethane resin aqueous dispersions are suitable for use as high-performance resins that take advantage of their ionic properties in inkjet treatment agents, metal surface treatment agents, etc. One of the features of the cationic urethane resin aqueous dispersions is their high miscibility with inorganic agents, which makes them suitable for use in metal surface treatment agents that incorporate a large amount of inorganic rust inhibitors to improve water resistance, chemical resistance, and corrosion resistance.

[0004] As the cationic urethane resin water dispersion, there is known a cationic urethane resin water dispersion in which a cationic urethane resin (B) containing a specific structural unit (A) in the molecule is dispersed in an aqueous medium, and the content of the cationic amino group contained in the structural unit (A) in the cationic polyurethane resin (B) is 0.005 to 1.5 equivalents / kg (for example, Patent Document 1). However, this does not satisfy the increasingly high performance requirements in recent years in terms of blend stability, corrosion resistance, and chemical resistance (alkali resistance).

[0005] Therefore, there has been a demand for materials that have even better compounding stability, corrosion resistance, and chemical resistance (alkali resistance). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2006-45509 A

Summary of the Invention

Problems to be Solved by the Invention

[0007] The problem to be solved by the present invention is to provide an aqueous urethane resin composition capable of forming a coating film having excellent blending stability, corrosion resistance, and chemical resistance (alkali resistance), a coating agent containing the aqueous urethane resin composition, and an article having a coating film of the coating agent.

Means for Solving the Problems

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using an aqueous urethane resin composition containing a specific cationic urethane resin and an aqueous medium, and have completed the present invention.

[0009] That is, the present invention relates to an aqueous urethane resin composition containing a cationic urethane resin (A) and an aqueous medium (B), wherein the cationic urethane resin (A) has a structural unit represented by the following general formula (1) in one molecule, the cationic urethane resin (A) uses a polyol compound (a1), a polyisocyanate compound (a2), and a nonionic group-containing compound (a3) as essential raw materials, the polyol compound (a1) contains a tertiary amino group-containing polyol compound, and the nonionic group-containing compound (a3) is a compound having one functional group capable of reacting with an isocyanate group. The present invention also relates to a coating agent containing the aqueous urethane resin composition and an article having a coating film of the coating agent.

[0010]

Chemical Formula

[0011] 〔In formula (1), R 1represents an alkylene group which may contain an aliphatic cyclic structure, a residue of a divalent phenol compound, or a polyoxyalkylene group, and R 2 and R 3 each independently represent an alkyl group which may contain an aliphatic cyclic structure, and R 4 each independently represents a hydrogen atom or a residue of a quaternizing agent introduced by a quaternization reaction, and X - represents an anionic counter ion. ]]

Advantages of the Invention

[0012] The aqueous urethane resin composition of the present invention has excellent blending stability, and its coating film has excellent corrosion resistance, chemical resistance, and (alkali resistance), and thus can be suitably used as a coating agent.

Embodiments for Carrying Out the Invention

[0013] The aqueous urethane resin composition of the present invention is characterized by containing a cationic urethane resin (A) and an aqueous medium (B).

[0014] As the cationic urethane resin (A), those having a structural unit represented by the following general formula (1) are essentially used.

[0015]

Chemical formula

[0016] 〔In formula (1), R 1 represents an alkylene group which may contain an aliphatic cyclic structure, a residue of a divalent phenol compound, or a polyoxyalkylene group, and R 2 and R 3 each independently represent an alkyl group which may contain an aliphatic cyclic structure, and R 4 each independently represents a hydrogen atom or a residue of a quaternizing agent introduced by a quaternization reaction, and X - represents an anionic counter ion. ]]

[0017] Since an aqueous urethane resin composition capable of forming a coating film excellent in corrosion resistance and chemical resistance can be obtained when the content of the cationic amino group contained in the structural unit represented by the general formula (1) above is in the range of 0.03 to 0.5 equivalents / kg in the cationic urethane resin (A), a range of 0.03 to 0.25 is more preferable.

[0018] In addition, as the cationic urethane resin (A), those using a polyol compound (a1), a polyisocyanate compound (a2), and a nonionic group-containing compound (a3) as essential raw materials are used.

[0019] As the polyol compound (a1), a tertiary amino group-containing polyol compound is used as essential.

[0020] Examples of the tertiary amino group-containing polyol compound include compounds obtained by reacting a compound having two epoxy groups in one molecule represented by the following general formula (4) with a secondary amine compound.

[0021]

Chemical formula

[0022] 〔In formula (4), R 7 represents an alkylene group which may contain an aliphatic cyclic structure, a residue of a divalent phenol compound, or a polyoxyalkylene group.〕

[0023] Said R 7Examples of the alkylene group which may contain an aliphatic cyclic structure include ethylene glycol-1,2-diglycidyl ether, propanediol-1,2-diglycidyl ether, propanediol-1,3-diglycidyl ether, butanediol-1,4-diglycidyl ether, pentanediol-1,5-diglycidyl ether, 3-methyl-pentanediol-1,5-diglycidyl ether, neopentyl glycol-diglycidyl ether, hexanediol-1,6-diglycidyl ether, polybutadiene-diglycidyl ether, cyclohexane-1,4-diglycidyl ether, cyclohexane-1,4-dimethanol diglycidyl ether, diglycidyl ether of 2,2-bis(4-hydroxycyclohexyl)-propane (hydrogenated bisphenol A), diglycidyl ether of an isomer mixture of hydrogenated dihydroxydiphenylmethane (hydrogenated bisphenol F), and the like.

[0024] Said R 7 Examples of the residue of the divalent phenol compound include resorcinol-diglycidyl ether, hydroquinone-diglycidyl ether, diglycidyl ether of 2,2-bis(4-hydroxyphenyl)-propane (bisphenol A), diglycidyl ether of an isomer mixture of dihydroxydiphenylmethane (bisphenol F), diglycidyl ether of 4,4-dihydroxy-3-3'-dimethyldiphenylpropane, diglycidyl ether of 4,4-dihydroxydiphenylcyclohexane, diglycidyl ether of 4,4-dihydroxydiphenyl, diglycidyl ether of 4,4-dihydroxydibenzophenone, diglycidyl ether of bis(4-hydroxyphenyl)-1,1-ethane, diglycidyl ether of bis(4-hydroxyphenyl)-1,1-isobutane, diglycidyl ether of bis(4-hydroxy-3-tert-butylphenyl)-2,2-propane, diglycidyl ether of bis(2-hydroxynaphthyl)methane, diglycidyl ether of bis(4-hydroxyphenyl)sulfone (bisphenol S), and the like.

[0025] Said R7 Examples of the polyoxyalkylene group include diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, and the like. Further, polyoxyalkylene glycol diglycidyl ethers having 3 to 60 repeating units of oxyalkylene can also be used. Examples of the polyoxyalkylene glycol diglycidyl ether having 3 to 60 repeating units of oxyalkylene include polyoxyethylene glycol diglycidyl ether, polyoxypropylene glycol diglycidyl ether, diglycidyl ether of ethylene oxide - propylene oxide copolymer, polyoxytetraethylene glycol diglycidyl ether, and the like.

[0026] Among these, since an aqueous urethane resin composition capable of forming a coating film excellent in corrosion resistance and chemical resistance can be obtained, the above-mentioned R 7 is a diglycidyl ether of polyoxyalkylene glycol having a polyoxyalkylene group, and in particular, polyoxyethylene glycol diglycidyl ether, polyoxypropylene glycol diglycidyl ether, and diglycidyl ether of ethylene oxide - propylene oxide copolymer are preferable.

[0027] The above-mentioned R 7 The epoxy equivalent of the diglycidyl ether of polyoxyalkylene glycol having a polyoxyalkylene group is preferably 1000 g / equivalent or less, more preferably 500 g / equivalent or less, and even more preferably 300 g / equivalent or less, since an aqueous urethane resin composition capable of forming a coating film excellent in corrosion resistance and chemical resistance can be obtained.

[0028] Examples of the secondary amine compound include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-tert-butylamine, di-sec-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-octylamine, diisooctylamine, dinonylamine, diisononylamine, di-n-decylamine, di-n-undecylamine, di-n-dodecylamine, di-n-pentadecylamine, di-n-octadecylamine, di-n-nonadecylamine, di-n-eicosylamine, etc. These secondary amine compounds can be used alone or in combination of two or more. Further, from the viewpoint of ease of reaction control, branched or linear aliphatic secondary amine compounds are preferred.

[0029] Regarding the reaction between the compound having two epoxy groups in one molecule represented by the general formula (4) and the secondary amine compound as the tertiary amino group-containing polyol compound, there is no particular limitation. For example, it can be obtained by formulating so that the NH group of the secondary amine compound is 1 equivalent with respect to 1 equivalent of the epoxy group of the compound having two epoxy groups in one molecule represented by the general formula (4), and performing a ring-opening addition reaction without a catalyst at normal temperature or under heating.

[0030] Further, the tertiary amino group-containing polyol compound can impart water dispersibility to the cationic urethane resin (A) obtained by reacting the tertiary amino group-containing polyol compound with the polyisocyanate compound (a2) by neutralizing part or all of the tertiary amino groups of the tertiary amino group-containing polyol compound with an acid or quaternizing them with a quaternizing agent.

[0031] Examples of the acid in the acid neutralization include organic acids such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, butyric acid, lactic acid, malic acid, citric acid, tartaric acid, malonic acid, adipic acid, etc., organic sulfonic acids such as sulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, etc., and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, phosphorous acid, hydrofluoric acid, etc. These acids can be used alone or in combination of two or more.

[0032] Examples of the quaternizing agent include dialkyl sulfates such as dimethyl sulfate, diethyl sulfate, etc., alkyl halides such as methyl chloride, ethyl chloride, benzyl chloride, methyl bromide, ethyl bromide, benzyl bromide, methyl iodide, ethyl iodide, benzyl iodide, etc., methyl or aryl sulfonic acid methyls such as methyl methanesulfonate, methyl p-toluenesulfonate, etc., epoxies such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, etc. These quaternizing agents can be used alone or in combination of two or more.

[0033] In order to exhibit excellent storage stability of the cationic urethane resin aqueous dispersion of the present invention, the usage amounts of the acid and the quaternizing agent are preferably in the range of 0.1 to 3 equivalents, more preferably in the range of 0.3 to 2 equivalents, per 1 equivalent of the tertiary amino group.

[0034] As the polyol compound (a1), a polyol compound other than the tertiary amino group-containing polyol compound (hereinafter abbreviated as "other polyol compound") can be used as necessary.

[0035] Examples of the other polyol compounds include polycarbonate polyols, polyester polyols, polyether polyols, polybutadiene polyols, etc. These polyol compounds can be used alone or in combination of two or more.

[0036] Examples of the polycarbonate polyols include polycarbonate polyols obtained by reacting a carbonate ester and / or phosgene with a diol compound.

[0037] Examples of the carbonate esters include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate, etc. These carbonate esters can be used alone or in combination of two or more.

[0038] Examples of the diol compounds include aliphatic diol compounds such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 1,10-decanediol, 2-ethyl-2-butyl-1,3-propanediol, and 1,12-dodecanediol; alicyclic diol compounds such as 1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol. These diol compounds can be used alone or in combination of two or more.

[0039] The number average molecular weight of the polycarbonate polyol is preferably in the range of 200 to 10,000, more preferably in the range of 300 to 5,000, since an aqueous urethane resin composition capable of forming a coating film excellent in corrosion resistance and chemical resistance can be obtained. In the present invention, the number average molecular weight of the polycarbonate polyol indicates a value measured by the gel permeation chromatography (GPC) method.

[0040] Examples of the polyester polyol include those obtained by subjecting a polyvalent carboxylic acid and a polyhydric alcohol to an esterification reaction.

[0041] Examples of the polyvalent carboxylic acid include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid or their esterified products, and aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, maleic acid, pimelic acid, suberic acid, azelaic acid, itaconic acid, sebacic acid, chlorendic acid, 1,2,4-butanetricarboxylic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, and fumaric acid or their esterified products. These polyvalent carboxylic acids or their esterified products can be used alone or in combination of two or more.

[0042] Examples of the polyhydric alcohol include aromatic diols such as benzenedimethanol, toluenedimethanol, and xylenedimethanol, and aliphatic polyols such as ethylene glycol, propylene glycol, 1,3-propylene diol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, and neopentyl glycol. These polyhydric alcohols can be used alone or in combination of two or more.

[0043] In the esterification reaction for producing the polyester polyol, it is preferable to use an esterification catalyst for the purpose of promoting the esterification reaction. Examples of the esterification catalyst include metals such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafnium, germanium, etc.; metal compounds such as titanium tetraisopropoxide, titanium tetrabutoxide, titanium oxyacetylacetonate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, tin octoate, 2-ethylhexyltin, zinc acetylacetonate, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, tetraethoxy germanium, etc. These esterification catalysts can be used alone or in combination of two or more.

[0044] Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, etc. These polyether polyols can be used alone or in combination of two or more.

[0045] Since the number average molecular weight of the other polyol compound can provide an aqueous urethane resin composition having excellent blending stability and capable of forming a coating film excellent in corrosion resistance and chemical resistance, the range of 200 to 10,000 is preferable, and the range of 300 to 5,000 is more preferable.

[0046] The content of the other polyol compound is preferably in the range of 30 to 80% by mass in the polyol compound (a1).

[0047] Since the content of the polyol compound (a1) can provide an aqueous urethane resin composition having excellent blending stability and capable of forming a coating film excellent in corrosion resistance and chemical resistance, the range of 30 to 80% by mass is preferable in the raw materials of the urethane resin (A), and the range of 40 to 70% by mass is more preferable.

[0048] Examples of the polyisocyanate compound (a2) include aromatic polyisocyanate compounds such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, dimethylbiphenyl diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidized diphenylmethane polyisocyanate; aliphatic polyisocyanate compounds such as pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate; and alicyclic diisocyanate compounds such as cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, dicyclohexylmethane diisocyanate, and norbornane diisocyanate. These polyisocyanate compounds can be used alone or in combination of two or more. Among them, alicyclic polyisocyanate compounds and aliphatic polyisocyanate compounds are preferred because an aqueous urethane resin composition capable of forming a coating film excellent in corrosion resistance and chemical resistance can be obtained.

[0049] As the content of the polyisocyanate compound (a2), a range of 20 to 60% by mass is preferable, and a range of 25 to 50% by mass is more preferable in the raw materials of the urethane resin (A) because an aqueous urethane resin composition capable of forming a coating film excellent in corrosion resistance and chemical resistance can be obtained.

[0050] As the nonionic group-containing compound (a3), a compound having one functional group capable of reacting with an isocyanate group is essentially used.

[0051] Examples of the functional group include a hydroxyl group, a primary amino group, and a secondary amino group.

[0052] Examples of the nonionic group-containing compound (a3) include polyoxyethylene or polyoxyethylene-polyoxypropylene copolymers having a number average molecular weight of 300 to 20,000, polyoxyethylene-polyoxybutylene copolymers, monoalkyl ethers of polyoxyethylene-polyoxyalkylene copolymers, and methoxypolyethylene glycol amine. These nonionic group-containing compounds (a3) can be used alone or in combination of two or more. Among these, polyoxyethylene monomethyl ether is preferred because an aqueous urethane resin composition having excellent blending stability and capable of forming a coating film excellent in corrosion resistance, chemical resistance, and weather resistance can be obtained.

[0053] The content of the nonionic group-containing compound (a3) is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 1 to 8% by mass, in the raw materials of the urethane resin (A) because an aqueous urethane resin composition having excellent blending stability and capable of forming a coating film excellent in corrosion resistance and chemical resistance can be obtained.

[0054] As the cationic urethane resin (A), those in which a structural unit represented by the following general formula (2) is introduced into the resin skeleton can also be used.

[0055] [Chemical formula]

[0056] [In formula (2), R 5 represents a monovalent organic residue selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group, and R 6 represents a functional group selected from the group consisting of a halogen atom, an alkoxyl group, an acyloxy group, a phenoxy group, an iminooxy group, or an alkenyloxy group, and n represents an integer of 0, 1, or 2.

[0057] As the compound for introducing the structural unit represented by the general formula (2) into the cationic urethane resin (A), it is preferable to use a compound represented by the following general formula (3).

[0058] [Chemical formula]

[0059] (In formula (3), R 5 represents a monovalent organic residue selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group, R 6 represents a functional group selected from the group consisting of a halogen atom, an alkoxyl group, an acyloxy group, a phenoxy group, an iminooxy group, or an alkenyloxy group, n represents an integer of 0, 1, or 2, and Y represents an organic residue containing at least one amino group.)

[0060] Examples of the compound represented by the general formula (3) include γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-hydroxyethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-hydroxyethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-(2-hydroxyethyl)aminopropylmethyldimethoxysilane, γ-(2-hydroxyethyl)aminopropylmethyldiethoxysilane, or γ-(N,N-di-2-hydroxyethyl)aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, or γ-(N-phenyl)aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptophenyltrimethoxysilane, and the like.

[0061] When producing the cationic urethane resin (A), for the purpose of designing a polyurethane resin having various physical properties such as various mechanical properties and thermal properties, a polyamine may be used as a chain extender.

[0062] Examples of polyamines that can be used as such chain extenders include diamines such as ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; diamines containing one primary amino group and one secondary amino group such as hydroxymethylaminoethylamine, hydroxyethylaminoethylamine, hydroxypropylaminopropylamine, ethylaminoethylamine, methylaminopropylamine;

[0063] polyamines such as diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazines such as hydrazine, N,N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine; dihydrazides such as succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; semicarbazides such as β-semicarbazidopropionic acid hydrazide, 3-semicarbazido-propyl-carbazinate, semicarbazido-3-semicarbazidomethyl-3,5,5-trimethylcyclohexane can be used.

[0064] When producing the cationic urethane resin (A), in addition to the above polyamine, for the purpose of adjusting various physical properties such as various mechanical properties and thermal properties of the polyurethane resin, other chain extenders containing active hydrogen atoms can also be used.

[0065] Examples of the other active hydrogen-containing chain extender that can be used include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, sucrose, methylene glycol, glycerin, and sorbitol; phenols such as bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, and hydroquinone; and water. These may be used alone or in combination within a range that does not reduce the storage stability of the cationic urethane resin aqueous dispersion of the present invention.

[0066] Examples of the aqueous medium (B) include ion-exchanged water and distilled water. These aqueous media can be used alone or in combination of two or more.

[0067] The mass ratio [(A) / (B)] of the cationic urethane resin (A) to the aqueous medium (B) is preferably in the range of 10 / 90 to 80 / 20, more preferably in the range of 20 / 80 to 60 / 40, since an aqueous urethane resin composition capable of forming a coating film having excellent film-forming properties, heat resistance, and heat and humidity resistance can be obtained.

[0068] The method for producing the aqueous urethane resin composition of the present invention is not particularly limited, and any method may be used. For example, the following methods (Method 1, Method 2) can be mentioned.

[0069] In Method 1, a polyol compound (a1), a polyisocyanate compound (a2), a nonionic group-containing compound (a3), and, if necessary, a silane compound and a polyamine are charged all at once or dividedly, and reacted in a solvent or without a solvent to produce a cationic urethane resin (A). After neutralizing part or all of the tertiary amino groups in the urethane resin (A) with an acid and / or quaternizing them with a quaternizing agent, water is added and dispersed to obtain the product.

[0070] As the method 2, a urethane prepolymer having an isocyanate group at the terminal is produced by charging a polyol compound (a1), a polyisocyanate compound (a2), and, if necessary, a silane compound all at once or separately, and reacting them in a solvent or without a solvent. After that, a part or all of the tertiary amino groups in the urethane prepolymer are neutralized with an acid and / or quaternized with a quaternizing agent, and then water is added to disperse it in water. Then, a nonionic group-containing compound (a3) and, if necessary, a polyamine are reacted to obtain the product. Examples of such methods include those obtained by reacting them.

[0071] In such a reaction, the reaction temperature is preferably in the range of 20 to 120 °C, more preferably in the range of 20 to 90 °C.

[0072] As the silane compound, those similar to those exemplified as the "compound represented by the general formula (3)" described above can be used.

[0073] The cationic urethane resin (A) can be produced under solvent-free conditions, but for the purpose of facilitating reaction control, or for the purpose of reducing the stirring load due to a decrease in viscosity and reacting uniformly, it can also be produced under an organic solvent.

[0074] Examples of the organic solvent include ketone compounds such as acetone, diethyl ketone, methyl ethyl ketone, and methyl isobutyl ketone; ether compounds such as diethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, tetrahydrofuran, and dioxane; acetate ester compounds such as ethyl acetate, butyl acetate, and propyl acetate; nitrile compounds such as acetonitrile; hydrocarbon compounds such as n-pentane, n-hexane, cyclohexane, n-heptane, benzene, toluene, and xylene; chlorinated hydrocarbon compounds such as carbon tetrachloride, dichloromethane, chloroform, and trichloroethane; amide compounds such as dimethylformamide and N-methylpyrrolidone. The organic solvent is preferably removed by a method such as heating under reduced pressure during or after the reaction, if necessary.

[0075] The cationic urethane resin (A) can be produced without a catalyst, but known catalysts such as stannous octylate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin phthalate, dibutyltin dimethoxide, dibutyltin diacetylacetate, dibutyltin versatate and other tin compounds, tetrabutyl titanate, tetraisopropyl titanate, triethanolamine titanate and other titanate compounds, and other tertiary amines, quaternary ammonium salts, etc. can also be used.

[0076] The aqueous urethane resin composition of the present invention can also contain other additives as necessary.

[0077] Examples of the other additives include surfactants, emulsifiers, thickeners, fillers, flame retardants, leveling agents, antiblocking agents, etc. These additives can be used alone or in combination of two or more.

[0078] Examples of the surfactant include nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, polyethylene - polypropylene copolymer; fatty acid salts such as sodium oleate, alkyl sulfate esters, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkanesulfonate sodium salts, sodium alkyl diphenyl ether sulfonate and other anionic surfactants; cationic surfactants such as alkylamine salts, alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts, etc.

[0079] Examples of the emulsifier include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, and polyethylene-polypropylene copolymer; fatty acid salts such as sodium oleate, alkyl sulfate esters, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, sodium alkane sulfonates, and sodium alkyl diphenyl ether sulfonates; and cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts. These emulsifiers can be used alone or in combination of two or more.

[0080] Examples of the thickener include associative thickeners and acid thickeners.

[0081] Examples of the filler include calcium carbonate, silica, and the like.

[0082] Examples of the flame retardant include phosphorus-based flame retardants and the like.

[0083] Examples of the leveling agent include silicone leveling agents and the like.

[0084] Examples of the anti-blocking agent include acrylics, cellulose esters, and the like.

[0085] As the coating agent of the present invention, those containing the aqueous urethane resin composition are used.

[0086] Examples of the base material on which the coating agent can be applied to form a coating film include glass base materials, metal base materials, plastic base materials, paper, wood base materials, fibrous base materials, and the like. In addition, base materials having a porous structure such as urethane foam can also be used.

[0087] As the plastic substrate, for example, a polycarbonate substrate, a polyester substrate, an acrylonitrile-butadiene-styrene substrate, a polyacrylic substrate, a polystyrene substrate, a polyurethane substrate, an epoxy resin substrate, a polyvinyl chloride substrate, and a polyamide substrate can be used.

[0088] As the metal substrate, for example, plated steel sheets such as galvanized steel sheets and aluminum-zinc alloy steel sheets, iron plates, aluminum plates, aluminum alloy plates, electromagnetic steel sheets, copper plates, stainless steel sheets, etc. can be used.

[0089] The substrate may be a flat one made of the above materials or may have a curved portion, and may also be a substrate made of fibers such as non-woven fabric.

[0090] The coating agent of the present invention can form a coating film, for example, by directly applying it to the surface of the substrate or to the surface of a substrate provided with a primer layer or the like in advance, and then drying it.

[0091] Also, by applying the coating agent on the release paper, then drying and curing it to form a coating film on the surface of the release paper, and further applying an adhesive or an adhesive on the coating film and laminating it on a substrate made of fibers such as non-woven fabric, and peeling off the release paper, a coating film formed using the coating agent can be laminated on the surface of the desired substrate.

[0092] Examples of the method for applying the coating agent onto the substrate include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, a dipping method, etc.

[0093] The thickness of the coating film that can be formed using the coating agent of the present invention can be appropriately adjusted according to the use of the substrate and the like, but it is usually preferably about 0.1 μm to 100 μm.

[0094] Examples of the article of the present invention include those having a coating film of the coating agent. Specifically, steel sheets for home appliances, steel sheets for building members, glass fibers for reinforced plastics, etc. are included.

Example

[0095] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Note that the present invention is not limited to the Examples listed below.

[0096] (Synthesis Example 1: Synthesis of tertiary amino group-containing polyol (1)) Into a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a dropping device, 590 parts by mass of polypropylene glycol diglycidyl ether (epoxy equivalent 201 g / equivalent) was charged, and then the inside of the flask was purged with nitrogen. Next, after heating using an oil bath until the temperature inside the flask reached 70°C, 380 parts by mass of di-n-butylamine was dropped using a dropping device over 30 minutes. After the dropping was completed, the reaction was carried out at 90°C for 10 hours. After the reaction was completed, using an infrared spectrophotometer (FT / IR-460Plus, manufactured by JASCO Corporation), it was confirmed that the absorption peak near 842 cm -1 attributable to the epoxy group of the reaction product had disappeared, and tertiary amino group-containing polyol (1) (amine equivalent 339 g / equivalent, hydroxyl group equivalent 339 g / equivalent) was prepared.

[0097] (Synthesis Example 2: Synthesis of tertiary amino group-containing polyol (2)) Tertiary amino group-containing polyol (2) (amine equivalent 315 g / equivalent, hydroxyl group equivalent 315 g / equivalent) was prepared in the same manner as in Synthesis Example 1, except that 543 parts by mass of polyethylene glycol diglycidyl ether (epoxy equivalent 185 g / equivalent) was used instead of polypropylene glycol diglycidyl ether (epoxy equivalent 201 g / equivalent).

[0098] (Example 1: Preparation of aqueous urethane resin composition (1)) Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 477 parts by mass of "ETERNACOLL UH-200" [manufactured by UBE Industries, Ltd., a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent] and 230 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 546 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 190 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 70 parts by mass of the tertiary amino group-containing polyol (1) obtained in Synthesis Example 1 and 45 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 2000 g / equivalent) were added, and after reacting for 4 hours, it was cooled to 55 °C, and 32 parts by mass of "KBE-903" [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 11 parts by mass of hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour. Next, 1274 parts by mass of ethyl acetate and 13 parts by mass of acetic acid were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2383 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (1) having a non-volatile content of 35% by mass and a pH of 4.3 was prepared. The pH is a value measured using a pH meter (model M-12, manufactured by Horiba, Ltd.) under an environment of 25 °C. Hereinafter, the pH was measured in the same manner.

[0099] (Example 2: Preparation of aqueous urethane resin composition (2)) Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 515 parts by mass of "ETERNACOLL UH-200" [a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent, manufactured by UBE Industries, Ltd.] and 249 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 546 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 136 parts by mass of tolylene diisocyanate and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 63 parts by mass of the tertiary amino group-containing polyol (2) obtained in Synthesis Example 2 and 46 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 2000 g / equivalent) were added, and after reacting for 4 hours, it was cooled to 55 °C, and 35 parts by mass of "KBE-903" [γ-aminopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 12 parts by mass of hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour. Next, 1274 parts by mass of ethyl acetate and 13 parts by mass of acetic acid were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2381 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (2) having a non-volatile content of 35% by mass and a pH of 4.1 was prepared.

[0100] (Example 3: Preparation of aqueous urethane resin composition (3)) Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 448 parts by mass of "ETERNACOLL UH-200" [manufactured by UBE Industries, Ltd., a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent] and 216 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 549 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 179 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 116 parts by mass of the tertiary amino group-containing polyol (1) obtained in Synthesis Example 1 and 59 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 4000 g / equivalent) were added, and after reacting for 4 hours, it was cooled to 55 °C, and 30 parts by mass of "KBE-903" [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 6 parts by mass of hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour. Next, 1282 parts by mass of ethyl acetate and 22 parts by mass of acetic acid were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2373 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (3) having a nonvolatile content of 35% by mass and a pH of 4.3 was prepared.

[0101] (Example 4: Preparation of aqueous urethane resin composition (4)) Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 488 parts by mass of "ETERNACOLL UH-200" [manufactured by UBE Industries, Ltd., a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent], and 236 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 544 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 195 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 54 parts by mass of the tertiary amino group-containing polyol (1) obtained in Synthesis Example 1 and 38 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 550 g / equivalent) were added, and after reacting for 4 hours, it was cooled to 55 °C, and 33 parts by mass of "KBE-903" [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 11 parts by mass of hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour. Next, 1269 parts by mass of ethyl acetate and 10 parts by mass of acetic acid were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2384 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (4) having a non-volatile content of 35% by mass and a pH of 4.2 was prepared.

[0102] (Example 5: Preparation of aqueous urethane resin composition (5)) Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 458 parts by mass of "ETERNACOLL UH-200" [manufactured by UBE Industries, Ltd., a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent], and 221 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 543 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 183 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 36 parts by mass of the tertiary amino group-containing polyol (1) obtained in Synthesis Example 1 and 116 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 2000 g / equivalent) were added, and after reacting for 4 hours, it was cooled to 55 °C, and 31 parts by mass of "KBE-903" [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 12 parts by mass of hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour. Next, 1267 parts by mass of ethyl acetate and 7 parts by mass of acetic acid were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2392 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin aqueous dispersion (5) having a non-volatile content of 35% by mass and a pH of 4.0 was prepared.

[0103] (Example 6: Preparation of aqueous urethane resin composition (6)) In a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 475 parts by mass of "ETERNACOLL UH-200" [manufactured by UBE Industries, Ltd., a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent] and 229 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, the mixture was cooled to 70 °C, 545 parts by mass of ethyl acetate was added, and the mixture was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 189 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 58 parts by mass of the tertiary amino group-containing polyol (1) obtained in Synthesis Example 1 was added, and after reacting for 4 hours, the mixture was cooled to 55 °C, and 32 parts by mass of "KBE-903" [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 1273 parts by mass of ethyl acetate and 11 parts by mass of acetic acid were added, and the mixture was held at 55 °C for 1 hour, then cooled to 40 °C, and 2387 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. After aqueous dispersion, methoxypolyethylene glycol amine (amine value 2000 g / equivalent) and 11 parts by mass of hydrazine hydrate were added, and the reaction was carried out at 55 °C for 1 hour. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (6) having a nonvolatile content of 35% by mass and a pH of 4.0 was prepared.

[0104] (Example 7: Preparation of aqueous urethane resin composition (7)) In a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 370 parts by mass of "ETERNACOLL UH-100" [manufactured by UBE Industries, Ltd., a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 493 g / equivalent] and 179 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 555 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 246 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 185 parts by mass of the tertiary amino group-containing polyol (1) obtained in Synthesis Example 1 and 27 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 2000 g / equivalent) were added, and after reacting for 4 hours, it was cooled to 55 °C, and 41 parts by mass of "KBE-903" [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 6 parts by mass of hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour. Next, 1296 parts by mass of ethyl acetate and 34 parts by mass of acetic acid were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2349 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (7) having a non-volatile content of 35% by mass and a pH of 4.1 was prepared.

[0105] (Example 8: Preparation of aqueous urethane resin composition (8)) In a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 490 parts by mass of "ETERNACOLL UH-200" [manufactured by UBE Industries, Ltd., a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent], and 236 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 541 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 195 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 8 parts by mass of the tertiary amino group-containing polyol (1) obtained in Synthesis Example 1 and 79 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 2000 g / equivalent) were added, and after reacting for 4 hours, it was cooled to 55 °C, and 33 parts by mass of "KBE-903" [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 16 parts by mass of hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour. Next, 1263 parts by mass of ethyl acetate and 1 part by mass of acetic acid were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2396 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (8) having a nonvolatile content of 35% by mass and a pH of 4.1 was prepared.

[0106] (Example 9: Preparation of aqueous urethane resin composition (9)) Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 507 parts by mass of "ETERNACOLL UH-200" [manufactured by UBE Industries, Ltd., a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent], and 245 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 545 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 129 parts by mass of isophorone diisocyanate, 32 parts by mass of hexamethylene diisocyanate, and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 57 parts by mass of the tertiary amino group-containing polyol (1) obtained in Synthesis Example 1 and 39 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 1000 g / equivalent) were added, and after reacting for 4 hours, it was cooled to 55 °C, and 34 parts by mass of "KBE-903" [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 13 parts by mass of hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour. Next, 1271 parts by mass of ethyl acetate and 11 parts by mass of acetic acid were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2382 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin aqueous dispersion (9) having a non-volatile content of 35% by mass and a pH of 4.2 was prepared.

[0107] (Example 10: Preparation of aqueous urethane resin composition (10)) Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 709 parts by mass of "PTMG-2000" [manufactured by Mitsubishi Chemical Corporation, polytetramethylene glycol, hydroxyl equivalent 1000 g / equivalent] was added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 539 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 186 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 57 parts by mass of the tertiary amino group-containing polyol (1) obtained in Synthesis Example 1 and 40 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 2000 g / equivalent) were added, and after reacting for 4 hours, it was cooled to 55 °C, and 31 parts by mass of "KBE-903" [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 12 parts by mass of hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour. Next, 1257 parts by mass of ethyl acetate and 21 parts by mass of dimethyl sulfate were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2401 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (10) having a nonvolatile content of 35% by mass and a pH of 5.9 was prepared.

[0108] (Example 11: Preparation of aqueous urethane resin composition (11)) In a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 672 parts by mass of "ETERNACOLL UH-200" [a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent, manufactured by UBE Industries, Ltd.] was added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 539 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 178 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 55 parts by mass of the tertiary amino group-containing polyol (1) obtained in Synthesis Example 1 and 92 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 2000 g / equivalent) were added, and after reacting for 4 hours, it was cooled to 55 °C, and 30 parts by mass of "KBE-903" [γ-aminopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 10 parts by mass of hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour. Next, 1257 parts by mass of ethyl acetate and 18 parts by mass of an 89 mass% aqueous orthophosphoric acid solution were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2403 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (11) having a non-volatile content of 35 mass% and a pH of 3.1 was prepared.

[0109] (Example 12: Preparation of aqueous urethane resin composition (12)) Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 707 parts by mass of "DURANOL T-4692" [a polycarbonate polyol obtained by reacting 1,6-hexanediol, 1,4-butanediol, and ethylene carbonate, hydroxyl equivalent 1000 / equivalent, manufactured by Asahi Kasei Corporation] was added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 537 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 185 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 78 parts by mass of the tertiary amino group-containing polyol (1) obtained in Synthesis Example 1 and 8 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 2000 g / equivalent) were added, and after reacting for 4 hours, it was cooled to 55 °C, and 31 parts by mass of "KBE-903" [γ-aminopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 16 parts by mass of aminoethyl ethanolamine was added to the urethane prepolymer solution, and the chain extension reaction was carried out for 1 hour. Next, 1253 parts by mass of ethyl acetate and 25 parts by mass of an 89% by mass aqueous orthophosphoric acid solution were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2415 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin aqueous dispersion (12) having a non-volatile content of 35% by mass and a pH of 3.2 was prepared.

[0110] (Example 13: Preparation of aqueous urethane resin composition (13)) Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 461 parts by mass of "ETERNACOLL UH-200" [manufactured by UBE Industries, Ltd., a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent], and 223 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 210 parts by mass of methyl ethyl ketone was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 184 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 63 parts by mass of the tertiary amino group-containing polyol (1) obtained in Synthesis Example 1, 37 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 1000 g / equivalent), and 473 parts by mass of methyl ethyl ketone were added, and after reacting for 4 hours, it was cooled to 55 °C, and 31 parts by mass of "KBE-903" [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 28 parts by mass of isophoronediamine was added to the urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour. Next, 368 parts by mass of methyl ethyl ketone, 525 parts by mass of isopropanol, and 23 parts by mass of dimethyl sulfate were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2624 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (13) having a non-volatile content of 35% by mass and a pH of 5.8 was prepared.

[0111] (Example 14: Preparation of aqueous urethane resin composition (14)) Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 494 parts by mass of "ETERNACOLL UH-200" [manufactured by UBE Industries, Ltd., a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent] and 238 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 547 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 197 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 66 parts by mass of the tertiary amino group-containing polyol (1) obtained in Synthesis Example 1 and 47 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 2000 g / equivalent) were added, and after reacting for 4 hours, it was cooled to 55 °C to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 16 parts by mass of hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour. Next, 1275 parts by mass of ethyl acetate and 12 parts by mass of acetic acid were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2377 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (14) having a non-volatile content of 35% by mass and a pH of 4.2 was prepared.

[0112] (Example 15: Preparation of aqueous urethane resin composition (15)) In a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 364 parts by mass of "ETERNACOLL UH-200" [manufactured by UBE Industries, Ltd., a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent] and 176 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 155 parts by mass of polypropylene glycol (hydroxyl equivalent 500 g / equivalent) and 541 parts by mass of ethyl acetate were added, and the mixture was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 227 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After the reaction was completed, 54 parts by mass of the tertiary amino group-containing polyol (1) obtained in Synthesis Example 1, 49 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 2000 g / equivalent), and 541 parts by mass of ethyl acetate were added, and the reaction was carried out for 4 hours. Then, it was cooled to 55 °C, and 24 parts by mass of "KBE-903" [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane] was added and reacted for 1 hour. After the reaction was completed, using an infrared spectrophotometer (FT / IR-460Plus, manufactured by JASCO Corporation), it was confirmed that the absorption peak near 2280 cm -1 due to the isocyanate group of the reaction product had disappeared. Next, 1263 parts by mass of ethyl acetate and 10 parts by mass of acetic acid were added, and the mixture was held at 55 °C for 1 hour. Then, it was cooled to 40 °C, and 2394 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (15) having a non-volatile content of 35% by mass and a pH of 4.1 was prepared.

[0113] (Example 16: Preparation of aqueous urethane resin composition (16)) Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 403 parts by mass of "ETERNACOLL UH-200" [manufactured by UBE Industries, Ltd., a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent] and 195 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 172 parts by mass of polypropylene glycol (hydroxyl equivalent 500 g / equivalent) and 541 parts by mass of ethyl acetate were added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 167 parts by mass of tolylene diisocyanate and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 49 parts by mass of the tertiary amino group-containing polyol (2) obtained in Synthesis Example 2, 36 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 2000 g / equivalent), and 541 parts by mass of ethyl acetate were added, and after reacting for 4 hours, it was cooled to 55 °C, and 27 parts by mass of "KBE-903" [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane] was added and reacted for 1 hour. After completion of the reaction, using an infrared spectrophotometer (FT / IR-460Plus, manufactured by JASCO Corporation), it was confirmed that the absorption peak near 2280 cm -1 due to the isocyanate group of the reaction product had disappeared. Next, 1262 parts by mass of ethyl acetate and 10 parts by mass of acetic acid were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2392 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (16) having a non-volatile content of 35% by mass and a pH of 4.3 was prepared.

[0114] (Comparative Example 1: Preparation of Aqueous Urethane Resin Composition (R1)) Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 509 parts by mass of "ETERNACOLL UH-200" [manufactured by UBE Industries, Ltd., a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent] and 245 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 548 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 203 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 15 parts by mass of N-methyl-diethanolamine and 39 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 2000 g / equivalent) were added, and after reacting for 4 hours, it was cooled to 55 °C, and 34 parts by mass of "KBE-903" [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 10 parts by mass of hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour. Next, 1278 parts by volume of ethyl acetate and 16 parts by mass of acetic acid were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2378 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (R1) having a non-volatile content of 35% by mass and a pH of 4.2 was prepared.

[0115] (Comparative Example 2: Preparation of Aqueous Urethane Resin Composition (R2)) Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 526 parts by mass of "ETERNACOLL UH-200" [manufactured by UBE Industries, Ltd., a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent], and 254 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 540 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 139 parts by mass of tolylene diisocyanate and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 13 parts by mass of N-methyl-diethanolamine and 49 parts by mass of polyoxyethylene monomethyl ether (hydroxyl equivalent 4000 g / equivalent) were added, and after reacting for 4 hours, it was cooled to 55 °C, and 35 parts by mass of "KBE-903" [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 13 parts by mass of hydrazine hydrate was added to the urethane prepolymer solution, and the chain extension reaction was carried out for 1 hour. Next, 1259 parts by volume of ethyl acetate and 27 parts by mass of dimethyl sulfate were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2403 parts by volume of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (R2) having a non-volatile content of 35% by mass and a pH of 6.5 was prepared.

[0116] (Comparative Example 3: Preparation of Aqueous Urethane Resin Composition (R3)) Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 463 parts by mass of "ETERNACOLL UH-200" [manufactured by UBE Industries, Ltd., a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent] and 223 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 546 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 184 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 84 parts by mass of the tertiary amino group-containing polyol (1) obtained in Synthesis Example 1 and 63 parts by mass of "Ymer N120" (manufactured by Perstorp, a diol containing a polyoxyethylene group, hydroxyl value 500 g / equivalent) were added, and after reacting for 4 hours, it was cooled to 55 °C, and 31 parts by mass of "KBE-903" [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 6 parts by mass of hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour. Next, 1274 parts by mass of ethyl acetate and 16 parts by mass of acetic acid were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2383 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (R3) having a non-volatile content of 35% by mass and a pH of 4.3 was prepared.

[0117] (Comparative Example 4: Preparation of Aqueous Urethane Resin Composition (R4)) Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 488 parts by mass of "ETERNACOLL UH-200" [manufactured by UBE Industries, Ltd., a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent] and 236 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 547 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 195 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 93 parts by mass of the tertiary amino group-containing polyol (1) obtained in Synthesis Example 1 was added, and after reacting for 4 hours, it was cooled to 55 °C, and 33 parts by mass of "KBE-903" [manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltriethoxysilane] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 10 parts by mass of hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour. Next, 1275 parts by volume of ethyl acetate and 17 parts by mass of acetic acid were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 2371 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, an aqueous polyurethane resin dispersion (R4) having a non-volatile content of 35% by mass and a pH of 4.3 was prepared.

[0118] Using the aqueous urethane resin compositions (1) to (16) and (R1) to (R4) obtained in the above Examples and Comparative Examples, the following evaluations were carried out.

[0119] [Evaluation method for water resistance] A polypropylene film having an outer frame with a height of 1 mm was attached to a glass plate of A4 size, and an aqueous urethane resin composition was applied at 6 g / 100 cm on the polypropylene film. 2It was poured in so as to obtain a film having a thickness of about 200 μm by drying at 25°C for 1 day. Subsequently, the film was peeled off from the polypropylene film, and a test piece cut into 3.0 cm in length and 3.0 cm in width was used as a test piece.

[0120] Next, the test piece was immersed in warm water at 40°C for 24 hours, and then its dimensions were measured. Using the dimensions of the test piece before and after immersion, the area swelling rate of the test piece was calculated according to the following formula (1). Also, after the test piece after immersion was dried at 108°C for 1 hour, the mass of the test piece was measured. Using the masses of the test piece before and after immersion, the elution rate of the test piece was calculated according to the following formula (2).

[0121] Formula (1) Area swelling rate (%) = (L1 × L2 / 9.0 cm 2 ) × 100 - 100 L1: Longitudinal length of the test piece after immersion (cm) L2: Lateral length of the test piece after immersion (cm)

[0122] Formula (2) Elution rate (mass %) = [(W4 - W5) / W4] × 100 W4: Mass of the test piece before immersion (g) W5: Mass of the test piece after immersion and dried at 107°C for 1 hour (g)

[0123] [Evaluation method for blending stability] The obtained aqueous urethane resin composition was diluted with ion-exchanged water so that the nonvolatile content was 5% by mass. To 100 parts by mass of the nonvolatile content of the cationic urethane resin, 80 parts by mass of KBE-903, 40 parts by mass of KBM-403, 3 parts by mass of vanadium(III) acetylacetonate as titanium diisopropoxide bis(acetylacetonate), 200 parts by mass of 10% by mass orthophosphoric acid aqueous solution, and 250 parts by mass of 10% by mass acetic acid aqueous solution were added and uniformly mixed to obtain a metal coating agent. The presence or absence of precipitation and aggregates immediately after production, and the presence or absence of precipitation and aggregates after standing for 3 months (100 ml of the metal coating agent was put into a 140 ml glass sample bottle, sealed, and left in an environment at 40 °C for 3 months) were evaluated according to the following evaluation criteria.

[0124] A: There was no precipitation or aggregation. B: Partially aggregated and gelled. C: Entirely gelled.

[0125] [Preparation of test plates for evaluation of corrosion resistance and alkali resistance] As the metal substrates, two types shown below were used. Metal substrate (1): A hot-dip galvanized steel sheet containing 45% by mass of zinc and 55% by mass of aluminum (abbreviated as "GL"), 1.70 mm × 150 mm × 0.8 mm, manufactured by Nippon Test Panel Co., Ltd. Metal substrate (2): An electro-galvanized steel sheet (abbreviated as "EG"), 1.70 mm × 150 mm × 0.8 mm, manufactured by Nippon Test Panel Co., Ltd.

[0126] The metal substrates (1) and (2) were immersed in an alkaline degreasing agent at 55 °C for 5 minutes for degreasing, and then the surfaces of the metal substrates were washed with water. Thereafter, the surfaces were washed with ion-exchanged water and dried at 107 °C for 15 minutes.

[0127] On one side of each of the metal substrates (1) and (2), the metal coating agent was applied to a film thickness of 5 μm (0.05 g / 100 cm 2) It was applied using a bar coater so as to be , and test plates (1) and (2) were produced by baking at 180 °C for 20 seconds.

[0128] [Evaluation method for corrosion resistance] On the film made of the metal coating agent formed on the surface of each test plate, according to the salt spray test method described in JIS Z2371, an aqueous 5% NaCl solution was sprayed onto the test plate at an ambient temperature of 35 °C, and the white rust generation rate after 240 hours was measured and evaluated according to the following evaluation criteria. In addition, the uncoated parts of the metal coating agent (end face part, back face part) were tape-sealed.

[0129] A: No white rust occurred. B: The white rust generation rate was less than 5%. C: The white rust generation rate was 5% or more and less than 20%. D: The white rust generation rate was 20% or more.

[0130] [Evaluation method for alkali resistance] 0.5 ml of a 10% by mass sodium hydroxide aqueous solution was dropped onto the film made of the metal coating agent formed on the surface of each test plate and left for 1 hour. After leaving, the appearance of the film at the part where the acetic acid adhered was evaluated according to the following evaluation criteria.

[0131] A: There was no change in the dropped part. B: The film changed to black or the area where it dissolved was less than 10% of the area of the original film. C: The film changed to black or the area where it dissolved was 10% or more and less than 30% of the area of the original film. D: The film changed to black or the area where it dissolved was 30% or more of the area of the original film.

[0132] The evaluation results of the aqueous urethane resin compositions (1) to (16) and (R1) to (R4) obtained in the above examples and comparative examples are shown in Table 1.

[0133]

Table 1

[0134]

Table 2

[0135]

Table 3

[0136] From the evaluation results of the above Tables 1 and 2, it was confirmed that the aqueous urethane resin composition of the present invention can form a coating film having excellent blending stability, corrosion resistance, and chemical resistance (alkali resistance).

[0137] On the other hand, Comparative Examples 1 and 2 shown in Table 3 are examples of aqueous urethane resin compositions containing a cationic urethane resin having no structural unit represented by the general formula (1), but the blending stability is insufficient, and the corrosion resistance and alkali resistance of the obtained coating film were also extremely insufficient.

[0138] Comparative Example 3 is an example of an aqueous urethane resin composition containing a cationic urethane resin using a nonionic group-containing compound having two or more functional groups capable of reacting with an isocyanate group, but the blending stability when left standing at 40 °C for 3 months is insufficient, and the corrosion resistance and alkali resistance of the obtained coating film were also extremely insufficient.

[0139] Comparative Example 4 is an example of an aqueous urethane resin composition containing a cationic urethane resin having no nonionic group-containing compound (a3), but the corrosion resistance and alkali resistance of the obtained coating film were extremely insufficient.

Claims

1. An aqueous urethane resin composition containing a cationic urethane resin (A) and an aqueous medium (B), wherein the cationic urethane resin (A) has a structural unit represented by the following general formula (1) in one molecule, the cationic urethane resin (A) uses a polyol compound (a1), a polyisocyanate compound (a2), and a nonionic group-containing compound (a3) as essential raw materials, the polyol compound (a1) contains a tertiary amino group-containing polyol compound, and the nonionic group-containing compound (a3) is a compound having one functional group capable of reacting with an isocyanate group, which is characterized by the aqueous urethane resin composition.

2. 【Chemical 1】 [In formula (1), R １ represents an alkylene group which may contain an aliphatic cyclic structure, a residue of a divalent phenol compound, or a polyoxyalkylene group, R ２ and R ３ each independently represent an alkyl group which may contain an aliphatic cyclic structure, R ４ each independently represent a hydrogen atom or a residue of a quaternizing agent introduced by a quaternization reaction, and X － represents an anionic counter ion.] The aqueous urethane resin composition according to claim 1, wherein the polyisocyanate compound (a2) is an alicyclic polyisocyanate compound and / or an aliphatic polyisocyanate compound.

3. The aqueous urethane resin composition according to claim 1, wherein the content of the nonionic group-containing compound (a3) is in the range of 0.1 to 10% by mass in the essential raw materials.

4. The aqueous urethane resin composition according to claim 1, wherein the content of the cationic amino group contained in the structural unit represented by the general formula (1) is in the range of 0.03 to 0.5 equivalents / kg in the cationic urethane resin (A).

5. The aqueous urethane resin composition according to claim 1, wherein the cationic urethane resin (A) has a structural unit derived from a polyol that is an esterification reaction product of a carbonic acid ester and an aliphatic diol.

6. The aqueous urethane resin composition according to claim 1, wherein the cationic urethane resin (A) further has a structural unit represented by the following general formula (2).

7. 【Chemical 2】 [In formula (2), R ５ represents a monovalent organic residue selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group, and R ６ represents a functional group selected from the group consisting of a halogen atom, an alkoxyl group, an acyloxy group, a phenoxy group, an iminooxy group, or an alkenyloxy group, and n represents an integer of 0, 1, or 2.] The aqueous urethane resin composition according to claim 1, wherein the cationic urethane resin (A) further has a structural unit obtained by reacting a compound represented by the following general formula (3) with an isocyanate group of the polyisocyanate compound (a2).

8. [Chemical 3] [In formula (3), R ５ represents a monovalent organic residue selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group, and R ６ represents a functional group selected from the group consisting of a halogen atom, an alkoxyl group, an acyloxy group, a phenoxy group, an iminooxy group, or an alkenyloxy group, n represents an integer of 0, 1, or 2, and Y represents an organic residue containing at least one or more amino groups.] A coating agent characterized by containing the aqueous urethane resin composition according to any one of claims 1 to 7.

9. An article characterized by having a coating film of the coating agent according to claim 8. ​

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