JP2006182976A - Cross-linking method, aqueous resin composition and its production method, coating composition and paint composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous resin composition which has excellent storage stability, can be cross-linked at room temperature, after coated, can form cured coating films having excellent corrosion resistance, water resistance, solvent resistance and the like on substrates, and can additionally impart sufficient coating film hardness, even just after coated. <P>SOLUTION: This cross-linking method is characterized by evaporating an evaporable base (B) from an aqueous resin composition comprising the evaporable base (B) neutralization salt of a vinyl-modified epoxy ester (A) having an anionic functional group and a compound (C) having two or more vinyl ether groups, thereby reacting and cross-linking the vinyl ether groups with anionic groups. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a crosslinking method, an aqueous resin composition and a production method thereof, and a coating agent composition and a coating composition containing the aqueous resin composition.

Conventionally, coating films obtained with water-based paints have been considered to have poor corrosion resistance, but vinyl modified epoxy esters obtained by polymerizing vinyl monomers in the presence of fatty acid modified epoxy esters as an improvement of such corrosion resistance. Was developed. Since the vinyl-modified epoxy ester uses an epoxy resin, it has high corrosion resistance, can be dried at room temperature with a fatty acid ester, and the resulting resin can be made water-based by selecting a vinyl monomer. .

  However, as the field of application of water-based paints expands, the performance required for coating films becomes more severe, and high water resistance is required in addition to corrosion resistance. In particular, with respect to the problem of water whitening in a black coating film (whitening of the coating film in the presence of water), conventionally known vinyl-modified epoxy esters cannot be satisfied at all. Such water whitening can be improved by increasing the ratio of the fatty acid of the vinyl-modified epoxy ester, but there is a problem that the coating film hardness and corrosion resistance are lowered.

  The present applicant has previously proposed a vinyl-modified epoxy ester obtained by blending oils and fats when the vinyl monomer is polymerized in the presence of a fatty acid-modified epoxy ester and reacting them. (See Patent Document 1)

  Although the resin was excellent in coating film hardness and corrosion resistance, it could not be said that the coating film hardness (coating film initial hardness) immediately after coating was sufficient, and further improvement was required.

Japanese Patent Laid-Open No. 11-269249

  The present invention is excellent in storage stability, can be crosslinked at room temperature after coating, and can form a cured coating film excellent in corrosion resistance, water resistance, solvent resistance, etc. to the base material. It aims at providing the water-based resin composition which can provide sufficient coating-film hardness.

The present inventor has studied to solve the above-mentioned problems. As a result, a vinyl-modified epoxy ester having an anionic functional group neutralized with a specific base and a compound having a vinyl ether group (—O—CH═CH ₂ ) are obtained. It has been found that the above problems can be solved by using it.

  That is, the present invention provides an aqueous resin composition containing a volatile base (B) neutralized product of a vinyl-modified epoxy ester (A) having an anionic functional group and a compound (C) having two or more vinyl ether groups. A crosslinking method characterized in that a vinyl ether group and an anionic group react and crosslink by volatilization of a volatile base (B); a vinyl-modified epoxy ester (A) having an anionic functional group and an anionic functional group; By volatilizing the volatile base (B) from the aqueous resin composition containing the neutralized volatile base (B) of the compound (D) having a vinyl ether group and the compound (C) having two or more vinyl ether groups. Crosslinking method characterized in that vinyl ether group and anionic group react to crosslink; Vinyl-modified epoxy ester having anionic functional group When the volatile base (B) is volatilized from the aqueous resin composition containing the neutralized product of A) and the compound (D) having an anionic functional group and a vinyl ether group, the vinyl ether group and A crosslinking method characterized by reacting an anionic group to crosslink; a volatile base (B) neutralized product of a vinyl-modified epoxy ester (A) having an anionic functional group and a compound having two or more vinyl ether groups (C A vinyl-modified epoxy ester (A) having an anionic functional group, a volatile base (B) neutralized product of a compound (D) having an anionic functional group and a vinyl ether group, and a vinyl ether group. Aqueous resin composition containing compound (C) having two or more; vinyl-modified epoxy ester (A) having an anionic functional group and anionic An aqueous resin composition containing a volatile base (B) neutralized product of a compound (D) having a functional group and a vinyl ether group; a vinyl-modified epoxy ester (A) having an anionic functional group by a volatile base (B) A method for producing the aqueous resin composition comprising adding a compound (C) having two or more vinyl ether groups after neutralization; a vinyl-modified epoxy ester (A) having an anionic functional group and an anionic function The compound (D) having a group and a vinyl ether group is neutralized with a volatile base (B), and then the compound (C) having two or more vinyl ether groups is added. A volatile mixture containing a vinyl-modified epoxy ester (A) having an anionic functional group and a compound (C) having two or more vinyl ether groups The method for producing an aqueous resin composition according to any one of claims 7 to 12, wherein the aqueous resin composition is neutralized with a base (B); a coating agent composition containing the aqueous resin composition; It is related with the coating composition containing this.

  According to the present invention, it is excellent in storage stability, can be cross-linked at room temperature after coating, and can form a cured coating film excellent in corrosion resistance, solvent resistance, etc. to the base material. It is possible to provide an aqueous resin composition capable of imparting a satisfactory coating film hardness. The aqueous resin composition does not cross-link while the volatile base (B) is present. For example, when the volatile base (B) volatilizes after being applied to the substrate, the cross-linking occurs rapidly, and the film is formed. In order to form, it is suitable for various uses, such as a coating material, a coating agent, a binder for printing ink, an adhesive agent, a size agent, and a resin emulsion.

  The vinyl-modified epoxy ester (A) (hereinafter referred to as “component (A)”) having an anionic functional group used in the present invention is converted into a fatty acid-modified epoxy ester (a) (hereinafter referred to as “component (a)”). It is obtained by blending a vinyl monomer (b) (hereinafter referred to as component (b)) and, if necessary, an oil (c) (hereinafter referred to as component (c)) and reacting them. The component (a) used in the present invention is a monovalent fatty acid (a-1) (hereinafter referred to as component (a-1)) and an epoxy resin (a-2) (hereinafter referred to as component (a-2)). .) Is added and condensed, and the compound other than the component (a-1) and the component (a-2) which can react with the above (a-1) or (a-2) as necessary. (A-3) (hereinafter referred to as component (a-3)) is further reacted.

  As a component (a-1), if it is a monovalent fatty acid, it will not specifically limit, A well-known thing can be used. Specifically, fatty acids derived from various known drying oils, semi-drying oils or non-drying oils or synthetic fatty acids can be used, but fatty acids that can be derived from drying oils or semi-drying oils in that they can impart room temperature curability. Is preferably used. Representative examples include fatty acids that can be derived from drying oils such as soybean oil, linseed oil, dehydrated castor oil, safflower oil, and tung oil, or semi-drying oils. A component (a-1) may be used individually by 1 type, or may use 2 or more types together.

  The component (a-2) is not particularly limited as long as it is an epoxy resin, and known components can be used. A typical example is a bisphenol type epoxy resin. Specifically, the bisphenol type epoxy resin is an epoxy resin obtained by reaction of bisphenols such as bisphenol A and bisphenol F with epichlorohydrin and the like, for example, Epototo YD-011, Epototo YD-012, Epototo YD-014, Epototo Commercially available products such as YD-017, Epototo YDF-2001, Epototo YDF-2004 (all manufactured by Toto Kasei Co., Ltd.) and the like can be used. Examples of the component (a-2) include glycidyl ethers of aliphatic polyhydric alcohols and glycidyl ethers of aliphatic polybasic acids. A component (a-2) may be used individually by 1 type, or may use 2 or more types together.

  As the component (a-3), a known compound capable of reacting with the component (a-1) and the component (a-2) other than the component (a-1) and the component (a-2) can be used. For example, polybasic acids, polybasic acid anhydrides, monovalent to tetravalent alcohols, isocyanate compounds, and the like can be used. By making it react with a component (a-3), the dispersibility to the water of the obtained resin aqueous material can be adjusted, or the workability of the coating film obtained can be improved further. Examples of the component (a-3) include divalent to trivalent organic acids, monovalent to tetravalent alcohols, and isocyanate compounds. As the divalent to trivalent organic acid, various known polybasic carboxylic acids such as aliphatic, alicyclic or aromatic can be used, and examples thereof include dimer acid and trimellitic acid. As the monovalent to tetravalent alcohol, various known alcohols such as aliphatic, alicyclic or aromatic can be used, and examples thereof include neopentyl glycol, trimethylolpropane and pentaerythritol. As the isocyanate compound, various known aromatic, aliphatic or alicyclic polyisocyanates can be used, such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate and the like. It is done.

Since the use ratio of the component (a-1) and the component (a-2) is excellent in coating film hardness, corrosion resistance and the like, the component (a-1) is usually about 20 to 60% by weight and the component (a -2) It is preferable to set it as 40 to 80 weight%. More preferably, the usage-amount of a component (a-1) is 30 to 45 weight%, and the usage-amount of a component (a-2) is 55 to 70 weight%. Moreover, the component (a-3) used arbitrarily is in the range in which the component (a-1) and the component (a-2) are in the above ratio, and the range is 10% by weight or less of the component (a). Can be used in

  For the addition / condensation reaction of the component (a-1), the component (a-2), and the component (a-3) used as necessary, various known means can be employed. For example, you may mix and react a component (a-1)-a component (a-3) simultaneously, and after making a component (a-1) and a component (a-2) react, as needed You may make a component (a-3) etc. react. The reaction temperature is usually about 130 to 250 ° C., and a known organic solvent such as xylene may be used in the reaction. The reaction is usually terminated when the acid value is 5 or less, preferably 1 or less.

  The component (b) is not particularly limited as long as it is a vinyl monomer other than the component (a), and known ones can be used, but in order to introduce an anionic functional group into the component (A), It is necessary to contain a vinyl monomer having an anionic functional group. Examples of vinyl monomers having an anionic functional group include carboxyl group-containing vinyl monomers such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. Examples of monomers other than vinyl monomers having an anionic functional group include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, and acrylic acid. Acrylic esters such as 2-ethylhexyl; methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate Styrene-based vinyl monomers such as styrene, vinyltoluene, α-methylstyrene; others, vinyl acetate, β-hydroxyethyl acrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, N, N-diethylmethacrylamide, Acrylo Examples include nitrile and methacrylonitrile. These components (b) may be used individually by 1 type, or may use 2 or more types together.

  The carboxyl group-containing vinyl monomer not only serves as a crosslinking point that reacts with the vinyl ether group, but can impart good dispersibility to the resulting component (A), so that the acid value of the component (A) is 20 or more. Furthermore, it is preferable to use it after adjusting it to be in the range of 25 or more. On the other hand, in order to impart good water resistance and corrosion resistance to the component (A), the acid value of the component (A) is preferably adjusted to 45 or less, more preferably 40 or less.

  As the component (c), various known fats and oils that do not correspond to the component (b) can be used, but fats and oils having an unsaturated bond that can participate in polymerization together with the component (b) are preferable in the reaction. Such fats and oils include soybean oil, linseed oil, castor oil, dehydrated castor oil, safflower oil, tung oil and the like. Among these fats and oils, fats and oils having a conjugated double bond such as dehydrated castor oil are particularly preferable.

  The amount of component (b) and component (c) used is such that the ratio (weight ratio) of component (b) and component (c) to component (a) is usually (a): {(b) + (c) } = 90: 10 to 70:30. In addition, since a component (c) is an arbitrary component, it is not necessarily used, but it is preferable to make a component (c) into about 2 to 10 weight% in the component (A) obtained. When the use ratio of component (b) and component (c) and the use amount of component (c) are smaller than the above ranges, it is difficult to sufficiently improve the water resistance, and when it is increased, the coating film hardness is lowered and the corrosion resistance is lowered. Tend.

  The component (A) of the present invention is obtained by mixing the component (a) with the component (b) and the component (c) and reacting them. In the reaction, the component (b) and the component (c) are polymerized in the presence of a radical polymerization initiator, and the component (a) is modified with the polymer of the component (b) and the component (c).

  The radical polymerization initiator is not particularly limited, and representative examples thereof include azobisnitrile catalysts such as azobisisobutyronitrile and azobisvaleronitrile, benzoyl peroxide, t-butyl perbenzoate, and the like. Such as peroxides.

  The reaction is usually carried out in an organic solvent at a temperature of about 80 to 150 ° C. The organic solvents are not particularly limited, but hydrophilic solvents are preferably used from the viewpoint of making the resin aqueous. Specifically, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Examples thereof include mono n-butyl ether, propylene glycol mono t-butyl ether, methyl cellosolve, ethyl cellosolve, n-butyl cellosolve, t-butyl cellosolve, isopropyl alcohol, and butyl alcohol.

  The weight average molecular weight of the component (A) thus obtained is preferably 8,000 to 100,000, more preferably 30,000 to 80,000 from the viewpoints of dispersibility, corrosion resistance, and coating workability. . When the weight average molecular weight is less than 8,000 or exceeds 100,000, the dispersibility, rust prevention property, and coating workability tend to be inferior. The obtained component (A) is dissolved or dispersed in water to obtain an aqueous solution or aqueous dispersion. In addition, you may remove the solvent used in the case of reaction from the obtained component (A) by pressure reduction etc. as needed.

  The volatile base (B) (hereinafter referred to as component (B)) used in the present invention is not particularly limited as long as it is a volatile base, and known ones can be used. Specific examples include ammonia, primary amines, secondary amines, tertiary amines, and the like. Examples of primary amines include methylamine, ethylamine, propylamine, and butylamine; dimethylamine, diethylamine, dipropylamine, and dibutylamine. Examples of tertiary amines include trimethylamine, triethylamine, tripropylamine, pyridine, and tributylamine. Can be mentioned. Of these, tertiary amines are preferred from the viewpoint of storage stability.

The compound (C) having two or more vinyl ether groups (hereinafter referred to as component (C)) used in the present invention is not particularly limited as long as it has two or more vinyl ether groups. can do. Specifically, for example, the general formula (1): CH ₂ ═CH—O—X—O—CH═CH ₂ (X represents an alkylene group or an oxyalkylene group. The alkylene group and the oxyalkylene group are branched. And may have an unsaturated bond, and may have an aromatic group in the chain.). Specifically, for example, butanediol divinyl ether, cyclohexanedimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, hexanediol divinyl ether, trimethylolpropane trivinyl ether, Examples thereof include polyethylene glycol divinyl ether and polytetramethylene glycol divinyl ether. Among these, those having a larger number of carbon atoms of the alkylene group or oxyalkylene group are preferred because the corrosion resistance and solvent resistance are improved, and specifically those having 6 or more carbon atoms are preferred. Examples of these include cyclohexanedimethanol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, hexanediol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, polyethylene glycol divinyl ether, polytetramethylene glycol diester. Vinyl ether is mentioned.

  The compound (D) having an anionic functional group and a vinyl ether group (hereinafter referred to as component (D)) used in the present invention is not particularly limited as long as it is a compound having an anionic functional group and a vinyl ether group. Can be used. Specifically, it can be obtained, for example, by reacting a compound having a vinyl ether group and an active hydrogen group with a compound having an anionic functional group and an isocyanate group. In addition, even if it reacts a component (A) and a component (C) and stops reaction on the way, a target object will be obtained, but reaction control may become difficult.

The active hydrogen group is not particularly limited, and examples thereof include known groups such as amino group, hydroxyl group, mercapto group and the like.

Specific examples of component (D) include compounds having an anionic functional group and a vinyl ether group obtained by reacting a compound having an amino group and a vinyl ether group with an isocyanate having an anionic functional group in the molecule, a hydroxyl group and a vinyl ether. A compound having an anionic functional group obtained by reacting a compound having a group with an isocyanate having an anionic functional group in the molecule, a compound having a mercapto group and a vinyl ether group, and an isocyanate having an anionic functional group in the molecule A compound having an anionic functional group, for example, a compound obtained by reacting 3-aminopropyl vinyl ether with an isocyanate having an anionic functional group in the molecule, and an anionic functional group in the molecule having 4-hydroxybutyl vinyl ether. Having isocyanine Compound obtained by reacting the door, such as the compounds obtained by reacting an isocyanate having an anionic functional group in the 2-hydroxyethyl vinyl ether and molecules.

In the crosslinking method of the present invention, (1) the component (B) is volatilized from the aqueous resin composition containing the component (B) neutralized product and the component (C), and the vinyl ether group and the anion A reactive group reacts and crosslinks; (2) an aqueous resin composition containing the component (B) neutralized product and the component (D) (B) neutralized product and the component (C); When the component (B) is volatilized, the vinyl ether group and the anionic group react and cross-link; (3) In the component (A), the component (B), the neutralized product, and the component (D) in the component (B) When the aqueous resin composition containing the component (B) is volatilized from the Japanese product, the vinyl ether group and the anionic group react and crosslink.

Component (A) and component (D) must each be neutralized with component (B). Therefore, normally, the usage-amount of a component (B) makes the equivalent of the basic group contained in a component (B) more than the sum total equivalent of the anionic functional group contained in a component (A) and a component (D). It is necessary to do so. By using the component (B) in excess, the storage stability can be maintained for a longer time. In addition, although a component (B) normally volatilizes at room temperature, in order to advance bridge | crosslinking rapidly, you may perform a heating, pressure reduction, etc. as needed. In addition, when heating, it is preferable to set it as 150 degrees C or less.

The aqueous resin composition of the present invention comprises an aqueous resin composition containing the component (B) neutralized product and the component (C) of the component (A); the component (B) neutralized product and the component (D) ) Component (B) neutralized product and component (C) aqueous resin composition; component (A) component (B) neutralized product and component (D) component (B) neutralized product It is an aqueous resin composition. The usage-amount of a component (A), a component (D), and a component (B) is as above-mentioned, The usage-amount of a component (C) is not specifically limited, What is necessary is just to adjust suitably according to the desired crosslinking degree. However, it is usually preferable to contain about 1 to 10% in the solid content. If it is used in a large amount exceeding 10%, the resin film tends to be brittle. If it is less than 1%, the crosslinking density is too low, and the effects of the present invention may be difficult to obtain.

In the aqueous resin composition of the present invention, the component (A) is neutralized with the component (B), and then the component (C) is added, or the component (A) and the component (D) are combined with the component (B). After neutralization, it is obtained by adding component (C). Moreover, even if the mixture of component (A) and component (C) is neutralized with component (B), the mixture of component (A), component (D) and component (C) is neutralized with component (B). Can also be obtained.

The aqueous resin composition of the present invention can be used in various applications such as a coating agent, a coating composition, a binder for printing ink, an adhesive, and a resin emulsion.

When used as a coating agent, an additive for a coating agent may be added to the aqueous resin composition of the present invention as necessary.

When used as a coating composition, a coating additive may be added to the aqueous resin composition of the present invention as necessary.

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. In each example, “parts” and “%” are based on weight.

Example 1
(1) Synthesis of fatty acid-modified epoxy ester In a 1 liter glass flask equipped with a stirrer, thermometer, reflux dehydrator and nitrogen gas inlet tube, 200 g of bisphenol A type epoxy resin (Epototo YD-014), soybean oil fatty acid 96 g and 0.15 g of sodium hydrogen carbonate were added, heated at 220 ° C. while blowing nitrogen gas, and addition / condensation was performed until the acid value became 1 or less to obtain a fatty acid-modified epoxy ester.

(2) Synthesis of vinyl-modified epoxy ester In a 1 liter glass flask equipped with a stirrer, a thermometer and a nitrogen gas introduction tube, 250 g of the fatty acid-modified epoxy ester obtained in (1) and 50 g of t-butyl cellosolve were added. The mixture was heated and stirred at 130 ° C. A mixed solution consisting of 18 g of styrene, 14 g of acrylic acid, 3 g of t-butyl peroxybenzoate and 80 g of t-butyl cellosolve was added dropwise thereto over 1 hour, and the mixture was further kept warm for 4 hours. After cooling to 80 ° C., 18 g of triethylamine was added, and 400 g of water was added and dispersed. After cooling to 35 ° C., 19.6 g of triethylene glycol divinyl ether was added, the non-volatile content was 34.8%, and the viscosity was 0.30 Pa · s. An aqueous dispersion of a vinyl-modified epoxy ester having a pH of 9.5 and a solid acid value of 35 mgKOH / g (hereinafter, units are omitted) was obtained.

Example 2
The same procedure was carried out except that 24.6 g of cyclohexanedimethanol divinyl ether was added instead of triethylene glycol divinyl ether added after dispersion in Example 1, and the non-volatile content was 35.0%, the viscosity was 0.32 Pa · s, and the pH was 9.5. An aqueous dispersion of a vinyl-modified epoxy ester having a solid acid value of 35 was obtained.

Example 3
(3) Synthesis of fatty acid-modified epoxy ester In a 1 liter glass flask equipped with a stirrer, thermometer, reflux dehydrator and nitrogen gas inlet tube, 200 g of bisphenol A type epoxy resin (Epototo YD-011), soybean oil fatty acid 150 g and 0.15 g of sodium hydrogen carbonate were added and heated at 220 ° C. while blowing nitrogen gas, and addition and condensation were performed until the acid value became 1 or less to obtain a fatty acid-modified epoxy ester.

(4) Synthesis of vinyl-modified epoxy ester In a 1-liter glass flask equipped with a stirrer, a thermometer and a nitrogen gas introduction tube, 250 g of the fatty acid-modified epoxy ester obtained in (3) and 40 g of t-butyl cellosolve were added. The mixture was heated and stirred at 130 ° C. A mixed solution consisting of 18 g of styrene, 14 g of acrylic acid, 3 g of t-butyl peroxybenzoate and 80 g of t-butyl cellosolve was added dropwise thereto over 1 hour, and the mixture was further kept warm for 4 hours. After cooling to 80 ° C., 18 g of triethylamine was added, 370 g of water was added and dispersed. After cooling to 35 ° C., 19.6 g of triethylene glycol divinyl ether was added, and the non-volatile content was 36.4% and the viscosity was 0.45 Pa · s. An aqueous dispersion of a vinyl-modified epoxy ester having a pH of 9.5 and a solid acid value of 35 was obtained.

Example 4
In a 1 liter glass flask equipped with a stirrer, a thermometer and a nitrogen gas introduction tube, 250 g of the fatty acid-modified epoxy ester obtained in (1) of Example 1 and 50 g of t-butyl cellosolve were placed and stirred at 130 ° C. with heating. did. A mixed solution consisting of 18 g of styrene, 14 g of acrylic acid, 15 g of dehydrated castor oil, 3 g of t-butyl peroxybenzoate and 80 g of t-butyl cellosolve was added dropwise over 1 hour, and the mixture was further kept warm for 4 hours. After cooling to 80 ° C., 18 g of triethylamine was added, and 400 g of water was added and dispersed. After cooling to 35 ° C., 19.6 g of triethylene glycol divinyl ether was added, the non-volatile content was 35.0%, and the viscosity was 0.35 Pa · s. An aqueous dispersion of vinyl-modified epoxy ester having a pH of 9.5 and a solid acid value of 34 was obtained.

Example 5
(5) Synthesis of a compound having an anionic functional group and a vinyl ether group In a 1 liter glass flask equipped with a stirrer, thermometer and nitrogen gas introduction tube, 19.8 parts of dimethylolbutanoic acid, polytetramethylene glycol ( Product name: PTMG2000, manufactured by Mitsubishi Chemical Corporation, number average molecular weight 2000) 163.3 parts were charged and mixed and dissolved at 110 ° C. for 1 hour under a nitrogen stream. Next, after cooling to 85 ° C., 66.9 parts of isophorone diisocyanate was added and reacted at 85 ° C. for 5 hours to obtain 250 parts of urethane prepolymer having an isocyanate group terminal. Subsequently, the urethane prepolymer was added with stirring to an aqueous solution consisting of 568 parts of water, 117.8 parts of isopropyl alcohol, 13.5 parts of triethylamine, 11.9 parts of adipic acid dihydrazide, and 3.6 parts of aminopropyl vinyl ether. The mixture was dispersed and reacted at 50 ° C. for 3 hours to obtain an aqueous compound resin dispersion having an anionic functional group and a vinyl ether group.
200 g of the aqueous dispersion of the compound resin having the anionic functional group and the vinyl ether group obtained in the above (5) was mixed with 500 g of the aqueous dispersion of the vinyl-modified epoxy ester obtained in Example 1, and the nonvolatile content was 33.4%. An aqueous dispersion having a viscosity of 0.30 Pa · s, a pH of 9.0, and a solid acid value of 33 was obtained.

Comparative Example 1
In Example 1 (2), except that triethylene glycol divinyl ether was not added, the same procedure as in Example 1 (2) was followed, with a non-volatile content of 34.5%, a viscosity of 0.38 Pa · s, a pH of 9.5, a solid acid An aqueous dispersion of a vinyl-modified epoxy ester having a valence of 37 was obtained.

Comparative Example 2
In Example 3 (4), except that triethylene glycol divinyl ether was not added, the non-volatile content was 35.3%, the viscosity was 0.36 Pa · s, the pH was 9.5, and the solid acid was the same as Example 3 (4). An aqueous dispersion of a vinyl-modified epoxy ester having a valence of 37 was obtained.

  The vinyl-modified epoxy ester obtained in Examples and Comparative Examples was made into a paint with the following composition and tested. The evaluation results are shown in Table 1.

(Preparation of water-based paint)
After mixing the following (2) with the following (1), the glass beads were removed to obtain an aqueous paint. In addition, even when any aqueous dispersion of vinyl-modified epoxy ester was used, the aqueous paint was prepared so that the PWC was 57% and the paint concentration was 53%.
(1) An aqueous dispersion of vinyl-modified epoxy ester 44.6 g, carbon black 1.8 g, zinc phosphate 5.6 g, calcium carbonate 23.8 g, antifoaming agent 0.18 g, deionized water 1.8 g and glass beads After mixing 80 g, the mixture was kneaded with a paint shaker for 1 hour 30 minutes.
(2) Moreover, what added 0.22g of dryer (Hi-Cure MIXII, Toei Chemical Co., Ltd.) was prepared to 23g of vinyl-modified epoxy ester aqueous dispersions.

  The obtained water-based paint was applied to a degreased dull steel plate (SPCC-SD, 0.8 × 70 × 150 mm) with a bar coater so that the film thickness became 20 μm, and after forced drying (60 ° C. × 20 minutes) And left at room temperature (23 ° C., 60% RH) for 5 days. The following evaluation test was done about the obtained coating film.

  Coating film hardness: Measured according to JIS K5600-5-4.

  Corrosion resistance: Measured according to JIS K5600-7-1, and indicated by cellophane tape peel width (mm) after 20 days of salt spray test.

Water resistance: Performed according to JIS Z8736, and the whiteness (Lab value) of the coating film was measured with a double beam spectroscopic color difference meter (SZII-Σ80 TYPEIII, manufactured by Nippon Denshoku Industries Co., Ltd.). The smaller the whiteness (Lab value), the better the water resistance, 27 or more: large whitening of the coating film, 25 to 26: many whitenings of the coating film are observed, 24 or less: little or no whitening of the coating film Can be judged on the basis of not.

Paint stability: 100 g of the obtained water-based paint was placed in a sealed container and stored at 50 ° C. for 1 week, and its state was confirmed.
○: No problem △: Viscosity change is slightly observed ×: Viscosity change is significant or precipitation occurs

表中、耐水性のＬ値はＬａｂ値のことである。

In the table, the L value of water resistance is the Lab value.

Claims (18)

From an aqueous resin composition containing a volatile base (B) neutralized product of a vinyl-modified epoxy ester (A) having an anionic functional group and a compound (C) having two or more vinyl ether groups, a volatile base (B) A cross-linking method characterized in that a vinyl ether group and an anionic group react and cross-link by causing volatilization of. A vinyl-modified epoxy ester (A) having an anionic functional group, a volatile base (B) neutralized product of a compound (D) having an anionic functional group and a vinyl ether group, and a compound (C) having two or more vinyl ether groups A crosslinking method, wherein the volatile base (B) is volatilized from a contained aqueous resin composition, whereby a vinyl ether group and an anionic group are reacted and crosslinked. From an aqueous resin composition containing a vinyl-modified epoxy ester (A) having an anionic functional group and a volatile base (B) neutralized product of a compound (D) having an anionic functional group and a vinyl ether group, a volatile base ( A crosslinking method, wherein the vinyl ether group reacts with an anionic group to cause crosslinking by volatilization of B). The crosslinking method according to any one of claims 1 to 3, wherein the volatile base (B) is at least one selected from the group consisting of primary amines, secondary amines and tertiary amines. By the vinyl-modified epoxy ester (A) having an anionic functional group, the fatty acid-modified epoxy ester (a) is blended with the vinyl monomer (b) and, if necessary, fats and oils (c), and these are reacted. The crosslinking method according to any one of claims 1 to 4, which is obtained. Fatty acid-modified epoxy ester (a) is a fatty acid (a-1), an epoxy resin (a-2), and a compound (a-3) capable of reacting with the above (a-1) or (a-2) as necessary The crosslinking method according to any one of claims 1 to 5, which is obtained by reacting. A water-based resin composition comprising a volatile base (B) neutralized product of a vinyl-modified epoxy ester (A) having an anionic functional group and a compound (C) having two or more vinyl ether groups. A vinyl-modified epoxy ester (A) having an anionic functional group, a volatile base (B) neutralized product of a compound (D) having an anionic functional group and a vinyl ether group, and a compound (C) having two or more vinyl ether groups An aqueous resin composition to contain. An aqueous resin composition comprising a vinyl-modified epoxy ester (A) having an anionic functional group and a volatile base (B) neutralized product of a compound (D) having an anionic functional group and a vinyl ether group. The aqueous resin composition according to any one of claims 7 to 9, wherein the volatile base (B) is at least one selected from the group consisting of primary amines, secondary amines and tertiary amines. By the vinyl-modified epoxy ester (A) having an anionic functional group, the fatty acid-modified epoxy ester (a) is blended with the vinyl monomer (b) and, if necessary, fats and oils (c), and these are reacted. The aqueous resin composition according to any one of claims 7 to 10, which is obtained. Fatty acid-modified epoxy ester (a) is a fatty acid (a-1), an epoxy resin (a-2), and a compound (a-3) capable of reacting with the above (a-1) or (a-2) as necessary The water-based resin composition according to any one of claims 7 to 11, which is obtained by reacting. The compound (C) having two or more vinyl ether groups is added after neutralizing the vinyl-modified epoxy ester (A) having an anionic functional group with a volatile base (B). The manufacturing method of the aqueous resin composition in any one of. Compound (C) having two or more vinyl ether groups after neutralizing vinyl-modified epoxy ester (A) having an anionic functional group and compound (D) having an anionic functional group and a vinyl ether group with volatile base (B) ) Is added. The method for producing an aqueous resin composition according to any one of claims 7 to 12. A mixture containing a vinyl-modified epoxy ester (A) having an anionic functional group and a compound (C) having two or more vinyl ether groups is neutralized with a volatile base (B). The manufacturing method of the aqueous resin composition in any one of. A mixture containing a vinyl-modified epoxy ester (A) having an anionic functional group, a compound (D) having an anionic functional group and a vinyl ether group, and a compound (C) having two or more vinyl ether groups is a volatile base (B). The method for producing an aqueous resin composition according to any one of claims 7 to 12, wherein the aqueous resin composition is neutralized. The coating agent composition containing the aqueous resin composition in any one of Claims 7-12. The coating composition containing the aqueous resin composition in any one of Claims 7-12.