Vinyl-modified epoxy ester resin, resin composition, paint, and article coated with the paint

Abstract

To provide a resin composition which enables formation of a coating film excellent in water resistance and anticorrosive property, can be dried at normal temperature and can shorten a tack-free time.SOLUTION: A vinyl-modified epoxy ester resin has a condensed ring containing an epoxy ester resin having a polymerizable unsaturated group and a condensed ring, and a polymerizable monomer as reactive components, wherein the epoxy ester resin having the polymerizable unsaturated group and the condensed ring is a reactant of an epoxy resin, an unsaturated aliphatic acid and a monocarboxylic acid having a condensed ring having a melting point of 130-220°C, and a ratio of the monocarboxylic acid having the condensed ring in the total reactive components is within a range of 7-25 mass%.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In order to address air pollution, regulations on volatile organic compounds (VOCs) have been strengthened in the United States, Europe, China, etc. For paints that use large amounts of volatile organic compounds such as toluene, xylene, and ethyl acetate as solvents, there is a demand for water-based paints that do not use these organic solvents or reduce the use of organic solvents.

[0003] While water-based paints are in demand, for paints used on buildings, ships, aircraft, etc., since the paint film is exposed to rainwater, water resistance and corrosion resistance are required. In addition, for productivity improvement, room temperature drying properties that do not require heating are also demanded.

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

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] Water-based paints are paints in which resins are dissolved or dispersed in an aqueous medium. However, since water generally has inferior drying properties compared to organic solvents, there has been a problem in water-based paints that the time (tack-free time) until the paint film reaches a non-sticky state after painting is long. In particular, in the case of room temperature drying type water-based paints that utilize the above oxidative polymerization, since the carbon-carbon unsaturated double bonds possessed by the resins contained in the paint are derived from fatty acids, the glass transition temperature (Tg) of the resin becomes room temperature (25 ° C) or lower, and even when the solvent component has completely volatilized, the paint film does not become tack-free and it has been necessary to wait for curing by oxidative polymerization.

[0007] The problem to be solved by the present invention is to provide a resin composition that can form a paint film excellent in water resistance and corrosion resistance, can be dried at room temperature, and can shorten the tack-free time.

Means for Solving the Problems

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that by using an epoxy ester resin into which a condensed ring is introduced, a resin composition capable of forming a paint film excellent in water resistance and corrosion resistance, capable of room temperature drying, and capable of shortening the tack-free time can be obtained, and have completed the present invention.

[0009] That is, the present invention relates to a vinyl-modified epoxy ester resin having a condensed ring, which uses an epoxy ester resin having a polymerizable unsaturated group and a condensed ring and a polymerizable monomer as reaction components, wherein the epoxy ester resin having a polymerizable unsaturated group and a condensed ring is a reaction product of an epoxy resin, an unsaturated fatty acid, and a monocarboxylic acid having a condensed ring with a melting point in the range of 130 to 220 ° C, and the proportion of the monocarboxylic acid having a condensed ring in all reaction components is in the range of 7 to 25% by mass.

Effects of the Invention

[0010] According to the present invention, a vinyl-modified epoxy ester resin capable of forming a paint film excellent in water resistance and corrosion resistance, capable of room temperature drying, and capable of shortening the tack-free time can be provided.

Best Mode for Carrying Out the Invention

[0011] Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope that does not impair the effects of the present invention.

[0012] [Vinyl-Modified Epoxy Ester Resin] The vinyl-modified epoxy ester resin of the present invention is a vinyl-modified epoxy ester resin having a condensed ring, with an epoxy ester resin having a polymerizable unsaturated group and a condensed ring and a polymerizable monomer as reaction components. The epoxy ester resin having a polymerizable unsaturated group and a condensed ring is a reaction product of an epoxy resin, an unsaturated fatty acid, and a monocarboxylic acid having a condensed ring. It is presumed that the monocarboxylic acid having a condensed ring can increase the glass transition temperature of the vinyl-modified epoxy ester resin and shorten the tack-free time. Hereinafter, the reaction components of the vinyl-modified epoxy ester resin of the present invention will be described.

[0013] (Epoxy Ester Resin Having a Polymerizable Unsaturated Group and a Condensed Ring) The epoxy ester resin having a polymerizable unsaturated group and a condensed ring in the present invention is a reaction product of an epoxy resin, an unsaturated fatty acid, and a monocarboxylic acid having a condensed ring. The polymerizable unsaturated group of the epoxy ester resin is derived from the unsaturated fatty acid, and the condensed ring of the epoxy ester resin is derived from the monocarboxylic acid having a condensed ring.

[0014] The epoxy resin is a resin having at least one epoxy group in the molecule, preferably an epoxy resin having an epoxy equivalent in the range of 200 to 2,000 g / equivalent, and more preferably an epoxy resin having an epoxy equivalent in the range of 300 to 1,500 g / equivalent. The epoxy equivalent weight is the weight of the epoxy resin required to obtain 1 mol of epoxy groups. When using a mixture of two or more epoxy resins as the epoxy resin, the epoxy equivalent weight of the mixture is preferably within the above range.

[0015] Examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and bisphenol S type epoxy resin; epoxy ester resins obtained by modifying the bisphenol type epoxy resin with a dibasic acid or the like; novolak type epoxy resins such as cresol novolak type epoxy resin and phenol novolak type epoxy resin; alicyclic epoxy resins; polyglycol type epoxy resins; hydrogenated bisphenol A type epoxy resin; aliphatic type epoxy resins such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 - hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, and polyglycerin polyglycidyl ether; and epoxidized polybutadiene resin. Among these, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferred. The epoxy resin may be used alone or in combination of two or more.

[0016] Epoxy resins may be commercially available products. Examples of commercially available products of bisphenol A type epoxy resins include EPICLON 860, EPICLON 1050, EPICLON 1055, EPICLON 3050, EPICLON 4050, EPICLON 7050, EPICLON HM-091, EPICLON HM-101 (all manufactured by DIC Corporation), etc.; examples of commercially available products of bisphenol F type epoxy resins include EPICLON 830, EPICLON 835 (both manufactured by DIC Corporation), etc.

[0017] 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 12 to 20 carbon atoms. The degree of unsaturation of the unsaturated fatty acid is not particularly limited, but is, for example, in the range of 1 to 3.

[0018] The unsaturated fatty acid may be used alone or in combination of two or more. Also, a saturated fatty acid may be used in combination with the unsaturated fatty acid.

[0019] The unsaturated fatty acid is preferably at least one selected from the group consisting of sorbic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinoleic acid, etc., and 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.

[0020] From the viewpoint of obtaining an aqueous paint excellent in oxidative polymerizability by a metal drier, the unsaturated fatty acid is preferably a semi-drying oil or a drying oil having an iodine value in the range of 120 to 200.

[0021] The amount of the unsaturated fatty acid used is, for example, in the range of 10 to 60 parts by mass with respect to 100 parts by mass of the epoxy resin, and preferably in the range of 20 to 45 parts by mass.

[0022] The monocarboxylic acid having a condensed ring has a melting point in the range of 130 to 220 °C. By using the monocarboxylic acid having a condensed ring with a melting point in the above range, the glass transition temperature and softening point of the coating film obtained by using the composition of the present invention can be increased, and the tack-free time can be shortened. In addition, since the condensed ring structure has high hydrophobicity, the water resistance and corrosion resistance of the obtained coating film can also be enhanced. On the other hand, since the monocyclic monocarboxylic acid without a condensed ring has a low melting point, the effect of shortening the tack-free time cannot be obtained. Here, the "condensed ring" refers to a cyclic structure in which two or more monocyclic rings share two or more atoms with each other, and the monocyclic ring may be either an aromatic ring (e.g., benzene ring) or an alicyclic ring (e.g., cyclohexane ring). Further, the alicyclic ring may be saturated or unsaturated.

[0023] The melting point of the monocarboxylic acid having a condensed ring can be measured using the light transmission method defined in JIS K 0064 or the like.

[0024] The monocarboxylic acid having a condensed ring is preferably a monocarboxylic acid having a 2- to 4-ring condensed ring, more preferably a monocarboxylic acid having a 3- or 4-ring condensed ring, and still more preferably a monocarboxylic acid having a 3- or 4-ring alicyclic condensed ring.

[0025] The monocarboxylic acid having a condensed ring may be used alone or in combination of two or more.

[0026] The monocarboxylic acid having a condensed ring is preferably at least one selected from the group consisting of isopimaric acid (melting point 160 °C), abietic acid (melting point 173 °C), neoabietic acid (melting point 165 °C), pultruric acid (melting point 165 °C), dehydroabietic acid (melting point 166 °C), oleanonic acid (melting point 190 °C), fusidic acid (melting point 193 °C), podocarpic acid (melting point 193 °C), dihydroabietic acid (melting point 195 °C), camphanic acid (melting point 199 °C), helvolic acid (melting point 212 °C), and pimaric acid (melting point 219 °C).

[0027] Rosins such as gum rosin, wood rosin, tall oil rosin, and hydrogenated rosin (hydrated rosin) are all natural-derived components containing monocarboxylic acids having the above-mentioned condensed ring, and can be used as monocarboxylic acids having a condensed ring. Composition examples of gum rosin, wood rosin, tall oil rosin, and hydrogenated rosin are shown in Table 1. However, since rosins are plant-derived raw materials or their processed products, the component composition may vary depending on the region where they are collected and produced, and the rosins in the present invention are not limited to the compositions shown in Table 1.

[0028]

Table 1

[0029] In Table 1, Sources 1 and 2 in the Remarks column are as follows. Source 1: Inert Reassessment - Rosins and Rosin Derivatives, issued on November 29, 2005, by the US Environmental Protection Agency Source 2: Rosin, Hydrogenated Rosin and their Salts CATEGORY JUSTIFICATION DOCUMENT, H4R CONSORTIUM

[0030] The usage amount of the monocarboxylic acid having a condensed ring is, for example, 10 to 40 parts by mass, preferably 15 to 35 parts by mass, based on 100 parts by mass of the epoxy resin.

[0031] As reaction components, polycarboxylic acids may be used in addition to the epoxy resin, unsaturated fatty acid, and monocarboxylic acid having a condensed ring. The epoxy ester resin, which is a reaction product of an epoxy resin, an unsaturated fatty acid, a monocarboxylic acid having a condensed ring, and a polycarboxylic acid, can extend the polymer chain by the reaction of the carboxyl group of the polycarboxylic acid and the epoxy group of the epoxy resin, and the molecular weight can be controlled.

[0032] Examples of the polyvalent carboxylic acid include phthalic acid, 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, (anhydrous) maleic acid, fumaric acid, itaconic acid, etc. The polyvalent carboxylic acid may be used alone or in combination of two or more. Further, derivatives such as acid anhydrides of the polyvalent carboxylic acid may be used as the polyvalent carboxylic acid.

[0033] When using the polyvalent carboxylic acid as a reaction component, the amount of the polyvalent carboxylic acid used is, for example, 1 part by mass or less, preferably 0.6 part by mass or less, based on 100 parts by mass of the epoxy resin. The lower limit of the amount of the polyvalent carboxylic acid used is not particularly limited, but is, for example, 0.1 part by mass based on 100 parts by mass of the epoxy resin.

[0034] The epoxy ester resin having a polymerizable unsaturated group and a condensed ring may use an epoxy resin, an unsaturated fatty acid, a monocarboxylic acid having a condensed ring, and optionally a polyvalent carboxylic acid as reaction components, and other components may also be used as reaction components.

[0035] The acid value of the epoxy ester resin having a polymerizable unsaturated group and a condensed ring is, for example, in the range of 2 - 15 mgKOH / g, preferably in the range of 4 - 10 mgKOH / g. The acid value of the epoxy ester resin having a condensed ring is evaluated by the method described in the examples.

[0036] The molecular weight of the epoxy ester resin having a polymerizable unsaturated group and a condensed ring is not particularly limited, but is, for example, in the range of a weight average molecular weight of 9,000 - 40,000. The weight average molecular weight of the epoxy ester resin having a condensed ring is evaluated by the method described in the examples.

[0037] The reaction of an epoxy resin, an unsaturated fatty acid, and a monocarboxylic acid having a condensed ring can be carried out by a known method. For example, a polymerizable unsaturated group and a condensed ring can be obtained by heating a reaction system containing an epoxy resin, an unsaturated fatty acid, and a monocarboxylic acid having a condensed ring. An epoxy ester resin can be prepared.

[0038] (Vinyl-modified epoxy ester resin) The vinyl-modified epoxy ester resin of the present invention is a resin having an epoxy ester resin having the above polymerizable unsaturated group and condensed ring and a polymerizable monomer as reaction components. Here, "as a reaction component" means a component constituting the vinyl-modified epoxy ester resin, and does not include a solvent or a catalyst that does not constitute the vinyl-modified epoxy ester resin.

[0039] The polymerizable monomer means a compound having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group possessed by the monomer include (meth)acryloyl group, (meth)acryloyloxy group, (meth)acrylamide group, vinyl ether group, allyl group, styryl group, (meth)acrylamide group, maleimide group, etc. Among these, due to the easy availability of raw materials and good polymerization reactivity, (meth)acryloyl group, (meth)acryloyloxy group, and styryl group are preferred.

[0040] The polymerizable monomer may be used alone or in combination of two or more.

[0041] The above polymerizable monomer preferably contains a polymerizable monomer having an acidic functional group. By using a polymerizable monomer having an acidic functional group as the polymerizable monomer, the acidic functional group can react with an amine compound described later to impart water solubility to the vinyl-modified epoxy ester resin.

[0042] Examples of the polymerizable monomer 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, acryloyloxycaprolactonic acid; polymerizable monomers having a phosphate group such as 2-(meth)acryloyloxyethyl acid phosphate, 3-(meth)acryloyloxypropyl acid phosphate, (meth)acryloyloxypolyoxyethylene glycol acid phosphate, (meth)acryloyloxypolyoxypropylene glycol acid phosphate; monomers having a sulfonic acid group such as vinyl sulfonic acid, and the like. The polymerizable monomer having an acidic functional group includes derivatives such as acid anhydrides.

[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 the polymerizable monomer having a group containing a polyoxyalkylene chain and having a polymerizable unsaturated group of (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, poly(ethylene glycol·1,2-butylene glycol) mono(meth)acrylate, polyethylene glycol·poly1,2-butylene glycol mono(meth)acrylate, poly(tetraethylene glycol·1,2-butylene glycol) mono(meth)acrylate, polytetraethylene glycol·poly1,2-butylene glycol mono(meth)acrylate, poly1,2-butylene glycol mono(meth)acrylate, poly(ethylene glycol·trimethylene glycol) mono(meth)acrylate, polyethylene glycol·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, poly1,Examples include 2-butylene glycol-polytetramethylene 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, poly 1,2-butylene glycol-polytetramethylene glycol mono(meth)acrylate, etc. 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] As the above polymerizable monomer, other polymerizable monomers other than the polymerizable monomer having an acidic functional group and the polymerizable monomer having a group containing a polyoxyalkylene chain may be used as needed. Examples of the above other polymerizable monomers include polymerizable monomers having one or more selected from an alkyl group having 1 to 18 carbon atoms and an aromatic group having 6 to 18 carbon atoms, and having a polymerizable unsaturated group of (meth)acryloyl group. By using this polymerizable monomer, the hardness of the obtained coating film can be increased by designing a high theoretical Tg of the acrylic resin part, and the flexibility of the obtained coating film can be increased by designing a low theoretical Tg. In addition, the above alkyl group may be linear, branched or an aliphatic ring, and the above aromatic group includes a condensed ring.

[0046] 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, dodecyl (meth)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.

[0047] The other polymerizable monomers may further have a hydroxyl group. By using a polymerizable monomer having a hydroxyl group, the reactivity with a melamine-based curing agent or an isocyanate-based curing agent that reacts with the hydroxyl group can be adjusted. Increasing the hydroxyl group results in a resin composition excellent in curing rate and coating film durability, while decreasing the hydroxyl group can obtain a resin composition with a long pot life (so-called pot life) after mixing the curing agent.

[0048] Specific examples of the polymerizable monomer further 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 hydroxyl group at the terminal, and the like.

[0049] The polymerization form of the vinyl-modified epoxy ester resin of the present invention is not particularly limited, and 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 ring and a polymerizable monomer may be used.

[0050] In the reaction components of the vinyl-modified epoxy ester resin of the present invention, the mass ratio of the epoxy ester resin having a polymerizable unsaturated group and a condensed ring to the polymerizable monomer is, for example, in the range of epoxy ester resin: polymerizable monomer = 90:10 to 30:70, preferably in the range of 80:20 to 50:50.

[0051] The proportion of the monocarboxylic acid having a condensed ring in all the reaction components of the vinyl-modified epoxy ester resin of the present invention is in the range of 7 to 25% by mass, preferably in the range of 10 to 25% by mass, and more preferably in the range of 15 to 25% by mass.

[0052] Incidentally, the "total reaction components" mean all the reaction components constituting the vinyl-modified epoxy ester resin. For example, in the case of an epoxy ester resin (1) having a polymerizable unsaturated group and a condensed ring, which is a resin having an epoxy resin (1-1), an unsaturated fatty acid (1-2), and a monocarboxylic acid (1-3) having a condensed ring as reaction components, the total reaction components of the vinyl-modified epoxy ester resin are the epoxy resin (1-1), the unsaturated fatty acid (1-2), the monocarboxylic acid (1-3) having a condensed ring, and the polymerizable monomer (2).

[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 within this range, storage stability and high coating water resistance can be obtained. Incidentally, 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. 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 having an epoxy ester resin having a polymerizable unsaturated group and a condensed ring, a polymerizable monomer containing a polymerizable monomer having an acidic functional group, and an aliphatic amine as reaction components. Regarding the vinyl-modified epoxy ester resin of the present invention, a neutralized salt structure is formed by reacting an aliphatic amine with an acidic functional group derived from a polymerizable monomer having an acidic functional group. Since the neutralized salt structure exhibits hydrophilicity, water solubility or water dispersibility can be imparted 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, diazabicycloundecene, and the like. The aliphatic amine may be used alone or in combination of two or more.

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

[0058] The vinyl-modified epoxy ester resin of the present invention may use an epoxy ester resin having a condensed ring, a polymerizable monomer, and an optional aliphatic amine as reaction components, and is preferably a vinyl-modified epoxy ester resin composed of a reaction component comprising an epoxy ester resin having a condensed ring, a polymerizable monomer, and an optional aliphatic amine.

[0059] The reaction between the epoxy ester resin having a condensed ring and the polymerizable monomer in the production of the vinyl-modified epoxy ester resin of the present invention 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 condensed ring 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-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-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 initiator may be used alone or in combination of two or more.

[0061] The amount of the radical polymerization initiator used is not particularly limited, but for example, it may be used in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Within this range, it is possible to suppress the remaining of unreacted monomers and the occurrence of abnormal heat generation and reaction runaway.

[0062] [Resin Composition] The resin composition of the present invention contains the vinyl-modified epoxy ester resin of the present invention and can contain either an organic solvent or an aqueous solvent as the solvent. The vinyl-modified epoxy ester resin of the present invention can be dissolved or dispersed not only in an organic solvent but also in an aqueous solvent.

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

[0064] Examples of the aqueous solvent include water, an organic solvent miscible with water, and a mixture thereof. Water is not particularly limited, and any of general 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, ketone solvents, etc.

[0065] The solvent of the resin composition of the present invention is preferably only water or a mixed solvent of water and an organic solvent miscible with water.

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

[0067] (Other components) 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.

[0068] Examples of the curing agent include polyisocyanate compounds, melamine compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and the like.

[0069] The resin composition of the present invention may further contain various additives such as pigments (inorganic pigments, organic pigments, extender pigments), metal driers (which play a role in promoting the oxidative polymerization of carbon-carbon double bonds in the resin), waxes, surfactants, stabilizers, flow regulators, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, plasticizers, antistatic agents, defoamers, viscosity modifiers, lightfast stabilizers, weather stabilizers, heat stabilizers, pigment dispersants, thermosetting resins, and thermoplastic resins, as necessary.

[0070] [Paint] The resin composition of the present invention can be suitably used as a paint. By using the resin composition of the present invention as a paint, a cured coating film excellent in water resistance and corrosion resistance can be formed on the surface of various articles.

[0071] The paint of the present invention may be directly applied to an article to be coated, or may be applied after applying a primer coating material suitable for the article to be coated and then applying the aqueous paint of the present invention.

[0072] Examples of the materials of the article to be painted include various metals such as iron, copper, zinc, aluminum, magnesium, and their alloys; plastic substrates such as fiber-reinforced plastics (FRP) filled with fillers such as polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS), PC-ABS polymer alloy, polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyamide (PA), polypropylene (PP), glass fiber, and carbon fiber; and glass.

[0073] The painting methods of the paint of the present invention vary depending on the article to be painted. For example, methods such as 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, applicator, bar coater, brush, and roller can be mentioned.

[0074] Examples of the article having the paint film of the present invention include, for example, the casings and internal parts of household appliances such as televisions, refrigerators, washing machines, and air conditioners; the casings and internal parts of electronic devices such as smartphones, mobile phones, tablet terminals, personal computers, digital cameras, and game machines; the casings of OA devices such as printers and facsimile machines; leisure and sports goods; interior and exterior materials of various vehicles such as automobiles, ships, and railway vehicles; industrial machines; interior and exterior materials of buildings such as exterior walls, roofs, glass, and decorative boards; and civil engineering members such as sound insulation walls and drainage ditches.

Examples

[0075] Hereinafter, the present invention will be specifically described by way of examples and comparative examples. Note that the present invention is not limited to the following examples.

[0076] In the examples of the present application, the values of the acid value and the hydroxyl value are the values evaluated by the following methods. [Method for measuring acid value] Measured by a method according to JIS K0070-1992. [Method for measuring hydroxyl value] It was measured by a method in accordance with JIS K0070-1992.

[0077] In the examples of the present application, the number average molecular weight of the polyester is a value converted to polystyrene based on GPC measurement, and the measurement conditions are as follows. [GPC Measurement Conditions] Measuring device: High-speed GPC device "HLC-8320GPC" manufactured by Tosoh Corporation Column: "TSK GURADCOLUMN SuperHZ-L" manufactured by Tosoh Corporation + "TSK gel SuperHZM-M" manufactured by Tosoh Corporation + "TSK gel SuperHZM-M" manufactured by Tosoh Corporation + "TSK gel SuperHZ-2000" manufactured by Tosoh Corporation + "TSK gel SuperHZ-2000" manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: "EcoSEC Data Analysis version 1.07" manufactured by Tosoh Corporation Column temperature: 40 °C Developing solvent: Tetrahydrofuran Flow rate: 0.35 mL / min Measurement sample: A sample obtained by dissolving 7.5 mg of the sample in 10 ml of tetrahydrofuran and filtering the resulting solution through a microfilter was used as the measurement sample. Sample injection volume: 20 μl Standard sample: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual of the "HLC-8320GPC".

[0078] (Monodisperse Polystyrene) "A-300" manufactured by Tosoh Corporation "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "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 "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation "F-288" manufactured by Tosoh Corporation

[0079] Example 1 (Preparation of Resin Composition) Into a four-necked flask equipped with a stirrer, a thermometer, a temperature controller, and a nitrogen inlet tube, 7.02 parts by weight of soybean oil fatty acid, 15.13 parts by weight of pultruric acid, and 17.85 parts by weight of bisphenol A type epoxy resin ("EPICLON 1055" manufactured by DIC Corporation) were charged, and the temperature was raised to 230 °C with stirring and maintained. The reaction was terminated when the acid value of the reaction product reached 8.0 mgKOH / g or less, and an epoxy ester resin having a polymerizable unsaturated group derived from soybean oil fatty acid and a condensed ring derived from pultruric acid was obtained.

[0080] 40.00 parts by weight of the obtained epoxy ester resin was diluted with 25.25 parts by weight of butyl cellosolve and heated to 140 °C. Separately prepared, as a vinyl-modified component, 2.50 parts by weight of acrylic acid, 23.00 parts by weight of styrene, 7.00 parts by weight of methyl methacrylate, 17.50 parts by weight of ethyl acrylate, and 10.00 parts by weight of cyclohexyl methacrylate, and 1.20 parts by weight of tert-butyl peroxy-2-ethylhexyl monocarbonate ("Perbutyl E" manufactured by NOF Corporation) as a polymerization initiator were added to the four-necked flask over 3 hours, and the mixture was further reacted for 5 hours to obtain a solution of a vinyl-modified epoxy ester resin (acid value 22 mgKOH / g).

[0081] The obtained vinyl-modified epoxy ester resin solution was cooled to 50 °C, and 3.48 parts by weight of N,N-dimethylaminoethanol was added to neutralize the vinyl-modified epoxy ester resin. After neutralization, 123.30 parts by weight of ion-exchanged water was added, followed by phase inversion emulsification and then filtration to obtain a resin composition (1) in which the vinyl-modified epoxy ester resin was dispersed in particles in water.

[0082] The non-volatile 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.

[0083] Examples 2-8 and Comparative Examples 1-4 An epoxy ester resin having the composition shown in Table 2 was prepared in the same manner as in Example 1. Using the obtained epoxy ester resin, a vinyl-modified epoxy ester resin was prepared in the same manner as in Example 1 using the polymerizable monomer, radical polymerization initiator, and amine compound shown in Table 2, and resin compositions (2) to (8) and (1') to (4') having a non-volatile content of 40% by weight were each produced using the solvents shown in Table 2.

[0084] Comparative Example 5 49.64 parts by weight of gum rosin, 48.42 parts by weight of bisphenol A type epoxy resin ("EPICLON 1055" manufactured by DIC Corporation), and 1.94 parts by weight of maleic anhydride were charged into a four-necked flask equipped with a stirrer, thermometer, temperature controller, and nitrogen inlet tube. The temperature was raised to 230°C while melting and stirring the raw materials, and maintained. Since the resin gelled 12 hours after the start of the reaction, the target resin could not be obtained.

[0085] [Table 2]

[0086] In Table 2, the polymerizable monomers Aronix M-5300 and Light Ester P-1M are as follows. Aronix M-5300: ω-carboxy-polycaprolactone monoacrylate (manufactured by Toagosei Co., Ltd.) Light Ester P-1M: 2-methacryloyloxyethyl acid phosphate (manufactured by Kyoeisha Chemical Co., Ltd.)

[0087] The units of the numerical values 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.

[0088] (Preparation of Paint Composition and Formation of Paint Film) The obtained resin compositions (1) to (8) and (1') to (4') were each mixed with 53.4 parts by mass, 25.0 parts by mass of titanium oxide ("Ti-Pure R-960" manufactured by Chemours), 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, and kneaded with a paint shaker for 60 minutes to obtain a kneaded base (non-volatile content: 60% by mass). To the obtained kneaded base, 71.4 parts by mass of the resin compositions (1) to (8) and (1') to (4') were further added, 0.8 part by mass of a metal drier ("DICNATE 3111TL" manufactured by DIC Corporation), 0.5 part by mass of a leveling agent ("BYK-348" manufactured by BYK), and 8.4 parts by mass of water, and mixed to obtain the paint compositions (1) to (8) and (1') to (4'), respectively.

[0089] Using the obtained paint compositions (1) to (8) and (1') to (4'), they were applied onto a zinc phosphate-treated steel sheet with an applicator so that the film thickness became 20 μm. After application, they were left standing at room temperature of 25°C for 7 days to form a crosslinked paint film in which the carbon-carbon unsaturated bonds in the vinyl-modified epoxy ester resin were oxidatively polymerized with a metal drier.

[0090] The following evaluations were performed on the manufactured paint compositions (1) to (8) and (1') to (4'), and the paint films obtained using the paint compositions (1) to (8) and (1') to (4'). The results are shown in Table 3.

[0091] (Evaluation of Pigment Dispersibility) The coating composition was poured into a dedicated glass cell of a liquid dispersion stability evaluation apparatus (Turbiscan MA2000 manufactured by Eihiro Seiki Co., Ltd.), allowed to stand for 1 hour, and then the integrated value of the change in the backscattered light of the coating composition was measured and used as a reference value. After the coating composition in the glass cell was allowed to stand at 25°C for 7 days, the same measurement was performed again. The pigment dispersibility of the coating composition was evaluated by the relative change rate with respect to the reference value of the integrated value after 7 days. If the change rate was less than 15%, it was regarded as having a practically acceptable performance. Note that since the coating composition (4’) of Comparative Example 4 had poor pigment dispersibility, the evaluation after the tack-free arrival time was not carried out. A: Less than 15% B: Change rate of 15% or more.

[0092] (Tack-free arrival time) Using an applicator (gap: 150 μm), the coating composition was applied onto a glass plate (width: about 2 cm, length: about 35 cm). The glass plate coated with the coating composition was set in a coating drying time measuring instrument DTT-II type (manufactured by Taiyu Kikai Co., Ltd.), and the time until it became tack-free was measured. Note that the tack-free arrival time is a value based on ASTM D5895-03 (the time until the scratches on the coating film start to change from continuous linear to dashed is the tack-free arrival time).

[0093] (Substrate adhesion) Regarding the coating film formed in the shape of the above glass plate, the substrate adhesion was evaluated based on JIS K-5400. Specifically, a 1-mm-wide cut was made on the coating film with a cutter to make 100 grid squares, and cellophane tape was attached to cover all the grid squares and quickly peeled off. The number of grid squares remaining adhered after the test was expressed as a percentage. In terms of substrate adhesion, 100% means that there were no peeling parts of the coating film, and 0% means that the entire coating film was peeled off.

[0094] (Waterproofness) The water resistance of the coating film formed on the glass plate was evaluated based on ASTM D870-02. Specifically, the 60° gloss value of the coating film surface was measured in advance with 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 standing for 24 hours. After taking out the test sample, the substrate adhesion was evaluated by the above method (substrate adhesion after immersion in warm water). Next, the 60° gloss value of the coating film surface was measured, and the "gloss retention rate" was obtained by dividing the gloss value after immersion by the gloss value before immersion. In addition, if the substrate adhesion after immersion in the warm water bath is 90% or more and the gloss retention rate is 85% or more, it can be regarded as having a practically acceptable performance.

[0095] (Corrosion resistance) For the coating film formed on the glass plate, an X-shaped cut was made with the blade tip of a cutter knife so as to reach the substrate from above the coating film. This substrate was set in a salt spray tester CYP-90 type (manufactured by Suga Test Instruments Co., Ltd.) corresponding to JIS Z2371, and a 5% sodium chloride aqueous solution was continuously sprayed at 35°C for 10 days. After spraying, the substrate was washed with water and dried at 25°C for 2 hours, then cellophane tape was attached to the coating film, and the degree of peeling of the coating film when the cellophane tape was peeled off was evaluated according to the following criteria. S: The peeling width of the peeling test is less than 1 mm A: The peeling width of the peeling test is 1 mm or more and less than 3 mm B: The peeling width of the peeling test is 3 mm or more Here, the "peeling width" refers to the width of the peeled coating film with the cut made by the cutter knife as the center. If the peeling width is less than 3 mm, it can be regarded as having a practically acceptable performance.

[0096]

Table 3

[0097] From the results of Table 3, it can be seen that in Comparative Example 1 where the epoxy ester resin constituting the vinyl-modified epoxy ester resin has no condensed ring and is a monobenzene ring, the tack-free reaching time, waterproof property, and anticorrosive property are inferior. Also, it can be understood that in Comparative Example 2 where the epoxy ester resin constituting the vinyl-modified epoxy ester resin does not have a condensed ring, the tack-free reaching time, waterproof property, and anticorrosive property are also inferior. In Comparative Example 3, since there is little monocarboxylic acid having a condensed ring, the waterproof property and anticorrosive property are inferior. In Comparative Example 4, since there is a large amount of monocarboxylic acid having a condensed ring, the stability as a paint is lacking.

Claims

1. A vinyl-modified epoxy ester resin having an epoxy ester resin with a polymerizable unsaturated group and a condensed ring and a polymerizable monomer as reaction components, wherein the epoxy ester resin having the polymerizable unsaturated group and the condensed ring is a reaction product of an epoxy resin, an unsaturated fatty acid, and a monocarboxylic acid having a condensed ring with a melting point in the range of 130 to 220°C, and the proportion of the monocarboxylic acid having the condensed ring in all reaction components is in the range of 7 to 25% by mass.

2. The vinyl-modified epoxy ester resin according to claim 1, wherein the monocarboxylic acid having the condensed ring is a monocarboxylic acid having a tricyclic or tetracyclic condensed ring.

3. The vinyl-modified epoxy ester resin according to claim 1 or 2, wherein the monocarboxylic acid having the condensed ring is at least one selected from the group consisting of isopimaric acid, abietic acid, neoabietic acid, pultrunic acid, dehydroabietic acid, oleanonic acid, fusidic acid, podocarpic acid, dihydroabietic acid, camphanic acid, helvolic acid, and pimaric acid.

4. The vinyl-modified epoxy ester resin according to any one of claims 1 to 3, wherein the unsaturated fatty acid is an unsaturated aliphatic monocarboxylic acid having 6 to 40 carbon atoms.

5. The vinyl-modified epoxy ester resin according to any one of claims 1 to 4, wherein the polymerizable monomer has an acidic functional group and further contains an aliphatic amine as the reaction component.

6. The vinyl-modified epoxy ester resin according to claim 5, wherein the polymerizable monomer having the acidic functional group is at least one selected from the group consisting of (meth)acrylic acid, crotonic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, acryloyloxycaprolactonic acid, 2-(meth)acryloyloxyethyl acid phosphate, 3-(meth)acryloyloxypropyl acid phosphate, (meth)acryloyloxypolyoxyethylene glycol acid phosphate, (meth)acryloyloxypolyoxypropylene glycol acid phosphate, and vinylsulfonic acid.

7. A resin composition containing the vinyl-modified epoxy ester resin according to any one of claims 1 to 6.

8. The resin composition according to claim 7, which is an aqueous resin composition further containing water.

9. A paint containing the resin composition according to claim 7 or 8.

10. An article having a coating film of the coating material according to claim 9.

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