JP2000053909A - Aqueous coating material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin aqueous coating material having high adhesivity, excellent chemical resistance and strong toughness which are characteristic to an epoxy resin, with no use of emulsifier or the like which causes the deterioration of water resistance and corrosion resistance, excellent in membrane-forming property, smoothness, water resistance, corrosion resistance and flexibility, and free from the generation of pinholes. SOLUTION: This composition is obtained by compounding the following components in water: (a) an epoxy compound obtained by completely or partially epoxidizing the carbon-carbon double bond by oxidation reaction of an unsaturated acid expressed by the formula R1(CH=CHCH2)m(CH2)nCOOR3 [R1 is a 1-10C alkyl; R2 is a residue which is formed by removing a hydroxyl group from a mono alcohol or a polyol having at least one primary hydroxyl group; (m) and (n) are each an integer selected from 1 to 20; the sequence of the connection of (CH=CHCH2)m and (CH2)n is arbitrary] by oxidation reaction; (b) an acrylic resin having a carboxylic group and a hydroxyl group; (c) a melamine resin; and (d) a neutralizing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The aqueous coating composition according to the present invention relates to an aqueous coating composition capable of forming a cured film having excellent flexibility, adhesiveness to a substrate, solvent resistance and the like.
More specifically, films and other plastic molded products, metal machinery and parts, coating agents for wooden furniture, metals,
In addition to the fields where the original coating properties such as lining materials for ceramic products, printing inks, photoresist inks in the electronics field, insulating varnishes, insulating sheets, printed boards, etc. are exhibited, and more broadly, the fields that also make use of the adhesive properties, such as wood The present invention relates to a water-based coating composition that can be applied to various fields, such as an adhesive for products and a laminate for electric use in the electronics field.

[0002]

2. Description of the Related Art Epoxy resins are excellent in adhesiveness, chemical resistance, toughness, etc., and are used in the form of aqueous epoxy resin emulsions which are emulsified and dispersed using a large amount of emulsifiers and protective colloids in addition to solutions. ing. However, the conventional one emulsified and dispersed by using a large amount of emulsifier has poor stability against the electrolyte, and when this is cured with a curing agent, although the film forming property of the coating film is excellent, the water resistance and corrosion resistance of the coating film are excellent. Was not sufficient, and there was a practical problem. Further, Japanese Patent Application Laid-Open No. 64-2
No. 9468, an anionic water-based paint using an epoxy resin is excellent in stability, but does not cure at room temperature even when a curing agent is added. Smoothness was reduced, fine pinholes were also generated, and there were problems in terms of water resistance, corrosion resistance, and flexibility. On the other hand, an aqueous coating containing a hydroxyl group and carboxyl group-containing acrylic resin, a melamine resin, and a neutralizing agent has good curability, but its coating strength is not sufficient, and chipping resistance is high.
It has the disadvantage of low water resistance.

[0003]

SUMMARY OF THE INVENTION Accordingly, the present invention utilizes the high adhesiveness, chemical resistance, and toughness characteristic of epoxy resins, and does not use an emulsifier or the like which lowers water resistance and corrosion resistance. It is an object of the present invention to obtain an epoxy resin-based water-based paint that is excellent in smoothness, water resistance, corrosion resistance, and flexibility and does not generate pinholes.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a specific epoxy compound, a hydroxyl group- and carboxyl group-containing acrylic resin, a melamine resin, and a neutralizing agent were added to water. The present inventors have found that an aqueous coating composition containing the same is suitable and completed the present invention. The gist of the present invention is as follows. A first invention is an epoxy compound obtained by (a) completely or partially epoxidizing a carbon-carbon double bond of an unsaturated fatty acid ester represented by the following general formula (1) by an oxidation reaction;
The present invention relates to an aqueous coating composition comprising (b) an acrylic resin having a carboxyl group and a hydroxyl group, (c) a melamine resin, and (d) a neutralizing agent in water.

[0005] ^{R 1 - (CH = CH-} CH 2) m - (CH 2) n -CO-OR 2 (1) ( wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms, R ²
O- is a residue obtained by removing one H from the hydroxyl group of a monoalcohol or polyol having at least one primary hydroxyl group. m and n are each 1 to 2
It is an integer selected from 0, and the bonding order of each of the m and n groups is arbitrary. ) The second invention relates to a compound represented by the general formula (1)
The present invention relates to the aqueous coating composition according to the first aspect, wherein ² O- is a residue of the polyethylene glycol having a number average molecular weight of 500 to 5,000, except for one of the hydroxyl groups. Third
In the invention, R ² O— of the general formula (1) has a number average molecular weight of 20.
The present invention relates to the aqueous coating composition according to the first invention, which is a residue obtained by removing 1 H from the hydroxyl group of 0 to 5,000 polyglycerin or a partially esterified product thereof. In the fourth invention, the unsaturated fatty acid residue excluding R ² O— in the general formula (1) is derived from a higher unsaturated fatty acid obtained by refining fish oil or a derivative thereof. It relates to the aqueous coating composition according to the invention. The fifth invention is directed to the first aspect.
An epoxidized block polymer comprising a residue of an epoxy compound (a) and a residue of a thermoplastic resin having a number average molecular weight of 200 or more in place of the epoxy compound (a) described in the invention of the above (1), The present invention relates to an aqueous coating composition using the epoxidized block polymer (e) represented by any of (4) to (4).

DA (2) DAD (3) (D) _p -A (4) (In the general formulas (2) to (4), D represents the epoxy according to the first aspect of the present invention. R ¹ , R ² or OR from compound (a)
It is a residue of the epoxy compound (a) excluding ² ; A is a residue of a thermoplastic resin; and p is an integer of 2 or more. Formula (2) has D at one end of the molecule of A, formula (3) has D at both ends of the molecule of A, and formula (3) has p D at one end of the molecule of A.
Are connected in a broom shape. )

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The epoxy compound used in the present invention comprises an unsaturated fatty acid ester epoxy compound (a) represented by the above-mentioned general formula (1) and the above-mentioned general formula (2)
Epoxidized block polymers (e) belonging to the groups represented by (4) to (4). The unsaturated fatty acid of the unsaturated fatty acid ester represented by the general formula (1) used in the production of the epoxy compound (a) has a carbon number of 1
Those having a range of 6 to 22 are preferable, and those having a range of 20 to 22 are particularly preferable. Further, m is preferably in the range of 4 to 6, and n is preferably in the range of 1 to 7.

Specifically, hexadecatrienoic acid having 16 carbon atoms (6,10,14-hexadecatrienoic acid, 6,
9,12-hexadecatrienoic acid, 7,10,13-hexadecatrienoic acid), hexadecatetraenoic acid; octadecatetraenoic acid having 18 carbon atoms (4,8,12,15)
-Octadecatetraenoic acid), eicosatetraenoic acid having 20 carbon atoms (5,8,11,14-eicosatetraenoic acid, 4,8,12,16-eicosatetraenoic acid), eicosapentaenoic acid (5,8,11,14,17-eicosapentaenoic acid, 4,8,12,15,18-eicosapentaenoic acid), and C21-containing heneicosapentaenoic acid (6,9,12,15,18-henic acid) Eicosapentaenoic acid), docosatetraenoic acid having 22 carbon atoms (10,1
3,16,19-docosatetraenoic acid), docosapentaenoic acid (7,10,13,16,19-docosapentaenoic acid), docosahexaenoic acid (4,7,10,13,1)
6,19-docosahexaenoic acid, 4,8,12,15,
18,21-docosahexaenoic acid, 4,8,11,1
4,17,20-docosahexaenoic acid). These are obtained from natural fats and oils such as fish oils, and are used as the raw materials for components according to the present invention in any form as high-purity products, mixtures thereof, or distillation residues containing these unsaturated fatty acids and their derivatives. be able to.

R ^{1 in the} general formula (1) is an alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl. Group, decyl group and the like, and an alkyl group having 2 to 5 carbon atoms is preferable.

When the epoxy compound (a) is used as the epoxy compound in the present invention, its R ² O
-Represents one H of the hydroxyl group of the monoalcohol or polyol having at least one primary hydroxyl group.
Is the residue excluding. Here, the polyol is a polyol in a broad sense, and in addition to a polyol in a narrow sense not containing an ether bond such as ethylene glycol, propylene glycol, glycerin, and pentaerythritol, a polyether polyol containing an ether bond such as polyethylene glycol and polyglycerin. In the present invention, a polyether polyol is preferred. Among them, polyethylene glycol or polyglycerin having high affinity for water is particularly preferred. The monoalcohol or polyol needs to have at least one primary hydroxyl group, and more preferably two or more. This is because the presence of the primary hydroxyl group has the effect of efficiently promoting esterification or transesterification of unsaturated fatty acids.

The method of coupling the above unsaturated fatty acid with a polyol such as polyethylene glycol or polyglycerin is not particularly limited, but a method of direct esterification using an acid catalyst, a method of using a chlorinating agent, and the like. The esterification method of the obtained unsaturated fatty acid via an acid chloride and the transesterification method using an ester of the unsaturated fatty acid are preferred, and the esterification method and the transesterification method via an acid chloride are particularly preferably used.

When the ester group of the unsaturated fatty acid ester is transesterified with polyethylene glycol or polyglycerin, the transesterification catalyst may be a tin compound, a titanium compound, an antimony compound, an aluminum compound,
A zinc compound, a molybdenum compound, a zirconium compound and the like can be exemplified, but a tin compound, a titanium compound, and an antimony compound are preferably used in view of balance of easiness of handling, low toxicity, reactivity, non-coloring property, heat stability and the like.

Specific examples of the tin compound include stannous chloride and stannous octylate, monobutyltin compounds such as monobutyltin oxide and monobutyltin tris (2-ethylhexyl hexanate), and dibutyltin compounds such as dibutyltin oxide. Compounds can be exemplified. Further, specific examples of the titanium compound include tetrabutyl titanate and tetraisopropyl titanate. Specific examples of the antimony compound include antimony triacid number.

The transesterification conditions for obtaining the unsaturated fatty acid ester of the general formula (1) are not particularly limited, and the above transesterification catalysts can be used alone or as a mixture. By performing the transesterification reaction at a reduced pressure of preferably 100 mmHg or less, more preferably 10 mmHg or less, preferably at 100 to 300 ° C, more preferably 150 to 220 ° C in the presence of a catalyst, the compound represented by the general formula (1) It is possible to obtain the unsaturated fatty acid esters represented.

The epoxy compound of the unsaturated fatty acid ester of the general formula (1) according to the present invention is obtained by completely or partially epoxidizing the unsaturated fatty acid ester by a carbon-carbon double bond oxidation reaction. However, an example of the epoxidation reaction will be described. As the epoxidizing agent that can be used for the oxidation reaction of the carbon-carbon double bond, peracids and hydroperoxides are particularly preferably used. The peracids include formic acid, peracetic acid, perbenzoic acid,
Trifluoroperacetic acid and the like can be used, and among them, peracetic acid is a particularly preferable epoxidizing agent, which is commercially available at low cost and has high stability. As the hydroperoxides, hydrogen peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide and the like can be used.

The amount of the epoxidizing agent used is not strictly regulated, and the optimum amount in each case is determined not only by the individual epoxidized substances used, the individual epoxidizing agents, but also by the desired epoxidation degree. Etc. are appropriately determined according to variable factors. For example, the charged molar ratio of the epoxidizing agent to the unsaturated bond is determined depending on the desired degree of epoxidation, that is, how much the unsaturated bond is desired to remain. Specifically, when the purpose is to obtain a compound having a large number of epoxy groups, the epoxidizing agent is preferably added in an equimolar amount or more to the unsaturated group. However, from the viewpoint of economy and the problem of side reactions described below, two
It is usually disadvantageous to use more than twice the molar amount. In the case of peracetic acid, the molar ratio is preferably about 1 to 1.5 times.

In carrying out the epoxidation reaction, the reaction catalyst can be used if necessary. When the epoxidizing agent is a peracid, for example, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as the catalyst. In the case of hydroperoxide, a catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl in combination with tertiary butyl hydroperoxide. .

Further, the necessity of using an inert solvent in the epoxidation reaction and the degree of controlling the temperature of the reaction are determined according to the characteristics of the apparatus and the raw materials. The inert solvent can be used for the purpose of lowering the viscosity of the raw material, stabilizing by diluting the epoxidizing agent, and the like. Preferred solvents include hexane, cyclohexane, toluene, benzene, ethyl acetate, carbon tetrachloride, and chloroform. No.
When peracetic acid is used as the epoxidizing agent, aromatic compounds, ethers, esters and the like can be preferably used.

The temperature range suitable for the epoxidation reaction is determined by the reactivity of the epoxidizing agent used. For example, when using the preferred epoxidizing agent peracetic acid,
0 ° C. is preferred. If it is lower than 0 ° C., the reaction is slow, and if it is higher than 70 ° C., decomposition of peracetic acid may occur. Also, when using the hydroperoxide of the epoxidizing agent,
As described above, the tert-butyl hydroperoxide / molybdenum dioxide diacetylacetonate system, which is a combination system, is preferable.
150 ° C. is preferred.

In the above-mentioned epoxidation reaction, no special operation is required except for charging the raw materials, catalyst, solvent and the like into the reaction apparatus or performing the reaction after charging, while stirring to a necessary degree. The charged mixture may be stirred for about 1 to 6 hours. As a method for isolating the obtained epoxy compound, various known isolation means used after the chemical reaction can be used, for example, a method of adding a poor solvent, precipitating by utilizing the difference in solubility, and a method of heating under stirring. A method in which the solvent is introduced into water to separate and remove or evaporate the solvent, a method in which the solvent is directly removed, and the like can be preferably used.

As described above, the present invention provides an epoxidized block polymer (e) represented by the general formula (2), (3) or (4) in place of the epoxy compound (a) as the epoxy compound. Is used, and the epoxidized block polymer (e) represented by the general formulas (2) to (4) is obtained by converting the epoxy compound (a) into R ¹ , R ² or OR.
^It is composed of the epoxy compound (a) residue D excluding ² and the thermoplastic resin residue A. As the epoxy compound (a) residue D, a completely or partially epoxidized product is used.

As the thermoplastic resin, those having a number average molecular weight of 200 to less than 10,000, preferably 500 to less than 5,000 are used. Number average molecular weight is 2
If it is less than 00, it may not be water-soluble, and if it is 10,000 or more, it is difficult for the reaction to proceed during transesterification, and if it is used as a paint, the water resistance is poor. The thermoplastic resin is not particularly limited as long as it is water-soluble itself. Specific examples include polyethylene glycol, polypropylene glycol, polybutylene glycol, polyglycerin and the like.

Residue A of the thermoplastic resin refers to those obtained by removing the terminal hydrogen group, hydroxyl group, carboxyl group, and halogen group of these thermoplastic resins or derivatives thereof. (2)
(4) The epoxidized block polymer (e) is obtained. In the block polymer represented by the general formula (2), both residues are bonded one by one, and in the one represented by the general formula (3), the residue A of the thermoplastic resin is In the case of a divalent residue relating to two atoms, the residue A
Two residues D are linked to one. What is represented by the general formula (4) is a case where the residue A of the thermoplastic resin is a divalent or higher valent residue relating to one atom, and the residue A has two or more residues D per one residue. Are bonded, and residue A
On the other hand, residue D is bound like a broom. This form of connection
It is thought to be due to steric hindrance of multiple residues D.

The acrylic resin (b) containing a hydroxyl group and a carboxyl group used in the present invention will be described. The acrylic resin referred to in the present invention is a copolymer in which at least an acrylic ester monomer, a hydroxyl group-containing monomer and a carboxyl group-containing monomer are used as monomers for copolymerization. As the acrylic ester monomer, for example, acrylic acid or methacrylic acid and C1
Monoesters with monoalcohols of from 20 to 20 are preferred, and examples of the hydroxyl group-containing monomer include acrylic acid or methacrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate, and a C1-10 Monoesters with glycols can be suitably used, and further, as carboxyl group-containing monomers, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, anhydrides thereof, half-esterified products Etc. are preferably used.

In the above acrylic resin of the present invention, in addition to the acrylic ester monomer, the hydroxyl group-containing monomer and the carboxyl group-containing monomer, other copolymerizable monomers may be appropriately used in combination. It also includes the obtained copolymer. Examples of the other copolymerizable monomers include, for example, copolymerizable monomers such as styrene, vinyl toluene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, glycidyl acrylate, and glycidyl methacrylate. . When the above other copolymerizable monomer is used in combination, the amount used is the same as the total amount of the three types of copolymerizable monomers used as an essential component for constituting the acrylic resin or It is preferably less than that.

The above-mentioned acrylic resin is neutralized by a neutralizing agent, which is a constituent component of the present invention, to be in a state of being dissolved or dispersed in water, and is used in that state. The number average molecular weight of the acrylic resin is about 3,0
00-100,000 is preferred, but about 5,000-5
000 is more preferred. Hydroxyl value is about 20-150
mgKOH / g is preferred, but about 30-100 mgKO
H / g is more preferred. Further, the acid value is about 5-100 mgK
OH / g is preferred, but about 10-80 mg KOH / g is more preferred.

In the composition according to the present invention, melamine resin (c) is further used as a crosslinking agent for the above-mentioned acrylic resin. Melamine resin referred to in the present invention is a resin-like uncured resin obtained by a condensation reaction of melamine and formalin,
It refers to methylolated melamine, alkyl etherified compounds in which a part or all of the methylol group is etherified with a monoalcohol having 1 to 10 carbon atoms, and the like, and the alkyl etherified compounds are preferable. The number average molecular weight of the melamine resin used is preferably about 400 to 3,000,
0 to 1,500 is more preferable. The melamine resin may be either hydrophobic or hydrophilic.

The composition according to the present invention additionally contains a neutralizing agent (d). The neutralizing agent here neutralizes a carboxyl group in the acrylic resin (b) and imparts solubility or dispersibility with water. Examples include ammonia, trimethylamine, triethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, diethylaminoethanol and the like. Of these, dimethylethanolamine is preferred.

Next, the component (a) or (e) and (b)
The mixing ratio with (c) and (d) will be described. Epoxy compound (a) or epoxidized block polymer (e)
(B) acrylic resin 8 with respect to 99.0 to 0.1 parts by weight
0 to 5 parts by weight, (c) melamine resin 80 to 10 parts by weight,
(D) 20 to 1 part by weight of a neutralizing agent is suitable, and more preferably 90 to 1 part by weight of component (a) or (e), 75 to 15 parts by weight of component (b), and 70 to 1 part by weight of component (c). 20 parts by weight,
(D) Component is 15 to 3 parts by weight. If the amount of component (a) or (e) exceeds 99.0 parts by weight, poor curing may occur, and if less than 0.1 part by weight, precipitation of the composition may occur. The amount of component (b) is 80
When the amount exceeds the weight part, the flexibility is insufficient, and the bending resistance and the chipping resistance are reduced. If the amount is less than 5 parts by weight, there may be a problem in water resistance. If the compounding amount of the component (c) exceeds 80 parts by weight, many uncured portions remain and physical properties such as water resistance and bending resistance are reduced. If the amount is less than 10 parts by weight, poor curing also occurs, and water resistance, bending resistance and the like are reduced. If the amount of component (d) is more than 20 parts by weight, the composition will have an odor, and if it is less than 1 part by weight, the solubility of the composition will be reduced, making it difficult to dissolve in water. These components (a) to (e) are added to water, and the concentration thereof is preferably 10 to 80% by weight, and when used, the components are appropriately diluted with water as needed.

The aqueous coating composition of the present invention may further contain a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a pigment, a thickener, an antisettling agent, an antifogging agent, if necessary. Agents, antistatic agents, organic solvents and the like can also be added. As a method for applying the aqueous coating composition according to the present invention, various known coating methods such as brush coating, spray coating, dip coating, spin coating, and curtain coating are used.

[0031]

EXAMPLES Next, the present invention will be described with reference to synthesis examples of the epoxy compounds (a) and (e) and the acrylic resin (b) used in the present invention, and examples and comparative examples relating to the use of the epoxy compounds. Is described, “%” in Synthesis Examples, Examples and Comparative Examples all means “% by weight”. The NMR used here was GXS270 manufactured by JEOL Ltd.
WB and IR are FTIR-5300 manufactured by JASCO Corporation, GPC
Is a HPLCLC-6A SYSTEM (column: polystyrene column, solvent: THF) manufactured by Shimadzu Corporation.

(Synthesis Example 1) 300 g of docosahexaenoic acid ethyl ester (GC purity: 70%, residue after distillation of active ingredient from fish oil, iodine value: 373), and polyethylene glycol (hereinafter referred to as PEG) (manufactured by NOF Corporation) 252.8 g of number average molecular weight Mn600) and 0.56 g of tetrabutoxytitanium were charged into a flask equipped with a dehydrating tube, and 20
The reaction was performed at 0 ° C. for 24 hours. The content of ethyl docosahexaenoate by GC analysis of the reaction product was 1.8% by weight. This docosahexaenoic acid PEG
160 g of ethyl acetate was charged to 320 g of the ester, and 796.8 g of peracetic acid (peracetic acid concentration: 29.3%) was added dropwise over about 2 hours so that the temperature in the reaction system became 50 ° C. while blowing nitrogen gas. . After completion of the dropwise addition of the peracetic acid solution, the mixture was aged at 40 ° C. for 2 hours to complete the reaction. The reaction crude liquid was washed with water at 40 ° C., and the low boiling components were removed at 70 ° C./10 mmHg to obtain 336 g of PEG ester A-1 of hexaepoxydocosahexaenoic acid. The properties of the obtained product were as follows: oxirane oxygen concentration: 9.56%, viscosity: 12,400 cp / 2
5 ° C.

(Synthesis Example 2) 300 g of docosahexaenoic acid ethyl ester (GC purity: 70%, iodine value of residue after distillation of active ingredient from fish oil: 373), and PEG (manufactured by NOF Corporation, number average molecular weight: Mn 1,000) ) 421 g,
0.72 g of tetrabutoxytitanium was charged into a flask with a dehydrating tube, and reacted at 210 ° C. for 24 hours. When the molecular weight distribution of the reaction product was measured by GPC, the peak at a molecular weight of around 350 in terms of styrene disappeared, and PEG docosahexaenoic acid could be obtained. Next, ethyl acetate 1 was added to 340 g of PEG docosahexaenoic acid.
70 g was charged and peracetic acid 649 was added for about 2 hours so that the temperature in the reaction system became 50 ° C. while blowing nitrogen gas.
g (peracetic acid concentration: 29.3%) was added dropwise. After completion of the dropwise addition of the peracetic acid solution, the reaction was completed by aging at 50 ° C. for 4 hours. The reaction crude solution was washed with water at 40 ° C., and 70 ° C./10 mmHg
To remove 322 g of PEG ester A-2 of hexaepoxydocosahexaenoic acid. The properties of the obtained product were as follows: oxirane oxygen concentration 7.21%, viscosity 8.8
It was 50 cp / 25 ° C.

(Synthesis Example 3) 300 g of ethyl docosahexaenoate (GC purity: 70%, iodine value of residue after distillation of active ingredient from fish oil: 373), 300 g of PEG (manufactured by NOF Corporation, Mn 2,000) 187 g and 1.4 g of tetrabutoxytitanium were charged into a flask with a dehydrating tube,
The reaction was performed at 210 ° C. for 24 hours. When the molecular weight distribution of the reaction product was measured by GPC, the peak at a molecular weight of around 350 in terms of styrene disappeared, and PEG docosahexaenoic acid could be obtained. Next, 150 g of ethyl acetate was charged into 300 g of PEG docosahexaenoic acid, and the temperature in the reaction system was raised to 50 ° C. while blowing nitrogen gas.
285 g of peracetic acid (peracetic acid concentration: 29.3%) was added dropwise over about 2 hours. After the addition of peracetic acid, 5
The reaction was completed by aging at 0 ° C. for 4 hours. The reaction crude solution was washed with water at 50 ° C., and the low boiling components were removed at 70 ° C./10 mmHg to obtain 299 g of PEG ester A-3 of hexaepoxydocosahexaenoic acid. The properties of the obtained product were as follows: oxirane oxygen concentration 3.87%, viscosity 5,780 cp / 25 ° C.
Met.

(Synthesis Example 4) 300 g of docosahexaenoic acid ethyl ester (GC purity: 70%, iodine value of residue after distillation of active ingredient from fish oil: 373), and polyglycerin (hereinafter, referred to as PGL) (PGL manufactured by Daicel Chemical Industries, Ltd.)
04, Mn400) 132.2 g and tetrabutoxytitanium 0.43 g were charged into a flask equipped with a dehydrating tube,
For 24 hours. When the molecular weight distribution of the reaction product was measured by GPC, the peak at a molecular weight of around 350 in terms of styrene disappeared, and docosahexaenoic acid PGL ester 4
03 g were obtained. Next, 150 g of ethyl acetate was charged into 300 g of docosahexaenoic acid PGL ester, and the temperature in the reaction system was raised to 40 ° C. while blowing nitrogen gas.
862 g of peracetic acid (peracetic acid concentration: 29.1%) was added dropwise over about 2 hours. After completion of the dropwise addition of the peracetic acid solution, the mixture was aged at 40 ° C. for 3 hours to complete the reaction. The reaction crude liquid was washed with water at 40 ° C., and the low boiling components were removed at 70 ° C./10 mmHg to obtain 312.1 g of hexaepoxydocosahexaenoic acid PGL ester A-4. The properties of the obtained product are
Oxirane oxygen concentration 10.2%, viscosity 8,040 cp /
25 ° C.

(Synthesis Example 5) 300 g of docosahexaenoic acid ethyl ester (GC purity: 70%, iodine value of residue after distillation of active ingredient from fish oil: 373), and PGL (PGL10, Mn1,000, manufactured by Daicel Chemical Industries) 319.1
g and 0.62 g of tetrabutoxytitanium were charged into a flask equipped with a dehydration tube and reacted at 210 ° C. for 24 hours. When the molecular weight distribution of the reaction product was measured by GPC, the peak at a molecular weight of around 350 in terms of styrene disappeared, and 591 g of docosahexaenoic acid PGL ester could be obtained. Then, 150 g of ethyl acetate was charged into 300 g of docosahexaenoic acid PGL ester, and 529 g of peracetic acid (peracetic acid concentration: 29.3%) was added over about 2 hours so that the temperature in the reaction system became 40 ° C. while blowing nitrogen gas. It was dropped.
After completion of the dropwise addition of the peracetic acid solution, the reaction was aged at 50 ° C. for 3 hours to complete the reaction. The reaction crude solution was washed with water at 50 ° C.
A low boiling component was removed at mmHg to obtain 302.8 g of hexaepoxydocosahexaenoic acid PGL ester A-5.
The properties of the obtained product were oxirane oxygen concentration 4.15.
%, Viscosity 3,800 cp / 25 ° C.

Synthesis Example 6 300 g of docosahexaenoic acid ethyl ester (GC purity: 70%, iodine value of residue after distillation of active ingredient from fish oil: 373), 300 g of PGL (manufactured by Daicel Chemical Industries, PGL06, Mn600): 194 g, tetrabutoxytitanium 0.49 g was charged into a flask with a dehydration tube, and reacted at 200 ° C. for 24 hours. When the molecular weight distribution of the reactant was measured by GPC, the molecular weight was 35 in terms of styrene.
The peak near zero disappeared, indicating that docosahexaenoic acid P
461 g of GL ester could be obtained. Next, 150 g of ethyl acetate was charged into 300 g of docosahexaenoic acid PGL ester, and peracetic acid was added to the reaction system over a period of about 3 hours while blowing nitrogen gas so that the temperature in the reaction system became 40 ° C.
4 g (peracetic acid concentration: 29.3%) was added dropwise. After the completion of the dropwise addition of the peracetic acid solution, the mixture was aged at 50 ° C. for 2 hours to complete the reaction. The reaction crude solution was washed with water at 40 ° C., and 70 ° C./10 mmHg
To remove low boiling components, to obtain 304 g of hexaepoxydocosahexaenoic acid PGL ester A-6. The properties of the obtained product were as follows: oxirane oxygen concentration 6.96%, viscosity 5.1
70 cp / 25 ° C.

(Synthesis Example of Acrylic Resin Aqueous Solution) In a reactor equipped with a reflux cooling pipe and a nitrogen gas introducing pipe, butyl cellosolve 500 g, styrene 100 g, methyl methacrylate 250 g, n-butyl methacrylate 200 g, n-butyl acrylate 250 g, acrylic acid Azobisisobutyronitrile as a radical polymerization initiator in a mixture of 100 g of hydroxyethyl methacrylate and 150 g of hydroxyethyl methacrylate.
0 g, and polymerized at 110 ° C. for 4 hours to obtain a number average molecular weight of 1
5,000 hydroxyl and carboxyl group-containing acrylic resins B-1 were obtained. 1,000 g of water was added to this resin solution, and the solution was neutralized by equivalent amount with dimethylethanolamine to obtain an acrylic resin aqueous solution having an acrylic resin concentration of 42.0%.
g.

(Examples 1 to 6, Comparative Examples 1 and 2) In Examples and Comparative Examples, paints comprising an aqueous paint composition in which the respective components were blended in the weight ratios shown in Table 1 were used. The coating was dried on a material and baked at 150 ° C. for 15 minutes to evaluate various properties of the coating film obtained. The base materials used here are two types, an aluminum plate and a steel plate (SPCC). The evaluation results are shown in Table-2.

The evaluation characteristics and their contents are as follows. (1) Adhesion: Using a treated substrate and an untreated substrate, a cross cut reaching the substrate at 1 mm intervals was made on the applied cured coating of the test plate, and a 1 mm square cross section was cut by 1 mm.
Then, a cellophane tape was stuck thereon and then rapidly peeled off by a 180 ° peeling method, and evaluated by the number of grids peeled off. The evaluation criteria and indications are 5 for 0 peels, 4 for 1 to 25, 3 for 25 to 50, 2 for 50 to 75, and 75 to 100 for A display method of 1 was adopted. (2) Bending resistance: Using a bending tester, JIS K540
A bending test was performed according to 0, and the state of cracks and peeling of the coating film was visually examined and evaluated. ：: No cracking or peeling of the coating film △: Cracking of the coating film was observed ×: Peeling of the coating film was observed (3) Water resistance The test plate was immersed in warm water of 40 ° C. for 15 days to obtain an appearance such as a blister. Observed. The evaluation criteria and indications are as follows. ：: No abnormalities were observed. Δ: Slight blisters. ×: Blisters are clearly observed in both number and size. (4) Chipping resistance As a test device, a QGR gravelometer (manufactured by Q Panel Co., Ltd.) was used.
00 g was sprayed on a test plate under the conditions of an air pressure of 4 kg / cm ² , a temperature of −20 ° C., and a spray angle of 45 ° to give an impact to the coating film, and the state of the coating film surface was observed. The evaluation criteria and indication of this result are as follows. ：: Some scratches due to impact were observed in the coating film. Δ: Peeling due to impact is slightly observed in the coating film. X: Many peeling by impact is recognized in the coating film.

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[Table 1]

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[Table 2]

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The aqueous coating composition according to the present invention is excellent in good adhesion to substrates, flexibility, water resistance, chipping resistance and the like, and can be used in various coating and adhesive fields. .

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J038 CG031 CG032 CG061 CG062 CG071 CG072 CG141 CG142 CH121 CH122 DA161 DA162 DB241 DB242 DB261 DB262 DB471 DB472 GA03 GA06 JB03 JB09 MA08 MA10 NA04 NA12 PB05 PB09 PC02 PC08 PC08

Claims (5)

[Claims] (A) an epoxy compound obtained by completely or partially epoxidizing a carbon-carbon double bond of an unsaturated fatty acid ester represented by the following general formula (1) by an oxidation reaction: (b) An acrylic resin having a carboxyl group and a hydroxyl group, (c) a melamine resin, and (d)
An aqueous coating composition comprising a neutralizing agent in water. ^{R 1 - (CH = CH-} CH 2) m - (CH 2) n -CO-OR 2 (1) ( wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms, R ²
O- is a residue obtained by removing one H from the hydroxyl group of a monoalcohol or polyol having at least one primary hydroxyl group. m and n are each 1 to 2
It is an integer selected from 0, and the bonding order of each of the m and n groups is arbitrary. ) 2. The aqueous coating composition according to claim 1, wherein R ² O— in the general formula (1) is a residue of polyethylene glycol having a number average molecular weight of 500 to 5,000, except for one H of a hydroxyl group. . 3. The compound according to claim 1, wherein R ² O— in the general formula (1) is a residue of polyglycerin having a number average molecular weight of 200 to 5,000 or a partial esterified product thereof except for one H of a hydroxyl group. Aqueous paint composition. 4. The method according to claim 1, wherein the unsaturated fatty acid residue excluding R ² O— in the general formula (1) is derived from a higher unsaturated fatty acid obtained by refining fish oil or a derivative thereof. Aqueous coating composition. 5. An epoxy compound (a) residue and a number average molecular weight of 20 instead of the epoxy compound (a) according to claim 1.
An epoxidized block polymer consisting of 0 or more residues of a thermoplastic resin, wherein an epoxidized block polymer (e) represented by any of the following general formulas (2) to (4) is used. An aqueous coating composition characterized by the following. DA (2) DAD (3) (D) _p -A (4) (In the general formulas (2) to (4), D represents R from the epoxy compound (a) according to claim 1) ¹ , a residue of an epoxy compound (a) excluding R ² or R ² O, A is a residue of a thermoplastic resin, and p is an integer of 2 or more. (D is attached to one end of the molecule, formula (3) shows that D is attached to both ends of the molecule of A, and formula (3) shows that p D's are attached to the end of the molecule of A in a broom shape.)