Epoxy ester resin, vinyl-modified epoxy ester resin, resin composition, paint, and article coated with said paint

Abstract

To provide an epoxy ester resin and a vinyl-modified epoxy ester resin capable of obtaining a resin composition in which a pigment is sufficiently dispersed even when a pigment having low dispersibility is used and forming a coating film having excellent gloss.SOLUTION: There are provided an epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure and a vinyl-modified epoxy ester resin having a condensed alicyclic structure containing the epoxy ester resin and a polymerizable monomer as reaction components, wherein the mass ratio [epoxy ester resin:polymerizable monomer] of the epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure to the polymerizable monomer is in the range of 20:80 to 80:20.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an epoxy ester resin, a vinyl-modified epoxy ester resin, a resin composition, a paint, and an article coated with the paint. [Background technology]

[0002] As a measure to combat air pollution, regulations on volatile organic compounds (VOCs) are being strengthened in the United States, Europe, China, and other countries. As a result, paints that use large amounts of volatile organic compounds such as toluene, xylene, and ethyl acetate as solvents are being required to be water-based, eliminating or reducing the use of these organic solvents.

[0003] While there is a demand for water-based paints, paints used on buildings, ships, aircraft, etc., are exposed to rainwater, so they need to be water-resistant and corrosion-resistant.In addition, when painted outdoors, they need to be able to dry at room temperature without the need for heating.

[0004] A room-temperature drying water-based paint that can be used for buildings, ships, aircraft, etc. has been proposed, in which carbon-carbon unsaturated double bonds in the resin skeleton are oxidatively polymerized with a metal complex compound (Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-124658 Summary of the Invention [Problem to be solved by the invention]

[0006] Water-based paints are paints in which resins are dissolved or dispersed in an aqueous medium, but they generally have inferior drying and corrosion resistance compared to solvent-based paints. Therefore, extender pigments such as calcium carbonate are often blended to improve drying speed, and anti-rust pigments such as metal chromates and metal phosphates are often blended to improve corrosion resistance.

[0007] However, extender pigments and anti-rust pigments have poor dispersibility, and when extender pigments and / or anti-rust pigments are used in water-based paints, the pigment dispersion is insufficient, resulting in fine irregularities on the paint surface and a decrease in the paint gloss. There are also problems with stability over time, such as the pigment components in the paint settling and separating during storage. This problem is not limited to water-based paints, but also occurs in solvent-based paints.

[0008] The problem to be solved by the present invention is to provide an epoxy ester resin and a vinyl-modified epoxy ester resin which can obtain a resin composition in which the pigment is sufficiently dispersed even when a pigment with low dispersibility is used, and which can form a coating film having excellent gloss and / or corrosion resistance. Another problem to be solved by the present invention is to provide a resin composition and a coating material that can form a coating film that is excellent in gloss and / or corrosion resistance. [Means for solving the problem]

[0009] As a result of intensive investigations to solve the above problems, the present inventors have found that by using an epoxy ester resin having a fused alicyclic structure introduced therein, a resin composition in which even a pigment with low dispersibility is sufficiently dispersed can be obtained, and have thus completed the present invention.

[0010] That is, the present invention relates to (1) an epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure, and (2) a vinyl-modified epoxy ester resin having a condensed alicyclic structure, in which the epoxy ester resin and a polymerizable monomer are reactants, and the mass ratio of the epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure to the polymerizable monomer [epoxy ester resin:polymerizable monomer] is in the range of 20:80 to 80:20. [Effects of the Invention]

[0011] According to the present invention, a resin composition in which the pigment is sufficiently dispersed can be obtained even when a pigment with low dispersibility is used, and an epoxy ester resin and a vinyl-modified epoxy ester resin capable of forming a coating film with excellent gloss and / or corrosion resistance can be provided. The present invention can provide a resin composition and a coating material that can form a coating film that is excellent in gloss and / or corrosion resistance. DETAILED DESCRIPTION OF THE INVENTION

[0012] An embodiment of the present invention will be described below. The present invention is not limited to the following embodiment, and can be implemented by making appropriate modifications within the scope that does not impair the effects of the present invention.

[0013] [Epoxy ester resin] The epoxy ester resin of the present invention is an epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure. As the epoxy ester resin used in the coating material, a bisphenol type epoxy ester resin is generally used, but in the present invention, by using an epoxy ester resin having a condensed alicyclic structure, it is possible to improve the pigment dispersibility.

[0014] The epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure of the present invention is preferably a reaction product of an epoxy resin having a condensed alicyclic structure with an unsaturated fatty acid, or a reaction product of an epoxy resin having a condensed alicyclic structure with an unsaturated fatty acid and a polycarboxylic acid.

[0015] In condensed alicyclic structures such as those of dicyclopentadiene, tricyclodecane (tetrahydrodicyclopentadiene), norbornene, adamantane, and tetrahydroindene, adjacent ring structures are generally bent, and it is presumed that the condensed alicyclic structures of epoxy ester resins obtained by reacting monomers having these structures are efficiently adsorbed onto the surface of pigment particles, thereby improving pigment dispersibility. It is presumed that the two benzene rings of the bisphenol structure repel each other due to steric hindrance, which is why they are only partially adsorbed to the pigment particles.

[0016] The epoxy resin is a resin having at least one epoxy group in the molecule, and the epoxy resin having a condensed alicyclic structure is preferably a dicyclopentadiene-type epoxy resin having a dicyclopentadiene structure. In the present application, the term "dicyclopentadiene-type epoxy resin" refers to an epoxy resin having a plurality of epoxy groups and a tricyclodecane (tetrahydrodicyclopentadiene) skeleton derived from dicyclopentadiene in the molecule.

[0017] The dicyclopentadiene type epoxy resin is preferably a dicyclopentadiene type epoxy resin represented by the following general formula (1).

[0018] [ka] (In the general formula (1), R 1 , R 2 and R 3 are each independently an alkyl group having 1 to 6 carbon atoms, n1, n2, and n3 each independently represent an integer of 0 to 3, n is the number of repetitions.)

[0019] The dicyclopentadiene-type epoxy resin represented by general formula (1) can be produced, for example, by polymerizing dicyclopentadiene with a phenolic compound and reacting the resulting polymer with a halogenated epoxy compound such as epichlorohydrin.

[0020] The epoxy equivalent of the epoxy resin having a condensed alicyclic structure is preferably in the range of 200 to 2,000 g / equivalent, and more preferably in the range of 300 to 1,500 g / equivalent. The epoxy equivalent is the weight of the epoxy resin required to obtain 1 mole of epoxy groups, and when a mixture of two or more epoxy resins is used as the epoxy resin, it is preferable that the epoxy equivalent of the mixture is within the above range.

[0021] The epoxy resin having a condensed alicyclic structure preferably does not contain a bisphenol structure. Bisphenol-type epoxy resins are suspected of being endocrine disruptors, and this suspicion can be avoided by not using epoxy resins containing bisphenol structures.

[0022] The epoxy resin having a condensed alicyclic structure may be a commercially available product, and examples of such commercially available products include dicyclopentadiene-type epoxy resins such as EPICLON HP-7200 series (manufactured by DIC Corporation) and TACTIX 556 and 756 (both manufactured by HUNTSMAN).

[0023] The unsaturated fatty acid is preferably an unsaturated aliphatic monocarboxylic acid, more preferably an unsaturated aliphatic monocarboxylic acid having 6 to 40 carbon atoms, and even more preferably an unsaturated aliphatic monocarboxylic acid having 10 to 22 carbon atoms. The degree of unsaturation of the unsaturated fatty acid is not particularly limited, but is in the range of 1 to 3, for example.

[0024] The unsaturated fatty acids may be used alone or in combination of two or more. In addition, saturated fatty acids may be used in combination with unsaturated fatty acids.

[0025] Specific examples of unsaturated fatty acids include sorbic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinoleic acid, tung oil fatty acid, linseed oil fatty acid, dehydrated castor oil fatty acid, castor oil fatty acid, tall oil fatty acid, cottonseed oil fatty acid, soybean oil fatty acid, olive oil fatty acid, safflower oil fatty acid, and rice bran oil fatty acid. Tung oil fatty acids, linseed oil fatty acids, dehydrated castor oil fatty acids, castor oil fatty acids, tall oil fatty acids, cottonseed oil fatty acids, soybean oil fatty acids, olive oil fatty acids, safflower oil fatty acids, and rice bran oil fatty acids are mixtures of unsaturated aliphatic monocarboxylic acids having 10 to 22 carbon atoms.

[0026] The unsaturated fatty acid may be either a naturally occurring unsaturated fatty acid or a synthetic unsaturated fatty acid (including a fatty acid that is not naturally occurring).

[0027] From the viewpoint of obtaining a water-based coating material that is excellent in oxidative polymerization properties when used with a metal dryer, the unsaturated fatty acid is preferably a semi-drying oil or a drying oil having an iodine value in the range of 120-200.

[0028] The amount of unsaturated fatty acid used is, for example, in the range of 10 to 60 parts by mass, and preferably in the range of 20 to 45 parts by mass, relative to 100 parts by mass of the epoxy resin.

[0029] As a reactive component of the epoxy ester resin, a polycarboxylic acid may be used in addition to the epoxy resin and the unsaturated fatty acid. Epoxy ester resins, which are reaction products of epoxy resins, unsaturated fatty acids, and polycarboxylic acids, undergo polymer chain extension through the reaction between the carboxyl groups of the polycarboxylic acids and the epoxy groups of the epoxy resins, making it possible to control the molecular weight.

[0030] Examples of the polycarboxylic acid include phthalic acid (anhydride), isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, tetrachlorophthalic acid, 1,1-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, HET acid, 5-norbornene-2,3-dicarboxylic acid, hydrogenated trimellitic acid, adipic acid, azelaic acid, sebacic acid, maleic acid (anhydride), fumaric acid, and itaconic acid. The polycarboxylic acid may be used alone or in combination of two or more thereof. Furthermore, a derivative of a polycarboxylic acid such as an acid anhydride may also be used as the polycarboxylic acid.

[0031] When a polycarboxylic acid is used as a reaction component, the amount of the polycarboxylic acid used is, for example, 10 parts by mass or less, and preferably 6 parts by mass or less, relative to 100 parts by mass of the epoxy resin. The lower limit of the amount of the polycarboxylic acid used is not particularly limited, but is, for example, 1 part by mass or more relative to 100 parts by mass of the epoxy resin.

[0032] In the reaction components of the epoxy ester resin, the molar ratio of the epoxy groups of the epoxy resin having a condensed alicyclic structure to the total carboxyl groups of the unsaturated fatty acid and polycarboxylic acid [epoxy groups:carboxyl groups] is preferably in the range of 1:1 to 1:2. By ensuring that the molar ratio of epoxy groups to carboxyl groups is within the above range, both the pigment dispersibility and coating drying properties of the resulting epoxy ester resin can be ensured.

[0033] The epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure may contain an epoxy resin having a condensed alicyclic structure, an unsaturated fatty acid, and optionally a polycarboxylic acid as reaction components, but other components may also be used as reaction components.

[0034] The acid value of the epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure is, for example, in the range of 2 to 15 mgKOH / g, and preferably in the range of 4 to 10 mgKOH / g. The acid value of the epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure is evaluated by the method described in the examples.

[0035] The molecular weight of the epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure is not particularly limited, but for example, the weight average molecular weight is in the range of 3,000 to 20,000. The weight average molecular weight of the epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure is evaluated by the method described in the examples.

[0036] The reaction of the epoxy resin having a condensed alicyclic structure, the unsaturated fatty acid, and the optional polycarboxylic acid can be carried out by a known method. For example, the epoxy ester resin of the present invention can be prepared by heating a reaction system containing the epoxy resin, the unsaturated fatty acid, and the optional polycarboxylic acid.

[0037] [Vinyl-modified epoxy ester resin] The vinyl-modified epoxy ester resin of the present invention is a resin obtained by reacting the epoxy ester resin having the above-mentioned polymerizable unsaturated group and condensed alicyclic structure with a polymerizable monomer as reaction components. Here, "reaction components" means components that constitute the vinyl-modified epoxy ester resin, and does not include solvents or catalysts that do not constitute the vinyl-modified epoxy ester resin.

[0038] The polymerizable monomer means a compound having a polymerizable unsaturated group, and examples of the polymerizable unsaturated group of the monomer include a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinyl ether group, an allyl group, a styryl group, a (meth)acryloylamide group, a maleimide group, etc. Among these, a (meth)acryloyl group, a (meth)acryloyloxy group, or a styryl group is preferred because of the ease of availability of raw materials and good polymerization reactivity.

[0039] The polymerizable monomers may be used alone or in combination of two or more.

[0040] The polymerizable monomer preferably includes a polymerizable monomer having an acidic functional group. By using a polymerizable monomer having an acidic functional group as the polymerizable monomer, the amine compound described below reacts with the acidic functional group to form a neutralized salt structure, thereby imparting water solubility to the vinyl-modified epoxy ester resin.

[0041] Examples of polymerizable monomers having an acidic functional group include polymerizable monomers having a carboxyl group, such as (meth)acrylic acid, crotonic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, and acryloyloxycaprolactonic acid; polymerizable monomers having a phosphoric acid group, such as 2-(meth)acryloyloxyethyl acid phosphate, 3-(meth)acryloyloxypropyl acid phosphate, (meth)acryloyloxypolyoxyethylene glycol acid phosphate, and (meth)acryloyloxypolyoxypropylene glycol acid phosphate; and monomers having a sulfonic acid group, such as vinyl sulfonic acid. The polymerizable monomer having an acidic functional group also includes derivatives such as acid anhydrides.

[0042] When a polymerizable monomer having an acidic functional group is contained as the polymerizable monomer, the content of the polymerizable monomer having an acidic functional group is, for example, in the range of 1 to 50 mass %, and preferably 3 to 40 mass %, of the total amount of polymerizable monomers.

[0043] As the polymerizable monomer, a polymerizable monomer having a group containing a polyoxyalkylene chain may be used. Since the polyoxyalkylene chain exhibits hydrophilicity, the hydrophilicity of the vinyl-modified epoxy ester resin can be adjusted by using a polymerizable monomer having a group containing a polyoxyalkylene chain.

[0044] Examples of polymerizable monomers having a group containing a polyoxyalkylene chain and in which the polymerizable unsaturated group is a (meth)acryloyl group include polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polytrimethylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol·propylene glycol) mono(meth)acrylate, polyethylene glycol·polypropylene glycol mono(meth)acrylate, poly(ethylene glycol·tetramethylene glycol) mono(meth)acrylate, polyethylene glycol·polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol·tetramethylene glycol) mono(meth)acrylate, polypropylene glycol·polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol·1,2-butylene glycol) mono(meth)acrylate, polypropylene glycol·poly1,2-butylene glycol mono(meth)acrylate, (Ethylene glycol·1,2-butylene glycol) mono(meth)acrylate, polyethylene glycol·poly 1,2-butylene glycol mono(meth)acrylate, poly(tetraethylene glycol·1,2-butylene glycol) mono(meth)acrylate, polytetraethylene glycol·poly 1,2-butylene glycol mono(meth)acrylate, poly 1,2-butylene glycol mono(meth)acrylate, poly(ethylene glycol·trimethylene glycol) mono(meth)acrylate, polyethylene glycol Licor·Polytrimethylene glycol mono(meth)acrylate, Poly(propylene glycol·trimethylene glycol) mono(meth)acrylate, Polypropylene glycol·Polytrimethylene glycol mono(meth)acrylate, Poly(trimethylene glycol·tetramethylene glycol) mono(meth)acrylate, Polytrimethylene glycol·Polytetramethylene glycol mono(meth)acrylate, Poly(1,2-butylene glycol·trimethylene glycol) mono(meth)acrylate, Poly 1,Examples include 2-butylene glycol polytrimethylene glycol mono(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, poly(1,2-butylene glycol tetramethylene glycol) mono(meth)acrylate, and poly(1,2-butylene glycol polytetramethylene glycol mono(meth)acrylate). In addition, the above "poly(ethylene glycol-propylene glycol)" means a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol-polypropylene glycol" means a block copolymer of ethylene glycol and propylene glycol.

[0045] When the polymerizable monomer contains a polymerizable monomer having a group containing a polyoxyalkylene chain and a polymerizable unsaturated group of which the polymerizable unsaturated group is a (meth)acryloyl group, the content of the polymerizable monomer having a group containing a polyoxyalkylene chain and a polymerizable unsaturated group of which the polymerizable unsaturated group is a (meth)acryloyl group is, for example, in the range of 5 to 40 mass %, and preferably 10 to 35 mass %, of the total amount of polymerizable monomers.

[0046] As the polymerizable monomer, other polymerizable monomers than the polymerizable monomer having an acidic functional group and the polymerizable monomer having a group containing a polyoxyalkylene chain may be used as necessary. Examples of the other polymerizable monomers include those having one or more groups selected from alkyl groups having 1 to 18 carbon atoms and aromatic groups having 6 to 18 carbon atoms, and in which the polymerizable unsaturated group is a (meth)acryloyl group. By using such polymerizable monomers, the hardness of the resulting coating film can be adjusted. The alkyl group may be straight-chain, branched, or an aliphatic ring, and the aromatic group includes a condensed ring.

[0047] Specific examples of the other polymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, and dodecyl (meth)acrylate. acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, and the like.

[0048] The other polymerizable monomer may further have a hydroxyl group. By using polymerizable monomers with hydroxyl groups, it is possible to adjust the reactivity with melamine-based curing agents and isocyanate-based curing agents, which react with the hydroxyl groups. Increasing the number of hydroxyl groups results in a resin composition with excellent curing speed and coating durability, while decreasing the number of hydroxyl groups results in a resin composition with a long usable time (so-called pot life) after mixing with the curing agent.

[0049] Specific examples of the polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, glycerin mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, lactone-modified (meth)acrylate having a terminal hydroxyl group, and 2-methacryloyloxyethyl acid phosphate.

[0050] When the polymerizable monomer contains a polymerizable monomer having one or more groups selected from an alkyl group having 1 to 18 carbon atoms and an aromatic group having 6 to 18 carbon atoms, and the polymerizable unsaturated group is a (meth)acryloyl group, the content of the polymerizable monomer having one or more groups selected from an alkyl group having 1 to 18 carbon atoms and an aromatic group having 6 to 18 carbon atoms, and the polymerizable unsaturated group is a (meth)acryloyl group is, for example, in the range of 50 to 99 mass %, and preferably 60 to 97 mass %, of the total amount of polymerizable monomers.

[0051] The polymerization form of the vinyl-modified epoxy ester resin of the present invention is not particularly limited, and may be any of a random copolymer, a block copolymer, and a graft copolymer of an epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure and a polymerizable monomer.

[0052] The mass ratio of the epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure to the polymerizable monomer in the reaction components of the vinyl-modified epoxy ester resin of the present invention is, for example, in the range of epoxy ester resin:polymerizable monomer=20:80 to 80:20, and preferably in the range of 30:70 to 80:20. When the mass ratio of the epoxy ester resin to the polymerizable monomer is within the above range, a balance of performance can be achieved between the epoxy ester resin, which is responsible for pigment dispersibility, and the polymerizable monomer, which is responsible for stability to solvents (e.g., water, polar solvents, etc.).

[0053] The acid value of the vinyl-modified epoxy ester resin is, for example, in the range of 15 to 80 mgKOH / g, preferably in the range of 20 to 70 mgKOH / g, and more preferably in the range of 20 to 60 mgKOH / g. When the acid value of the vinyl-modified epoxy ester resin is in this range, storage stability and high water resistance of the coating film can be obtained. The acid value of the vinyl-modified epoxy ester resin is evaluated by the method described in the examples.

[0054] The weight average molecular weight of the vinyl-modified epoxy ester resin is not particularly limited, and is, for example, in the range of 10,000 to 100,000, and preferably in the range of 9,000 to 40,000. The weight average molecular weight of the vinyl-modified epoxy ester resin is evaluated by the method described in the examples.

[0055] The vinyl-modified epoxy ester resin of the present invention is preferably a resin containing, as reactive components, an epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure, a polymerizable monomer including a polymerizable monomer having an acidic functional group, and an aliphatic amine. In the vinyl-modified epoxy ester resin of the present invention, a neutralized salt structure is formed by reaction of an aliphatic amine with an acidic functional group derived from a polymerizable monomer having an acidic functional group. The neutralized salt structure exhibits hydrophilicity, thereby imparting water solubility or water dispersibility to the vinyl-modified epoxy ester resin.

[0056] Examples of aliphatic amines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, 2-aminoethanol, 2-amino-2-methyl-1-propanol, 2-(N,N-dimethylamino)-2-methyl-1-propanol, diethanolamine, diisopropanolamine, dibutanolamine, triethanolamine, diazabicyclononene, and diazabicycloundecene. The aliphatic amines may be used alone or in combination of two or more.

[0057] The amount of aliphatic amine used is set so that the neutralization rate of the acidic functional groups in the vinyl epoxy ester resin of the present invention is in the range of 50 to 100%, preferably in the range of 60 to 100%.

[0058] The vinyl-modified epoxy ester resin of the present invention may contain, as reaction components, an epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure, a polymerizable monomer, and an arbitrary aliphatic amine, and is preferably a vinyl-modified epoxy ester resin having, as reaction components, an epoxy ester resin having a condensed ring, a polymerizable monomer, and an arbitrary aliphatic amine.

[0059]

[0033] When producing the vinyl-modified epoxy ester resin of the present invention, the reaction of the epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure with the polymerizable monomer can be carried out by a known method, for example, by adding a radical polymerization initiator to a reaction system containing the epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure and the polymerizable monomer.

[0060] Examples of the radical polymerization initiator include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), and azobiscyanovaleric acid; organic peroxides such as tert-butyl peroxypivalate, tert-butyl peroxybenzoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexyl monocarbonate, normal butyl 4,4-di(tert-butylperoxy)valerate, di-tert-butyl peroxide, di-tert-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, and tert-butyl hydroperoxide; and inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate. The radical polymerization initiators may be used alone or in combination of two or more.

[0061] The amount of radical polymerization initiator used is not particularly limited, but it is recommended to use it in the range of 0.5 to 10 parts by mass per 100 parts by mass of polymerizable monomer, for example. Within this range, it is possible to prevent unreacted monomer from remaining, and to prevent abnormal heat generation and runaway reaction.

[0062] [Resin composition] The resin composition of the present invention contains the epoxy ester resin of the present invention and / or the vinyl-modified epoxy ester resin of the present invention. In particular, the vinyl-modified epoxy ester resin of the present invention can be dissolved or dispersed not only in organic solvents but also in aqueous solvents.

[0063] Examples of the organic solvent include alcohol solvents such as methanol, ethanol, propanol, n-butanol, iso-butanol, tert-butanol, and 3-methoxybutanol; glycol solvents such as ethylene glycol and propylene glycol; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol dimethyl ether; glycol ester solvents such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and tetrahydrofuran. The organic solvent may be used alone or in combination of two or more kinds.

[0064] Aqueous solvents include water, water-miscible organic solvents, and mixtures thereof. The water is not particularly limited, and any of ordinary tap water, industrial water, distilled water, etc. can be used. Examples of the organic solvent miscible with water include the above-mentioned alcohol solvents, glycol solvents, glycol ether solvents, glycol ester solvents, and ketone solvents.

[0065] The solvent for the resin composition of the present invention is preferably water alone or a mixed solvent of water and a water-miscible organic solvent.

[0066] In the resin composition of the present invention, the solvent is used so that the solid content concentration is, for example, 10 to 70 mass %, and preferably 30 to 60 mass %.

[0067] The resin composition of the present invention can ensure sufficient pigment dispersibility even when it contains an extender pigment and an anti-rust pigment, which are generally considered to have poor dispersibility. Here, the term "extender pigment" refers to a pigment that is blended with the purpose of modifying the resin composition (increasing the volume, coloring properties, drying properties, etc.), and the term "rust-preventive pigment" refers to a pigment that is blended with the resin composition to increase its corrosion resistance, and examples of such pigments include metal silicates, metal carbonates, metal sulfates, metal phosphates, and metal phosphites.

[0068] Specific examples of extender pigments include barium sulfate, barium carbonate, calcium carbonate, magnesium oxide, magnesium carbonate, magnesium hydroxide, barium titanate, calcium hydroxide, calcium sulfite, calcium sulfate, calcium oxide, calcium silicate, titanium oxide, silica, zeolite, and talc. The resin composition may contain one kind of extender pigment alone or two or more kinds of extender pigments.

[0069] Specific examples of anti-rust pigments include phosphates, hydrogen phosphates, phosphosilicates, borosilicates, borates, metaborates, molybdates, chromates, polyphosphates, etc. of one or more metals selected from the group consisting of calcium, strontium, barium, zinc, aluminum, and magnesium. The resin composition may contain one kind of rust-preventive pigment alone or two or more kinds of pigments.

[0070] When the resin composition of the present invention contains an extender pigment and / or an anti-rust pigment, the total content of the extender pigment and the anti-rust pigment is, for example, in the range of 20 to 80 parts by mass per 100 parts by mass of the epoxy ester resin of the present invention and / or the vinyl-modified epoxy ester resin of the present invention.

[0071] (Other ingredients) The resin composition of the present invention may be in the form of a one-component paint that does not use a curing agent, or may be in the form of a multi-component paint that uses a curing agent.

[0072] Examples of the curing agent include polyisocyanate compounds, melamine compounds, epoxy compounds, oxazoline compounds, and carbodiimide compounds.

[0073] The resin composition of the present invention may further contain, as necessary, various additives such as color pigments, metal driers (which play a role in promoting oxidative polymerization of carbon-carbon double bonds in the resin), waxes, surfactants, stabilizers, flow modifiers, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, plasticizers, antistatic agents, antifoaming agents, viscosity modifiers, light resistance stabilizers, weather resistance stabilizers, heat resistance stabilizers, pigment dispersants, thermosetting resins, thermoplastic resins, etc. Known additives can be used for these.

[0074] [paint] The resin composition of the present invention can be suitably used as a resin composition for coatings, and by using the resin composition of the present invention as a coating, it is possible to form a cured coating film that is excellent in water resistance and corrosion resistance on the surface of various articles.

[0075] The paint of the present invention may be applied directly to the article to be coated, or a primer coating material suitable for the article to be coated may be applied first, and then the water-based paint of the present invention may be applied.

[0076] Examples of materials that can be used to coat include various metals such as iron, copper, zinc, aluminum, and magnesium, and their alloys; plastic substrates such as polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS), PC-ABS polymer alloy, polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyamide (PA), polypropylene (PP), and fiber-reinforced plastics (FRP) containing fillers such as glass fiber and carbon fiber; and glass.

[0077] The method for applying the coating material of the present invention varies depending on the article to be coated, but examples include methods using a gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin coater, dipping, screen printing, spraying, an applicator, a bar coater, a brush, a roller, and the like.

[0078] Examples of articles having a coating film of the paint of the present invention include the housings and internal parts of home appliances such as televisions, refrigerators, washing machines, and air conditioners; the housings and internal parts of electronic devices such as smartphones, mobile phones, tablet devices, personal computers, digital cameras, and game consoles; the housings of office equipment such as printers and facsimiles; leisure and sports goods; interior and exterior materials for various vehicles such as automobiles, ships, and railway cars; industrial machinery; interior and exterior materials for buildings such as exterior walls, roofs, glass, and decorative panels; and civil engineering components such as soundproof walls and drainage ditches. [Example]

[0079] The present invention will be specifically described below with reference to examples and comparative examples. The present invention is not limited to the following examples.

[0080] In the examples of the present application, the acid value and hydroxyl value were evaluated by the following methods. [Acid value measurement method] Measurement was carried out according to the method of JIS K0070-1992. [Method for measuring hydroxyl value] Measurement was carried out according to the method of JIS K0070-1992.

[0081] In the examples of the present application, the number average molecular weight of the polyester is a value calculated as polystyrene based on GPC measurement, and the measurement conditions are as follows. [GPC measurement conditions] Measurement equipment: Tosoh Corporation's high-speed GPC equipment "HLC-8320GPC" Column: Tosoh Corporation "TSK GURADCOLUMN SuperHZ-L" + Tosoh Corporation "TSK gel SuperHZM-M" + Tosoh Corporation "TSK gel SuperHZM-M" + Tosoh Corporation "TSK gel SuperHZ-2000" + Tosoh Corporation "TSK gel SuperHZ-2000" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "EcoSEC Data Analysis Version 1.07" Column temperature: 40℃ Developing solvent: tetrahydrofuran Flow rate: 0.35mL / min Measurement sample: 7.5 mg of the sample was dissolved in 10 ml of tetrahydrofuran, and the resulting solution was filtered through a microfilter to prepare a measurement sample. Sample injection volume: 20 μl Standard sample: In accordance with the measurement manual for the above-mentioned "HLC-8320GPC," the following monodisperse polystyrene with known molecular weight was used.

[0082] (monodisperse polystyrene) Tosoh Corporation "A-300" Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation Tosoh Corporation "F-80" Tosoh Corporation "F-128" Tosoh Corporation "F-288"

[0083] (Synthesis Example 1: Preparation of Water-Dispersed Resin Composition) A four-neck flask equipped with a stirrer, thermometer, temperature controller, and nitrogen inlet tube was charged with 10.33 parts by weight of dicyclopentadiene-type epoxy resin (EPICLON HP-7200HH, manufactured by DIC Corporation), 7.66 parts by weight of soybean oil fatty acid (manufactured by Tsuno Foods Industries Co., Ltd.), 1.91 parts by weight of dehydrated castor oil fatty acid (manufactured by Ito Oil Mills Co., Ltd.), and 0.10 parts by weight of maleic anhydride. The mixture was heated to 230°C with stirring and allowed to react for 8 hours while maintaining the same temperature. The reaction was terminated when the acid value of the resin reached 1.0 (mgKOH / g) or less, yielding a dicyclopentadiene-type epoxy ester resin having polymerizable unsaturated groups and a dicyclopentadiene structure.

[0084] 20.00 parts by mass of the obtained dicyclopentadiene-type epoxy ester resin was diluted with 25.25 parts by mass of propylene glycol-n-propyl ether, and the liquid temperature was adjusted to 140° C. A mixed solution of 3.00 parts by mass of acrylic acid, 25.00 parts by mass of styrene, 15.00 parts by mass of methyl methacrylate, 27.00 parts by mass of 2-ethylhexyl acrylate, 10.00 parts by mass of cyclohexyl methacrylate, and 1.60 parts by mass of tert-butylperoxy-2-ethylhexyl monocarbonate (Perbutyl E, manufactured by NOF Corporation) as a polymerization initiator, which had been prepared in advance in a separate container, was added dropwise to the four-neck flask over 3 hours, and the reaction was continued for a further 2 hours at the same temperature to obtain a solution of vinyl-modified epoxy ester resin (acid value 23.5 mgKOH / g).

[0085] The obtained vinyl-modified epoxy ester resin solution was cooled to 60°C, and 3.78 parts by mass of N,N-dimethylaminoethanol was added to neutralize the vinyl-modified epoxy ester resin. After neutralization, 123.30 parts by mass of ion-exchanged water was added to cause phase inversion emulsification, and the resulting mixture was filtered through a 200 mesh to obtain a water-dispersed resin composition (1) for aqueous coatings in which the vinyl-modified epoxy ester resin was dispersed in particulate form in water.

[0086] The nonvolatile content of the resin composition (1) was 40% by weight, and the weight average molecular weight of the neutralized vinyl-modified epoxy ester resin was 23,000.

[0087] (Synthesis Examples 2-9 and Comparative Synthesis Examples 1-3: Preparation of Aqueous Dispersion Resin Compositions) An epoxy ester resin having the composition shown in Table 1 was prepared in the same manner as in Synthesis Example 1. Using the obtained epoxy ester resin, a vinyl-modified epoxy ester resin was prepared in the same manner as in Synthesis Example 1 using the polymerizable monomers, radical polymerization initiator, and amine compound shown in Table 1, and resin compositions (2)-(9) and (1')-(3') having a nonvolatile content of 40% by weight were each produced using the solvents shown in Table 1.

[0088] [Table 1]

[0089] The numerical units of each component of the epoxy ester resin, polymerizable monomer, radical polymerization initiator, amine compound, organic solvent, and water in Table 1 are all parts by mass.

[0090] In Table 1, the epoxy resins are as follows. EPICLON HP-7200HHH: Dicyclopentadiene-type epoxy resin EPICLON HP-7200: Dicyclopentadiene-type epoxy resin EPICLON HP-7200L: Dicyclopentadiene-type epoxy resin EPICLON 1050: Bisphenol A-type epoxy resin

[0091] Incidentally, EPICLON HP-7200HHH, EPICLON HP-7200, and EPICLON HP-7200L are all dicyclopentadiene-type epoxy resins represented by the general formula (1), and only the molecular weights are different. Specifically, the molecular weights increase in the order of HP-7200L < HP-7200 < HP-7200HHH.

[0092] In Table 1, the polymerizable monomers are as follows. ARONIX M-5300: ω-Carboxy-polycaprolactone monoacrylate (manufactured by Toagosei Co., Ltd.) Light Ester P-1M: 2-Methacryloyloxyethyl Acid Phosphate (Kyoeisha Chemical Co., Ltd.) Aronix M-5300 and Light Ester P-1M correspond to polymerizable monomers having an acidic functional group.

[0093] (Examples 1-9 and Comparative Examples 1-3: Preparation of aqueous coating compositions, and formation and evaluation of coating films) Using the prepared resin compositions (1) to (9) and (1') to (3'), coating compositions were prepared by the following method, and coating films were formed and their physical properties were evaluated.

[0094] 53.4 parts by mass of each of the obtained resin compositions (1) to (9) and (1') to (3'), 25.0 parts by mass of titanium oxide ("Ti-Pure R-960" manufactured by Chemours Corporation), 25.0 parts by mass of calcium carbonate ("Super S" manufactured by Maruo Calcium Co., Ltd.), 0.1 part by mass of an antifoaming agent ("BYK-028" manufactured by BYK) and 15.4 parts by mass of water were mixed and kneaded for 60 minutes in a paint shaker to obtain a kneaded base (non-volatile content 60% by mass). To the obtained ground meat base, 71.4 parts by mass of each of resin compositions (1) to (9) and (1') to (3'), 0.8 parts by mass of a metal dryer (DIC Corporation's "DICNATE 3111TL"), 0.5 parts by mass of a leveling agent (BYK's "BYK-348"), and 8.4 parts by mass of water were added and mixed to obtain aqueous coating compositions (1-1) to (1-9) and (1-1') to (1-3'), each with a non-volatile content of 50% by mass.

[0095] The resulting aqueous coating compositions (1-1) to (1-9) and (1-1') to (1-3') were applied to zinc phosphate-treated steel sheets with an applicator to a film thickness of 20 μm. After application, the sheets were left to stand at room temperature (25°C) for 7 days, and the carbon-carbon unsaturated bonds in the vinyl-modified epoxy ester resin were oxidatively polymerized using a metal dryer to form a crosslinked coating film.

[0096] The aqueous coating compositions (1-1) to (1-9) and (1-1') to (1-3') produced, and the coating films obtained using the aqueous coating compositions (1-1) to (1-9) and (1-1') to (1-3'), were evaluated as follows. The results are shown in Table 2.

[0097] (Evaluation of pigment dispersibility) The coating composition was poured into a glass cell dedicated to a liquid dispersion stability evaluation device (Turbiscan MA2000 manufactured by Eiko Seiki Co., Ltd.) and allowed to stand for 1 hour, after which the integrated value of the change in backscattered light of the coating composition was measured and used as the reference value. The coating composition in the glass cell was allowed to stand for 7 days at 25°C, and the same measurement was performed again. The pigment dispersibility of the coating composition was evaluated as the relative rate of change in the integrated value after 7 days to the reference value. A rate of change of less than 15% was considered to be acceptable for practical use. Note that the coating composition of Comparative Example 2 (1-2') had extremely poor pigment dispersibility, so evaluation of the gloss value and subsequent steps described below was not performed. S: Less than 7% A: 7% or more but less than 15% B: 15% or more

[0098] (gloss value) The gloss of the coating film formed on the steel plate was measured at any five points using a gloss meter Micro-Tri-Gloss (manufactured by BYK) at an incident angle of 60° and a reflection angle of 60°, and the measured values ​​were taken as the gloss value.

[0099] (Tack-free arrival time) The coating composition was applied to a glass plate (approximately 2 cm wide and 35 cm long) using an applicator (gap: 150 μm), and the glass plate coated with the coating composition was set in a paint drying time measuring instrument DTT-II (manufactured by Taiyu Kizai Co., Ltd.) to measure the time until the glass plate became tack-free. The tack-free time is a value based on ASTM D5895-03 (the time it takes for scratches on the coating film to change from a continuous line to a broken line is the tack-free time).

[0100] (Adhesion to substrate) The coating film formed on the steel plate was evaluated for substrate adhesion according to JIS K-5400:1990. Specifically, 1 mm wide cuts were made on the coating film with a cutter to leave 100 squares, and cellophane tape was applied so that all the squares were covered, and then quickly peeled off. After the test, the number of squares remaining in contact with the substrate was expressed as a percentage. In terms of substrate adhesion, 100% means that no coating peeled off, and 0% means that the entire coating peeled off. Adhesion of 95% or more can be considered to be sufficient for practical use.

[0101] (water resistance) The water resistance of the coating film formed on the steel plate was evaluated according to ASTM D870-02. Specifically, the 60° gloss value of the coating surface was measured in advance using a gloss meter, Micro-Tri-Gloss (manufactured by BYK), and then the test sample was immersed in a warm water bath at 40°C and left to stand for 24 hours. After removing the test sample, the substrate adhesion was evaluated using the method described above (substrate adhesion after warm water immersion). Next, the 60° gloss value of the coating surface was measured, and the gloss value after immersion was divided by the gloss value before immersion to determine the "gloss retention rate." Furthermore, if the adhesion to the substrate after immersion in a warm water bath is 90% or more and the gloss retention rate is 90% or more, it can be considered that the performance is acceptable for practical use.

[0102] (corrosion resistance) An X-shaped cut was made in the coating film formed on the steel plate using the edge of a cutter knife, extending from the coating film down to the substrate. This substrate was placed in a JIS Z2371-compliant salt spray tester, Model CYP-90 (manufactured by Suga Test Instruments Co., Ltd.), and a 5% aqueous solution of sodium chloride was sprayed at 35°C for 15 days. After spraying, the substrate was washed with water and dried at 25°C for 2 hours. Cellophane tape was then applied to the coating film, and the degree of peeling of the coating film when the cellophane tape was removed was evaluated according to the following criteria. S: Peel width in peel test is less than 1 mm A: Peel width in peel test is 1mm or more but less than 3mm B: Peel width in peel test is 3mm or more The term "peeling width" used herein refers to the width of the peeled coating film, measured from the cut made with the cutter knife. If the peeling width is less than 3 mm, it can be considered that the performance is acceptable for practical use.

[0103] [Table 2]

[0104] The results in Table 2 show that the coating film obtained from the aqueous coating composition using the vinyl-modified epoxy ester resin of the present invention as the binder resin is excellent in gloss and corrosion resistance. On the other hand, in Comparative Example 1, the amount of polymerizable monomer used in the production of the vinyl-modified epoxy ester resin is large (the amount of epoxy ester resin is small), so the gloss and corrosion resistance are poor. In Comparative Example 2, the amount of polymerizable monomer used in the production of the vinyl-modified epoxy ester resin is small (the amount of epoxy ester resin is large), so pigment dispersibility is not achieved. In Comparative Example 3, the coating film does not have gloss because the vinyl-modified epoxy ester resin does not have a condensed alicyclic structure.

[0105] (Examples 10-18 and Comparative Examples 4-6: Preparation of aqueous coating compositions, and formation and evaluation of coating films) Using the prepared resin compositions (1) to (9) and (1') to (3'), coating compositions were prepared by the following method, and coating films were formed and their physical properties were evaluated.

[0106] 53.4 parts by mass of each of the obtained resin compositions (1) to (9) and (1') to (3'), 20.0 parts by mass of titanium oxide ("Ti-Pure R-960" manufactured by Chemours Corporation), 20.0 parts by mass of calcium carbonate ("Super S" manufactured by Maruo Calcium Co., Ltd.), 10.0 parts by mass of calcium hydrogen phosphate ("EXPERT NP-1020C" manufactured by Toho Pigment Industrial Co., Ltd.), 0.1 part by mass of an antifoaming agent ("BYK-028" manufactured by BYK), and 15.4 parts by mass of water were mixed and kneaded for 60 minutes in a paint shaker to obtain a kneaded base (non-volatile content 60% by mass). To the obtained ground meat base, 71.4 parts by mass of each of resin compositions (1) to (9) and (1') to (3'), 0.8 parts by mass of a metal dryer (DIC Corporation's "DICNATE 3111TL"), 0.5 parts by mass of a leveling agent (BYK's "BYK-348"), and 8.4 parts by mass of water were added and mixed to obtain aqueous coating compositions (2-1) to (2-9) and (2-1') to (2-3'), each with a non-volatile content of 50% by mass.

[0107] The aqueous coating compositions (2-1) to (2-9) and (2-1') to (2-3') produced, and the coating films obtained using the aqueous coating compositions (2-1) to (2-9) and (2-1') to (2-3'), were evaluated in the same manner as above. The results are shown in Table 3. The coating composition (2-2') of Comparative Example 5 had extremely poor pigment dispersibility, so evaluation of the gloss value and subsequent measurements was not carried out.

[0108] [Table 3]

[0109] The results in Table 3 are similar to those in Table 2. It can be seen that the coating film obtained from the aqueous coating composition using the vinyl-modified epoxy ester resin of the present invention as the binder resin is excellent in gloss and corrosion resistance. On the other hand, in Comparative Example 4, the amount of polymerizable monomer used in the production of the vinyl-modified epoxy ester resin is large (the amount of epoxy ester resin is small), so it is found that the gloss and corrosion resistance are poor. In Comparative Example 5, the amount of polymerizable monomer used in the production of the vinyl-modified epoxy ester resin is small (the amount of epoxy ester resin is large), so it can be seen that pigment dispersibility is not obtained. In Comparative Example 6, it can be seen that the coating film does not have gloss because the vinyl-modified epoxy ester resin does not have a condensed alicyclic structure.

[0110] (Synthesis Example 10 and Synthesis Comparative Example 4: Preparation of Solvent Dispersion Resin Composition) Epoxy ester resins having the compositions shown in Table 4 were prepared in the same manner as in Synthesis Example 1, and resin compositions (10) and (4') having nonvolatile contents of 70 mass % were produced using solvents shown in Table 4.

[0111] [Table 4]

[0112] (Example 19 and Comparative Example 7: Preparation of solvent-based coating composition, and formation and evaluation of coating film) Using the prepared resin compositions (10) and (4'), coating compositions were prepared in the following manner, and coating films were formed and their physical properties were evaluated.

[0113] 30.7 parts by mass of each of the obtained resin compositions (10) and (4'), 25.0 parts by mass of titanium oxide ("Ti-Pure R-960" manufactured by Chemours Corporation), 25.0 parts by mass of calcium carbonate ("Super S" manufactured by Maruo Calcium Co., Ltd.), and 38.2 parts by mass of a diluent (aromatic hydrocarbon solvent, "T-SOL100 FLUID" manufactured by ENEOS Corporation) were mixed and kneaded for 60 minutes in a paint shaker to obtain a kneaded base (non-volatile content 60% by mass). To the obtained ground meat base, 40.8 parts by mass of resin compositions (10) and (4'), 0.6 parts by mass of a metal dryer (DIC Corporation's "DICNATE SG-160"), 0.5 parts by mass of a leveling agent (BYK's "BYK-333"), and 39.2 parts by mass of butyl acetate were added and mixed to obtain solvent-based paint compositions (3-10) and (3-4'), respectively, with a non-volatile content of 50% by mass.

[0114] The solvent-based coating compositions (3-10) and (3-4') and the coating films obtained using the solvent-based coating compositions (3-10) and (3-4') were evaluated in the same manner as above. The results are shown in Table 5.

[0115] [Table 5]

[0116] The results in Table 5 show that the coating film obtained from the solvent-based coating composition using the epoxy ester resin of the present invention as the binder resin is excellent in gloss and corrosion resistance. On the other hand, in Comparative Example 7, the coating film does not have gloss because the epoxy ester resin does not have a condensed alicyclic structure.

Claims

1. An epoxy ester resin having a polymerizable unsaturated group and a condensed alicyclic structure but not containing a bisphenol structure, and a vinyl-modified epoxy ester resin having a condensed alicyclic structure, which is produced as reaction components from a polymerizable monomer and an aliphatic amine, the polymerizable monomer includes a polymerizable monomer having an acidic functional group, A vinyl-modified epoxy ester resin in which the mass ratio of the epoxy ester resin to the polymerizable monomer [epoxy ester resin:polymerizable monomer] is in the range of 20:80 to 80:

20.

2. A vinyl-modified epoxy ester resin as described in claim 1, wherein the epoxy ester resin is a reaction product of an epoxy resin having a condensed alicyclic structure with an unsaturated fatty acid, or a reaction product of an epoxy resin having a condensed alicyclic structure with an unsaturated fatty acid and a polycarboxylic acid.

3. 3. The vinyl-modified epoxy ester resin according to claim 2, wherein the epoxy resin having a condensed alicyclic structure is a dicyclopentadiene-type epoxy resin.

4. 4. The vinyl-modified epoxy ester resin according to claim 2, wherein the epoxy equivalent of the epoxy resin having a condensed alicyclic structure is in the range of 200 to 2,000 g / equivalent.

5. 5. The vinyl-modified epoxy ester resin according to claim 2, wherein the unsaturated fatty acid is an unsaturated aliphatic monocarboxylic acid having 6 to 40 carbon atoms.

6. The vinyl-modified epoxy ester resin according to any one of claims 2 to 5, wherein the molar ratio of epoxy groups contained in the epoxy resin having a condensed alicyclic structure to carboxyl groups contained in the unsaturated fatty acid and polycarboxylic acid [epoxy groups:carboxyl groups] is in the range of 1:1 to 1:

2.

7. 7. The vinyl-modified epoxy ester resin according to claim 1, having an acid value in the range of 20 to 60 mgKOH / g.

8. A resin composition comprising the vinyl-modified epoxy ester resin according to any one of claims 1 to 7.

9. 9. The resin composition according to claim 8, further comprising one or more pigments selected from the group consisting of metal silicates, metal carbonates, metal sulfates, metal phosphates, and metal phosphites.

10. The resin composition according to claim 8 or 9, which is an aqueous resin composition further containing water.

11. A paint comprising the resin composition according to any one of claims 8 to 10.

12. An article having a coating of the paint of claim 11.

Images