JP2005120340A - Water-based vinyl-modified epoxy resin, method for producing the same and water-based coating agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-based vinyl-modified epoxy resin having high initial hardness of its coated film, hardly causing whitening in water for its black coated film, having moderate flexibility and hardly giving cracks in using the same for a long time, i.e., having no reduction in corrosion resistance and a water-based coating agent comprising the water-based vinyl-modified epoxy resin. <P>SOLUTION: A polymerizable unsaturated group-containing modified epoxy resin (1) is prepared by reacting an aromatic epoxy resin (1a), an aliphatic epoxy resin (1b), a glycidyl group-containing vinyl monomer (1c) and an amine (1d). A copolymer (A) is prepared by copolymerizing the modified epoxy resin (1) with a carboxy group-containing vinyl monomer (2). The water-based vinyl-modified epoxy resin prepared by neutralizing the copolymer (A) with a basic compound and dispersing or dissolving the neutralized copolymer in water is used. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an aqueous vinyl-modified epoxy resin, a method for producing the same, and an aqueous coating agent containing the vinyl-modified epoxy resin.

  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 as a component, it has high corrosion resistance, can be dried at room temperature with a fatty acid ester component, and can be made aqueous by selecting a vinyl monomer component. .

  However, as the application field of water-based paints expands, the required performance for the coating film also increases, and a further increase in corrosion resistance and water resistance and high initial coating film hardness are required. For example, the conventional vinyl-modified epoxy ester has a low initial coating film hardness, and the coating film hardness gradually increases due to oxidative polymerization of the fatty acid component in the resin, and it takes several days to reach the target hardness. The initial damage was a problem. In addition, in the conventionally known vinyl-modified epoxy ester, a phenomenon that a black coating film prepared from the resin is whitened when immersed (hereinafter referred to as water whitening resistance) has also been a problem. Such water whitening is improved by increasing the ratio of the fatty acid component in the vinyl-modified epoxy ester, but there is a problem that the coating film hardness and the corrosion resistance tend to be lowered.

  Therefore, the present applicant has proposed a vinyl-modified epoxy resin aqueous material obtained by using a bisphenol-type epoxy resin as a vinyl-modified epoxy resin aqueous material having a high initial coating film hardness and hardly causing water whitening in a black coating film (patent) When the vinyl-modified epoxy resin aqueous material is used, the coating film hardness may be improved, but the coating film may become too hard. In some cases, the corrosion resistance deteriorated. Moreover, there is still room for improvement in terms of water whitening.

JP 2003-026739 A

  The present invention has a high initial coating film hardness, is less likely to cause whitening in a black coating film, has an appropriate flexibility, and does not easily crack even after long-term use, that is, has no deterioration in corrosion resistance. It aims at providing the aqueous | water-based coating agent which consists of the said vinyl modified epoxy resin aqueous material while providing a modified epoxy resin aqueous material.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has mixed a specific specific epoxy resin of different types and reacted it in the presence of a polymerizable unsaturated group-containing modified epoxy resin obtained by reaction. The present inventors have found that an aqueous dispersion salt or an aqueous solution of a reaction product obtained by polymerizing a monomer can solve the above-mentioned problems, and has completed the present invention.

  That is, the present invention provides a polymerizable unsaturated group-containing modified product obtained by reacting an aromatic epoxy resin (1a), an aliphatic epoxy resin (1b), a glycidyl group-containing vinyl monomer (1c) and an amine (1d). The copolymer (A) obtained by copolymerizing the epoxy resin (1) and the carboxyl group-containing vinyl monomer (2) is neutralized with a basic compound and dispersed or dissolved in water. The present invention relates to an aqueous vinyl-modified epoxy resin characterized by: a method for producing the aqueous product; and an aqueous coating agent containing the aqueous product.

  According to the aqueous vinyl-modified epoxy resin of the present invention, there is no deterioration in corrosion resistance, the initial coating film hardness is high, water whitening resistance in a black coating film hardly occurs, and cracking does not easily occur even after long-term use. In addition, a coating film with improved rust prevention can be obtained.

  The copolymer (A) used in the present invention is obtained by reacting an aromatic epoxy resin (1a), an aliphatic epoxy resin (1b), a glycidyl group-containing vinyl monomer (1c) and an amine (1d). Polymerized unsaturated group-containing modified epoxy resin (1) and carboxyl group-containing vinyl monomer (2) are copolymerized. In addition to the components (1a), (1b), (1c), (1d) and (2), the copolymer (A) is optionally capable of reacting with the component (1e), Another vinyl monomer (3) that can be copolymerized with the monomer (2) can be an additional component.

  As described above, the polymerizable unsaturated group-containing modified epoxy resin (1) includes the aromatic epoxy resin (1a), the aliphatic epoxy resin (1b), the glycidyl group-containing polymerizable vinyl monomer (1c), and amines. It is a reaction product composed of each component composed of (1d) and a component (1e) which can be reacted if necessary. That is, the epoxy group in the aromatic epoxy resin (1a) and the aliphatic epoxy resin (1b) is opened by the amines (1d), and at the same time, an amino group is introduced into the epoxy resin (1a). In addition, the adhesiveness, which is the original performance of the unmodified epoxy resin (1a), is further improved, and the aliphatic epoxy resin (1b) is incorporated into the molecule, so that it is suitable for the resulting modified epoxy resin (1). It is considered that the rust prevention property is improved without giving a softness, relaxing the stress generated in the coating film, and reducing the adhesion. In addition, since the glycidyl group-containing polymerizable vinyl monomer (1c) reacts with the epoxy group in the aromatic epoxy resin (1a) via the amine (1d), the polymerizable unsaturated monomer in the epoxy resin (1a) A group is introduced to impart copolymerizability.

  The aromatic epoxy resin (1a) used in the present invention is not particularly limited as long as it is an epoxy resin having an aromatic ring in the molecule, and various known ones can be used. Specifically, a bisphenol type epoxy resin, a novolac type epoxy resin, etc. are mentioned. Various known bisphenol-type epoxy resins can be used, and examples include reaction products of bisphenols and haloepoxides such as epichlorohydrin or β-methylepichlorohydrin. Examples of the bisphenols include reaction products of phenol or 2,6-dihalophenol with aldehydes or ketones such as formaldehyde, acetaldehyde, acetone, acetophenone, cyclohexanone, benzophenone, peroxides of dihydroxyphenyl sulfide, and hydroquinones. And the like. Examples of the novolak type epoxy resin include a novolak type epoxy resin obtained by a reaction between a novolak type phenol resin synthesized from phenol, cresol or the like and epichlorohydrin. The said epoxy resin can also use any 1 type independently, and can also use 2 or more types together suitably. Among these, bisphenol type epoxy resins are preferable in terms of adhesion to metal. The epoxy equivalent of the aromatic epoxy resin (1a) component is preferably 3000 or less in consideration of the molecular weight of the copolymer (A) to be obtained and workability during production. When the epoxy equivalent exceeds 3000, there is a disadvantage that the molecular weight of the obtained copolymer (A) is increased and gelation is likely to occur.

  The aliphatic epoxy resin (1b) is not particularly limited as long as it does not contain an aromatic ring in the molecule, and various known ones can be used. Specific examples include glycidyl ethers of polyhydric alcohols. Examples of the polyhydric alcohol include 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, cyclohexanedimethanol, hydrogenated bisphenol, and polyalkylene glycols. In addition, as polyalkylene glycols, well-known things, such as polyethylene glycol, polypropylene glycol, polybutylene glycol, can be used, for example. Among these, polyalkylene glycols are preferable because rust prevention due to stress relaxation of the coating film can be improved. Among the glycidyl ethers of polyalkylene glycols, when glycidyl ethers of polyethylene glycol are used, water resistance is improved, and when glycidyl ethers of polypropylene glycol are used, rust resistance is obtained. It is preferable because the improvement of the resistance is remarkable.

  In addition, when various known epoxidized oils and / or dimer acid glycidyl esters are used as a part of the above-described aliphatic epoxy resin (1b), the coating film becomes more flexible and water-whitening of the coating film is achieved. Can be further improved. Here, epoxidized oil is epoxidized natural or industrially synthesized oil, such as epoxidized soybean oil, epoxidized safflower oil, epoxidized flaxseed oil, epoxidized safflower oil, epoxidized cottonseed oil, etc. Can be illustrated. Moreover, as dimer acid glycidyl ester, the compound which has an epoxy group as a functional group formed by esterifying the carboxyl group of a well-known dimer acid with a well-known diepoxy compound can be used.

  As commercial products of epoxidized oil, for example, Adeka Sizer O-130P (epoxidized soybean oil) and Adeka Sizer O-180A (epoxidized linseed oil) (both manufactured by Asahi Denka Co., Ltd.) can be easily obtained. Moreover, as a commercial item of dimer acid glycidyl ester, Epototo YD-171,172 (both manufactured by Toto Kasei Co., Ltd.) and the like can be easily obtained.

The epoxy equivalent of the aliphatic epoxy resin (1b) component is preferably 3000 or less in consideration of the molecular weight of the copolymer (A) to be obtained and workability during production. When the epoxy equivalent exceeds 3000, there is a disadvantage that the molecular weight of the obtained copolymer (A) is increased and gelation is likely to occur.

  As the glycidyl group-containing vinyl monomer (1c), any known compound containing a glycidyl group and a polymerizable vinyl group in the molecule can be used without particular limitation. Specific examples include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (meth) allyl glycidyl ether, and the like.

  As the amines (1d), various known amines can be used without particular limitation. For example, alkanolamines, aliphatic amines, aromatic amines, alicyclic amines, aromatic nucleus-substituted aliphatic amines and the like can be mentioned, and these can be used by appropriately selecting one kind or two or more kinds. Specific examples of amines (1d) include alkanolamines such as diethanolamine, diisopropanolamine, di-2-hydroxybutylamine, N-methylethanolamine, N-ethylethanolamine, and N-benzylethanol. Examples include amines. Examples of aliphatic amines include primary amines such as ethylamine, propylamine, butylamine, hexylamine, laurylamine, stearylamine, palmitylamine, oleylamine, and erucylamine, and diethylamine, dipropylamine, and dibutylamine. Secondary amines can be mentioned. Examples of aromatic amines include toluidines, xylidines, cumidine (isopropylaniline), hexylanilines, nonylanilines, dodecylanilines and the like. Examples of the alicyclic amines include cyclopentylamines, cyclohexylamines, and norbornylamines. Examples of the aromatic nucleus-substituted aliphatic amines include benzylamine and phenethylamine.

  Moreover, in the polymerizable unsaturated group-containing modified epoxy resin (1), a reactive compound (1e) can be used as an additional component as described above. By modifying (high molecular weight) the polymerizable unsaturated group-containing modified epoxy resin (1) with the compound (1e), it is possible to adjust the dispersibility of the resulting aqueous resin in water, Workability can be further improved. Examples of the compound (1e) include monovalent to trivalent organic acids, monovalent to tetravalent alcohols, and isocyanate compounds. As the monovalent to trivalent organic acid, various known aliphatic, alicyclic or aromatic carboxylic acids 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.

  The production method of the polymerizable unsaturated group-containing modified epoxy resin (1) is not particularly limited, and various known methods can be applied. For example, the following conditions can be adopted. The use amount of the aliphatic epoxy resin (1b) is about 5 to 35% by weight of the total amount of the aromatic epoxy resin (1a) and the aliphatic epoxy resin (1b). It is preferable because flexibility can be imparted and rust prevention can be improved, and most preferable when the content is 15 to 30% by weight. When it exceeds 35% by weight, the coating film tends to be too soft, and when it is less than 5% by weight, the effect of imparting flexibility to the coating film hardly appears. In addition, when a part of the aliphatic epoxy resin (1b) is substituted with epoxidized oil and / or dimer acid glycidyl ester, the amount of epoxidized oil and / or dimer acid glycidyl ester used is changed to the aromatic epoxy resin. By making the resin (1a) and the total aliphatic epoxy resin (1b) (including epoxidized oil and / or dimer acid glycidyl ester) about 5 to 20% by weight, the coating film becomes more flexible, It is preferable because the water whitening resistance of the coating film is further improved, and is most preferable when the content is 10 to 15% by weight. If it exceeds 20% by weight, the water whitening resistance is improved, but the hardness and corrosion resistance of the coating film tend to be reduced, and if it is less than 5% by weight, the effect of imparting water whitening resistance is hardly exhibited. Moreover, the usage-amount ratio of the glycidyl group containing vinyl monomer (1c), amines (1d), and the other reactable compound (1e) is set to the following ranges, respectively. That is, the equivalent amount of active hydrogen derived from the amino group of the amines (1d) is 90 to 100 equivalents with respect to 100 equivalents of the total amount of epoxy groups contained in the aromatic epoxy resin (1a) and the glycidyl group-containing vinyl monomer (1c). It is preferable to use so that it may become about 110 equivalent. The epoxy equivalent of the glycidyl group-containing vinyl monomer (1c) is about 1 to 25 equivalents relative to 100 equivalents of the epoxy group of the aromatic epoxy resin (1a) and the aliphatic epoxy resin (1b). Is preferred. When the epoxy equivalent of the glycidyl group-containing vinyl monomer (1c) is less than 1, the storage stability of the modified epoxy resin aqueous product of the present invention is lowered, and when it exceeds 25, the modified epoxy resin (1) is produced. Sometimes it tends to gel. Moreover, the other compound (1e) which can react can be used as needed in the range which does not impair the effect of this invention.

The polymerizable unsaturated group-containing modified epoxy resin (1) can be easily produced by heating each of the above components in the presence of the following organic solvent. The reaction temperature is usually about 60 to 200 ° C., but if the reaction temperature is too low, an unreacted epoxy group tends to remain, and preferably 80 ° C. or higher. On the other hand, if the reaction temperature is too high, the reaction product is easily gelled due to the ring-opening reaction between the epoxy group in the modified epoxy resin (1) and the hydroxyl group in the other component or the ring-opening reaction between the epoxy groups. Therefore, the temperature is preferably 150 ° C. or lower. Moreover, although reaction time is dependent on reaction temperature, it is good to set it as 3 to 10 hours on the said temperature conditions.

  As the organic solvent, it is desirable to use a hydrophilic solvent from the viewpoint of making the finally obtained vinyl-modified epoxy resin aqueous. Specifically, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n -Butyl ether, propylene glycol mono-t-butyl ether, methyl cellosolve, ethyl cellosolve, n-butyl cellosolve, t-butyl cellosolve, isopropyl alcohol, butyl alcohol and the like.

  The copolymer (A) used in the present invention comprises a polymerizable unsaturated group-containing modified epoxy resin (1) obtained as described above, a carboxyl group-containing vinyl monomer (2), and, if necessary, It is produced by copolymerizing the monomer (2) with another vinyl monomer (3) that can be copolymerized. The copolymer (A) in the present invention corresponds to a vinyl graft-amine modified epoxy resin. In the present invention, the polymerizable unsaturated group of the polymerizable unsaturated group-containing modified epoxy resin (1) is copolymerized with the carboxyl group-containing vinyl monomer (2) and, if necessary, another monomer (3). It is important to produce a graft body. By such grafting, it is possible to obtain a copolymer (A) that can be stably dispersed or dissolved in water while maintaining high corrosion resistance and adhesion, which are the original properties of the epoxy resin (1a).

  Examples of the carboxyl group-containing vinyl monomer (2) copolymerized with the polymerizable unsaturated group-containing modified epoxy resin (1) include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. And carboxyl group-containing vinyl monomers. Other vinyl monomers (3) that are optional components that can be copolymerized with the carboxyl group-containing vinyl monomer (2) include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, and acrylic acid. acrylic esters such as n-butyl, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, Methacrylic acid esters such as tert-butyl methacrylate and 2-ethylhexyl methacrylate; Styrene vinyl monomers such as styrene, vinyltoluene and α-methylstyrene; Others, vinyl acetate, β-hydroxyethyl acrylate, acrylic acid Glycidyl, glycidyl methacrylate, a Examples include chloramide, N, N-diethylmethacrylamide, acrylonitrile, methacrylonitrile and the like. These vinyl monomers (2) and (3) can be used alone or in combination of two or more.

  The carboxyl group-containing vinyl monomer (2) is essential for facilitating aqueous formation (stable water dispersion or dissolution) of the resulting vinyl-modified epoxy resin. Therefore, the amount of the carboxyl group-containing vinyl monomer (2) used is determined from the viewpoint of making the resulting vinyl-modified epoxy resin aqueous, and the solid content acid value of the vinyl-modified epoxy resin is 15 or more, more preferably 20 or more. It is preferable to adjust so that. On the other hand, in order to impart good water resistance and corrosion resistance to the vinyl-modified epoxy resin, it is preferable to adjust the amount used so that the solid content acid value of the vinyl-modified epoxy resin is 45 or less, and further 40 or less. In addition, even when other vinyl monomer (3), which is an optional component, is used in combination with the carboxyl group-containing vinyl monomer (2), from the same viewpoint as described above, the amount of both these components can be determined, It is preferable to adjust the solid content acid value of the resulting vinyl-modified epoxy resin as appropriate within the same range as described above.

  In the copolymerization of the polymerizable unsaturated group-containing modified epoxy resin (1) with the carboxyl group-containing vinyl monomer (2) and, if necessary, other vinyl monomers (3), the polymerization initiator used is particularly There is no restriction | limiting, A well-known various organic peroxide and an azo compound can be used. Examples include benzoyl peroxide, tert-butyl peroctoate, 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), and the like.

  The copolymerization is not limited to a polymerization mode, but a solution polymerization method is preferable. For example, the polymerization can be performed at a reaction temperature of about 60 to 150 ° C. in the presence of the polymerization initiator as described above. About the organic solvent, the thing similar to what was used in manufacture of the said polymerizable unsaturated group containing modified epoxy resin (1) can be used. Polymerized unsaturated group-containing modified epoxy resin (1), carboxyl group-containing vinyl monomer (2), and other vinyl monomer (3) in use weight ratio ((1) / [(2) + (3 )]) Can be appropriately determined in view of the solid content acid value of the copolymer (A) obtained as described above, but is usually within the range of 99/1 to 80/20. If the amount of the monomer used is less than the lower limit, water dispersibility or water solubility becomes unstable and precipitation tends to occur in the product. On the other hand, if the vinyl monomer exceeds the upper limit, adhesion and corrosion resistance, which are the original characteristics of the vinyl-modified epoxy resin, are likely to be lowered.

  The copolymer (A) thus obtained is neutralized with a basic compound and dissolved or dispersed in water to give the intended aqueous vinyl-modified epoxy resin. That is, it is preferable to neutralize all or part of the carboxyl groups derived from the vinyl monomer (2) in the copolymer (A) so that the pH is about 7 to 10. As the basic compound which is a neutralizing agent, amines such as ammonia, triethylamine and dimethylethanolamine, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, etc. can be used. In view of volatility, ammonia and amines are preferable.

  The aqueous vinyl-modified epoxy resin of the present invention can be used in various applications as an aqueous coating agent (for example, coating agents such as paints and adhesives) for various materials such as wood, paper, fiber, plastic, ceramic, iron, and non-ferrous metals. . In application to various applications, it can be diluted with water and used as it is, and if necessary, pigments, plasticizers, solvents, colorants, antifoaming agents, etc. can be added, or other water-soluble or water-dispersible resins Can also be blended.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1
In a reactor equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas introduction tube, 125 g of butyl cellosolve, 210 g of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950), polyethylene glycol diglycidyl After adding 75 g of ether (Nagase Kasei Kogyo Co., Ltd .: Denacol EX-841) and 6.5 g of glycidyl methacrylate and dissolving at 100 ° C. under a nitrogen stream, 22.0 g of octylamine and 14.7 g of dibutylamine were added for 5 hours. Reaction was carried out to obtain a polymerizable unsaturated group-containing modified epoxy resin. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 500 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 1200 mPa · s, a pH of 9.7, and a solid content acid value of 31.

Example 2
In the same reactor as in Example 1, 125 g of butyl cellosolve, 210 g of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950), polyethylene glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd.): After adding 75 g of Denacol EX-841) and 6.5 g of glycidyl methacrylate and dissolving at 100 ° C. under a nitrogen stream, 14.7 g of octylamine, 3.5 g of monoethanolamine and 14.7 g of dibutylamine were added and reacted for 5 hours. Further, 5.0 g of hexamethylene diisocyanate was added and reacted for 5 hours to obtain a polymerizable unsaturated group-containing modified epoxy resin. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 495 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 2100 mPa · s, a pH of 9.7, and a solid content acid value of 30.

Example 3
In the same reactor as in Example 1, 125 g of butyl cellosolve, 188 g of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-017, epoxy equivalent 1950), polyethylene glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd.): After adding 97 g of Denacol EX-841) and 6.0 g of glycidyl methacrylate and dissolving at 100 ° C. under a nitrogen stream, 18.6 g of octylamine and 12.4 g of dibutylamine were added and reacted for 5 hours to modify the polymerizable unsaturated group. An epoxy resin was obtained. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 485 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 2000 mPa · s, a pH of 9.7, and a solid content acid value of 32.

Example 4
In the same reactor as in Example 1, 125 g of butyl cellosolve, 210 g of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950), polypropylene glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd.): After adding 75 g of Denacol EX-931) and 6.5 g of glycidyl methacrylate and dissolving at 100 ° C. under a nitrogen stream, 19.8 g of octylamine and 13.2 g of dibutylamine were added and reacted for 5 hours to modify the polymerizable unsaturated group. An epoxy resin was obtained. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 485 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 800 mPa · s, a pH of 9.7, and a solid content acid value of 31.

Example 5
In the same reactor as in Example 1, 125 g of butyl cellosolve, 210 g of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950), polypropylene glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd.): After adding 75 g of Denacol EX-921) and 6.5 g of glycidyl methacrylate and dissolving at 100 ° C. under a nitrogen stream, 30.6 g of octylamine and 20.4 g of dibutylamine were added and reacted for 5 hours to contain a polymerizable unsaturated group-containing modification. An epoxy resin was obtained. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 500 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 1200 mPa · s, a pH of 9.7, and a solid content acid value of 30.

Example 6
In the same reactor as in Example 1, 125 g of butyl cellosolve, 210 g of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950), 1,6-hexanediol diglycidyl ether (Nagase Chemical Industries) Co., Ltd .: 75 g of Denacol EX-212) and 6.5 g of glycidyl methacrylate were added and dissolved at 100 ° C. under a nitrogen stream, and then 37.1 g of octylamine and 24.7 g of dibutylamine were added and reacted for 5 hours. A saturated group-containing modified epoxy resin was obtained. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 540 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 1600 mPa · s, a pH of 9.7, and a solid content acid value of 29.

Example 7
In the same reactor as in Example 1, 125 g of butyl cellosolve, 180 g of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950), polyethylene glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd.): Denacol EX-841) and 105 g of glycidyl methacrylate were added and dissolved at 100 ° C. under a nitrogen stream. Then, 24.3 g of octylamine and 16.2 g of dibutylamine were added and reacted for 5 hours to contain a polymerizable unsaturated group. An epoxy resin was obtained. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 500 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 700 mPa · s, a pH of 9.7, and a solid content acid value of 32.

Example 8
In the same reactor as in Example 1, butyl cellosolve 125 g, bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950), 191 g, polyethylene glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd.): 94 g of Denacol EX-841) and 6.5 g of glycidyl methacrylate were added and dissolved at 100 ° C. under a nitrogen stream. Then, 23.5 g of octylamine and 15.7 g of dibutylamine were added and reacted for 5 hours to contain a polymerizable unsaturated group-containing modification. An epoxy resin was obtained. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 495 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 750 mPa · s, a pH of 9.7, and a solid content acid value of 32.

Example 9
In the same reaction apparatus as in Example 1, butyl cellosolve 125 g, bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950) 228 g, polyethylene glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd.): After adding 57 g of Denacol EX-841) and 6.5 g of glycidyl methacrylate and dissolving at 100 ° C. under a nitrogen stream, 20.8 g of octylamine and 13.9 g of dibutylamine were added and reacted for 5 hours to modify the polymerizable unsaturated group. An epoxy resin was obtained. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 490 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 950 mPa · s, a pH of 9.7, and a solid content acid value of 33.

Example 10
In the same reactor as in Example 1, 125 g of butyl cellosolve, 265 g of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950), polyethylene glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd.): 20 g of Denacol EX-841) and 6.5 g of glycidyl methacrylate were added and dissolved at 100 ° C. under a nitrogen stream. Then, 18.2 g of octylamine and 12.1 g of dibutylamine were added and reacted for 5 hours to modify the polymerizable unsaturated group. An epoxy resin was obtained. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 480 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 1050 mPa · s, a pH of 9.7, and a solid content acid value of 33.

Example 11
In the same reactor as in Example 1, 125 g of butyl cellosolve, 275 g of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950), polyethylene glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd.): After adding 10 g of Denacol EX-841) and 6.5 g of glycidyl methacrylate and dissolving at 100 ° C. under a nitrogen stream, 17.4 g of octylamine and 11.6 g of dibutylamine were added and reacted for 5 hours to modify the polymerizable unsaturated group. An epoxy resin was obtained. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 480 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 1200 mPa · s, a pH of 9.7, and a solid content acid value of 33.

Example 12
In the same reactor as in Example 1, 125 g of butyl cellosolve, 210 g of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950), polyethylene glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd.): 35 g of Denacol EX-841), 40 g of epoxidized oil (Asahi Denka Co., Ltd .: Adeka Sizer O-130P) and 6.5 g of glycidyl methacrylate were added and dissolved at 100 ° C. under a nitrogen stream, and then 31.4 g of octylamine, 21.0 g of butylamine was added and reacted for 5 hours to obtain a polymerizable unsaturated group-containing modified epoxy resin. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 430 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 39.0%, a viscosity of 950 mPa · s, a pH of 9.7, and a solid content acid value of 31.

Example 13
In the same reactor as in Example 1, 125 g of butyl cellosolve, 210 g of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950), polyethylene glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd.): After adding 35 g of Denacol EX-841), 40 g of dimer acid glycidyl ester (Toto Kasei Co., Ltd .: Epototo YD-171) and 6.5 g of glycidyl methacrylate and dissolving at 100 ° C. under a nitrogen stream, 22.0 g of octylamine, 14.6 g of butylamine was added and reacted for 5 hours to obtain a polymerizable unsaturated group-containing modified epoxy resin. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 450 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 37.0%, a viscosity of 1200 mPa · s, a pH of 9.7, and a solid content acid value of 33.

Example 14
In the same reactor as in Example 1, 125 g of butyl cellosolve, 210 g of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950), polyethylene glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd.): 35 g of Denacol EX-841), 20 g of epoxidized oil (Asahi Denka Co., Ltd .: Adeka Sizer O-130P), 20 g of dimer acid glycidyl ester (Toto Kasei Co., Ltd .: Epototo YD-171) and 6.5 g of glycidyl methacrylate are added. After dissolving at 100 ° C. under a nitrogen stream, 26.7 g of octylamine and 17.8 g of dibutylamine were added and reacted for 5 hours to obtain a polymerizable unsaturated group-containing modified epoxy resin. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 450 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 37.0%, a viscosity of 1050 mPa · s, a pH of 9.7, and a solid content acid value of 32.

Example 15
In the same reactor as in Example 1, 125 g of butyl cellosolve, 210 g of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950), polyethylene glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd.): After adding 10 g of Denacol EX-841), 60 g of epoxidized oil (Asahi Denka Co., Ltd .: Adeka Sizer O-130P) and 6.5 g of glycidyl methacrylate, the mixture was dissolved at 100 ° C. under a nitrogen stream, and then 33.6 g of octylamine, 16.7 g of butylamine was added and reacted for 5 hours to obtain a polymerizable unsaturated group-containing modified epoxy resin. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 430 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 38.0%, a viscosity of 850 mPa · s, a pH of 9.7, and a solid content acid value of 31.

Example 16
In the same reactor as in Example 1, 125 g of butyl cellosolve, 210 g of bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd .: Epototo YD-014, epoxy equivalent 950), polyethylene glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd.): 10 g of Denacol EX-841), 60 g of dimer acid glycidyl ester (Toto Kasei Co., Ltd .: Epototo YD-171) and 6.5 g of glycidyl methacrylate were dissolved at 100 ° C. under a nitrogen stream, and then 21.0 g of octylamine, 14.0 g of butylamine was added and reacted for 5 hours to obtain a polymerizable unsaturated group-containing modified epoxy resin. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 450 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 37.0%, a viscosity of 1100 mPa · s, a pH of 9.7, and a solid content acid value of 33.

Comparative Example 1
120 g of butyl cellosolve, 285 g of bisphenol A type epoxy resin (Etototo YD-014, epoxy equivalent 950) and 6.0 g of glycidyl methacrylate were added to the same reactor as in Example 1 at 100 ° C. under a nitrogen stream. After dissolution, 16.6 g of octylamine and 11.0 g of dibutylamine were added and reacted for 5 hours to obtain a polymerizable unsaturated group-containing modified epoxy resin. Then, a mixture consisting of 16 g of acrylic acid, 10 g of styrene, 10 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour and kept warm for 4 hours. . After cooling to 80 ° C., 21 g of triethylamine and 470 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 800 mPa · s, a pH of 9.7, and a solid content acid value of 33.

Comparative Example 2
125 g of butyl cellosolve, 280 g of polyethylene glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd .: Denacol EX-841) and 6.5 g of glycidyl methacrylate were added to the same reactor as in Example 1 and dissolved at 100 ° C. in a nitrogen stream. Then, 36.6 g of octylamine and 24.4 g of dibutylamine were added and reacted for 5 hours to obtain a polymerizable unsaturated group-containing modified epoxy resin. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 520 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 350 mPa · s, a pH of 9.7, and a solid content acid value of 30.

Comparative Example 3
125 g of butyl cellosolve, 280 g of polypropylene glycol diglycidyl ether (Nagase Kasei Kogyo Co., Ltd .: Denacol EX-931) and 6.5 g of glycidyl methacrylate were added to the same reactor as in Example 1 and dissolved at 100 ° C. in a nitrogen stream. Then, 27.9 g of octylamine and 18.6 g of dibutylamine were added and reacted for 5 hours to obtain a polymerizable unsaturated group-containing modified epoxy resin. Then, a mixture of 16 g of acrylic acid, 10.0 g of styrene, 10.0 g of butyl acrylate, 40 g of butyl cellosolve and 3 g of tert-butylperoxy-2-ethylhexanoate was dropped into the reaction system over 1 hour. Incubated for 4 hours. After cooling to 80 ° C., 21 g of triethylamine and 500 g of water were sequentially added and mixed to obtain an aqueous dispersion having a non-volatile content of 35.0%, a viscosity of 450 mPa · s, a pH of 9.7, and a solid content acid value of 31.

Table 1 shows the aromatic epoxy resin (1a) and aliphatic epoxy resin (1b) (epoxidized oil and / or dimer acid glycidyl ester and other fats used in Examples 1-15 and Comparative Examples 1-3. Of the aliphatic epoxy resin (1b) with respect to the total amount of (1a) and (1b), and the total amount of (1a) and (1b). The amount (% by weight) of epoxidized oil and / or dimer acid glycidyl ester is shown.

  Water-based paints were prepared from the vinyl-modified epoxy resin aqueous materials obtained in the above Examples and Comparative Examples by the following formulation, and the performance of the coating films obtained from the paints was evaluated by the following methods. The evaluation results are shown in Table 1.

(Preparation of water-based paint)
A mixture of 44.6 g of an aqueous vinyl-modified epoxy resin, 1.8 g of carbon black, 5.6 g of zinc phosphate, 23.8 g of calcium carbonate, 1.8 g of deionized water, and 80 g of glass beads, was mixed for 1 hour 30 with a paint shaker. Kneaded. Thereafter, 23 g of an aqueous dispersion of vinyl-modified epoxy resin was mixed, and then glass beads were removed to obtain an aqueous paint. In addition, when any vinyl-modified epoxy resin aqueous material is used, the PWC (pigment weight concentration) of the aqueous paint is 57%, and the paint concentration is 53.2% (solvent amount 10.2%). did. 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 after drying was 20 μm, and forced drying (80 ° C. × 20 minutes), and left at room temperature (20 ° C., 60% RH) for 5 days.

(Evaluation test of coating film)

  Coating hardness: Conforms to JIS K5400.

  Corrosion resistance: Performed according to JIS K5400, and indicated by cellophane tape peel width (mm) after 10 days and 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 (trade name “SZII-Σ80 TYPE III”, 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 Judged on the basis of no.

＊表中、“テープ幅”はテープ貼り付け部分がすべて剥離したことを示す。

* In the table, “tape width” indicates that the tape application part has all peeled off.

Claims (10)

A polymerizable unsaturated group-containing modified epoxy resin (1) obtained by reacting an aromatic epoxy resin (1a), an aliphatic epoxy resin (1b), a glycidyl group-containing vinyl monomer (1c) and an amine (1d); A vinyl-modified epoxy characterized in that a copolymer (A) obtained by copolymerizing a carboxyl group-containing vinyl monomer (2) is neutralized with a basic compound and dispersed or dissolved in water. Resin aqueous. The aqueous vinyl-modified epoxy resin according to claim 1, wherein the polymerizable unsaturated group-containing modified epoxy resin (1) is a compound (1e) capable of reacting as an additional component. The aqueous vinyl-modified epoxy resin according to claim 1 or 2, wherein a part of the aliphatic epoxy resin (1b) is substituted with an epoxidized oil and / or a dimer acid glycidyl ester. The amount of the aliphatic epoxy resin (1b) used is 5 to 35% by weight of the total amount of the aromatic epoxy resin (1a) and the aliphatic epoxy resin (1b). Vinyl-modified epoxy resin aqueous product. The vinyl according to claim 3 or 4, wherein the amount of the epoxidized oil and / or dimer acid glycidyl ester is 5 to 20% by weight of the total amount of the aromatic epoxy resin (1a) and the aliphatic epoxy resin (1b). Modified epoxy resin aqueous product. The additional vinyl monomer (3) copolymerizable with the monomer (2) is used as an additional component of the polymerizable unsaturated group-containing modified epoxy resin (1). The aqueous vinyl-modified epoxy resin according to any one of 5 above. The copolymer (A) is used in a weight ratio of the polymerizable unsaturated group-containing modified epoxy resin (1) to the carboxyl group-containing vinyl monomer (2) and the other vinyl monomer (3) ((1) / [(2) + (3)]) in the range of 99/1 to 80/20. The vinyl-modified epoxy resin aqueous product according to any one of claims 1 to 6. The vinyl-modified epoxy resin aqueous product according to any one of claims 1 to 7, wherein the copolymer (A) has an acid value (in terms of solid content) in the range of 15 to 45. A polymerizable unsaturated group-containing modified epoxy resin (1) obtained by reacting an aromatic epoxy resin (1a), an aliphatic epoxy resin (1b), a glycidyl group-containing vinyl monomer (1c) and an amine (1d); An aqueous vinyl-modified epoxy resin, characterized in that a copolymer (A) obtained by copolymerizing a carboxyl group-containing vinyl monomer (2) is neutralized with a basic compound and dispersed or dissolved in water. Manufacturing method. An aqueous coating agent comprising the aqueous vinyl-modified epoxy resin according to any one of claims 1 to 8.


















Indicates.