JP7192520B2 - Epoxy (meth)acrylate resin, curable resin composition, cured product and article - Google Patents

Description

The present invention comprises an epoxy (meth)acrylate resin having low viscosity and excellent curability and excellent elasticity in a cured product, a curable resin composition containing the same, and the curable resin composition. It relates to cured products and articles.

In recent years, curable compositions such as active energy ray-curable compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting compositions that can be cured by heat have been used in inks, paints, coating agents, adhesives, optical It is widely used in the field of parts and the like. Among them, as a coating agent application, generally, it can impart designability to various substrate surfaces, has excellent curability, and can form a coating film that can prevent deterioration of the substrate surface. is required. Furthermore, in recent years, the industrial world has demanded a material capable of forming a cured coating film having not only curability but also elasticity.

The material capable of forming a cured coating film having elasticity is obtained by reacting a lactone adduct (a1) of a hydroxyalkyl (meth)acrylate, a dicarboxylic anhydride (a2), and an epoxy resin (a3). An active energy ray-curable composition characterized by containing an epoxy acrylate resin (A) and a radically polymerizable monomer (B) as essential components is known (see, for example, Patent Document 1. ), it did not satisfy the performance requirements that are increasing more and more these days.

Therefore, there has been a demand for a material that has low viscosity and excellent curability and that can form a cured product having even more excellent elasticity.

Japanese Patent Application Laid-Open No. 2003-105230

The problem to be solved by the present invention is an epoxy (meth)acrylate resin having low viscosity and excellent curability and excellent elasticity in a cured product, a curable resin composition containing the same, and the cured An object of the present invention is to provide a cured product of a flexible resin composition and an article having a coating film of the cured product.

As a result of intensive studies to solve the above problems, the present inventors have found that an epoxy (meth)acrylate resin containing an aromatic compound having a hydroxyl group, an epihalohydrin, and an unsaturated monobasic acid as essential reaction raw materials. wherein the aromatic compound has at least two hydroxyl groups as substituents on the aromatic ring, and at least two of the hydroxyl groups of the aromatic compound are positioned ortho to each other. The present inventors have found that the above problems can be solved by using an epoxy (meth)acrylate resin that can be used to achieve the present invention.

That is, the present invention provides an epoxy (meth)acrylate resin comprising an aromatic compound (A) having a hydroxyl group, an epihalohydrin (B), and an unsaturated monobasic acid (C) as essential reaction raw materials, The aromatic compound (A) has at least two hydroxyl groups as substituents on the aromatic ring, and at least two of the hydroxyl groups of the aromatic compound (A) are positioned ortho to each other. The present invention relates to a characterized epoxy (meth)acrylate resin, a curable resin composition containing the same, and a cured product and article comprising the curable resin composition.

The epoxy (meth)acrylate resin of the present invention has low viscosity and excellent curability, and is excellent in elasticity in the cured product. The flexible resin composition can be used as a coating agent or an adhesive, and can be particularly preferably used as a coating agent.

13 is a ¹³ C-NMR chart of the epoxy resin produced in Synthesis Example 1. FIG. 13 is a ¹³ C-NMR chart of the epoxy resin produced in Synthesis Example 2. FIG.

The epoxy (meth)acrylate resin of the present invention is characterized by using an aromatic compound (A) having a hydroxyl group, an epihalohydrin (B), and an unsaturated monobasic acid (C) as essential reaction raw materials. .

In addition, in this invention, "(meth)acrylate" means an acrylate and/or a methacrylate. Moreover, "(meth)acryloyl" means acryloyl and/or methacryloyl. Furthermore, "(meth)acryl" means acryl and/or methacryl.

The aromatic compound (A) having a hydroxyl group has at least two hydroxyl groups as substituents on the aromatic ring, and at least two of the hydroxyl groups of the aromatic compound (A) are ortho-positioned to each other. It is located.

Examples of the aromatic compound (A) include compounds represented by the following structural formulas (1-1) to (1-7).

In the above structural formulas (1-1) to (1-7), R ¹ is each independently a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen and each R ² is independently a hydrogen atom or a methyl group. Also, q is 0 or an integer of 1 or more. The position of the substituent R ¹ on the aromatic ring in the above structural formula is arbitrary. In structural formulas (1-4) to (1-7), it indicates that any of the benzene rings present in one molecule may be substituted, and the benzene ring in one molecule It indicates that the number of substituents above is q+2.

Among the compounds represented by the above structural formulas (1-1) to (1-7), epoxy (meth)acrylates having low viscosity and excellent curability and capable of forming cured products having excellent elasticity Dihydroxybenzene in which q is 0 in structural formula (1-1) and trihydroxybenzene in which q is 1 in structural formula (1-1) are preferable, since a resin can be obtained. More specifically, 1,2-dihydroxybenzene having hydroxyl groups at the 1- and 2-positions (hereinafter sometimes referred to as "catechol"), 1,2,3-trihydroxy having hydroxyl groups at the 1-, 2- and 3-positions Benzene (hereinafter sometimes referred to as "pyrogallol") or 1,2,4-trihydroxybenzene having hydroxyl groups at the 1-, 2- and 4-positions is more preferred, and pyrogallol or 1,2,4- Trihydroxybenzene is particularly preferred.

In addition, as the aromatic compound (A), a novolac-type phenol resin or the like using one or more of the compounds represented by the structural formulas (1-1) to (1-7) as reaction raw materials is also used. be able to.

These aromatic compounds (A) can be used alone or in combination of two or more.

Examples of the epihalohydrin (B) include epichlorohydrin and epibromohydrin. These epihalohydrins (B) can be used alone or in combination of two or more. Moreover, among these, epichlorohydrin is preferable from the viewpoint of easy control of the reaction.

The unsaturated monobasic acid (C) refers to a compound having an acid group and a polymerizable unsaturated bond in one molecule. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Examples of the unsaturated monobasic acid (C) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid and the like. Esterified products, acid halides, acid anhydrides, etc. of the unsaturated monobasic acids can also be used. These unsaturated monobasic acids (C) can be used alone or in combination of two or more. Among these, acrylic acid and methacrylic acid are preferred because they yield an epoxy (meth)acrylate resin that has low viscosity, excellent curability, and can form a cured product having excellent elasticity.

The method for producing the epoxy (meth)acrylate resin of the present invention is not particularly limited, and any method may be used. For example, it may be produced by a method of reacting all of the reaction raw materials at once, or may be produced by a method of sequentially reacting the reaction raw materials. Among them, since the reaction is easy to control, the aromatic compound (A) and the epihalohydrin (B) are reacted (step 1), and the intermediate reaction product obtained in step 1 (hereinafter referred to as " Epoxy resin (I)”) and the unsaturated monobasic acid (C) are preferably reacted (step 2).

The step 1 is a reaction between the aromatic compound (A) and the epihalohydrin (B). From the viewpoint of the yield of the desired intermediate reaction product, that is, the epoxy resin (I), the reaction is carried out in the presence of a quaternary onium salt and/or a basic compound in step 1a, and It is preferable to have a step 1b in which the obtained reactant is ring-closed in the presence of a basic compound. Here, when the aromatic compound (A) and the epihalohydrin (B) are reacted, a reaction proceeds in which the hydroxyl groups of the aromatic compound (A) become glycidyl ether groups. At the same time, various reaction products are obtained depending on various reaction conditions, such as the progress of oligomerization due to the reaction of glycidyl ether groups and unreacted hydroxyl groups, or the addition reaction of epihalohydrin, and the ring closure process thereof. , these will be included as by-products. These by-products can be removed from the reaction system and reaction product, but the step of removing only a single component (for example, diglycidyl ether in the case of catechol and triglycidyl ether in the case of pyrogallol) is Industrially, this is a complicated process and is directly linked to product costs, so it is often used as an epoxy resin in a state containing by-products to the extent that it does not adversely affect the resulting cured product.

In addition, the single component (for example, diglycidyl ether in the case of catechol, triglycidyl ether in the case of pyrogallol) has high crystallinity, and when it is used as the epoxy (meth)acrylate resin or curable resin composition of the present invention, handling problems may also arise. From these points of view, it is preferable to use an epoxy resin containing a certain amount of by-products as described above from the point of view of handling or the point of elasticity of the resulting cured product.

From such a viewpoint, the epoxy resin (I) obtained in the step 1 is a cyclic compound (a1) having a cyclic structure containing two adjacent oxygen atoms derived from the aromatic compound (A) as constituent atoms. preferably included.

Examples of the quaternary onium salts include quaternary ammonium salts and quaternary phosphonium salts. These quaternary onium salts can be used alone or in combination of two or more.

Examples of the quaternary ammonium salts include tetramethylammonium cation, methyltriethylammonium cation, tetraethylammonium cation, tributylmethylammonium cation, tetrabutylammonium cation, phenyltrimethylammonium cation, benzyltrimethylammonium cation, phenyltriethylammonium cation, Benzyltriethylammonium cation, chloride salt of benzyltributylammonium cation, tetramethylammonium cation, trimethylpropylammonium cation, tetraethylammonium cation, bromide salt of tetrabutylammonium cation, and the like.

Examples of the quaternary phosphonium salts include tetraethylphosphonium cation, tetrabutylphosphonium cation, methyltriphenylphosphonium cation, tetraphenylphosphonium cation, ethyltriphenylphosphonium cation, butyltriphenylphosphonium cation, and bromine of benzyltriphenylphosphonium cation. compound salts and the like.

Among these quaternary onium salts, tetramethylammonium cation, benzyltrimethylammonium cation, chloride salt of benzyltriethylammonium cation, and bromide salt of tetrabutylammonium cation are preferred.

The amount of the quaternary onium salt to be used is the total amount of the aromatic compound (A) and the epihalohydrin (B) from the viewpoint that the reaction proceeds well and the residue in the product can be reduced. It is preferably 0.15 to 5 parts by mass, more preferably 0.18 to 3 parts by mass, per 100 parts by mass.

Examples of the basic compound include potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate and the like. These basic compounds can be used alone or in combination of two or more. Moreover, among these, potassium hydroxide and sodium hydroxide are preferable.

Further, the amount of the basic compound to be added is 0.01 per 1 mol of the hydroxyl group of the aromatic compound (A), from the viewpoint that the reaction proceeds well and the residue in the product can be reduced. It is preferably from 0.3 mol, more preferably from 0.02 to 0.2 mol.

The quaternary onium and the basic compound may be used alone or in combination of two or more.

The reaction of step 1a is mainly a reaction in which epihalohydrin is added to the hydroxyl group of the aromatic compound. The reaction temperature in step 1a is preferably 20 to 80°C, more preferably 40 to 75°C. The reaction time in step 1a is preferably 0.5 hours or more, more preferably 1 to 50 hours.

Moreover, the reaction of the step 1a may be carried out in an organic solvent, if necessary. Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; toluene, xylene and solvent. Aromatic solvents such as naphtha; Alicyclic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as carbitol, cellosolve, methanol, ethanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkyl ethers and dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, dimethyl sulfone; These organic solvents can be used alone or in combination of two or more.

When the organic solvent is used, the amount used is preferably in the range of 5 to 150 parts by mass, more preferably in the range of 7.5 to 100 parts by mass, based on 100 parts by mass of the epihalohydrin (B). Preferably, it is more preferably in the range of 10 to 50 parts by mass.

The step 1b is a step of ring-closing the reaction product obtained in the step 1a in the presence of a basic compound, and the reaction product obtained in the step 1a as it is or unreacted epihalohydrin present in the system. or part or all of the reaction solvent may be removed before step 1b.

As the basic compound used in step 1b, the same basic compounds as described above can be used, and the basic compounds can be used alone or in combination of two or more.

The amount of the basic compound used is not particularly limited, but it is preferably 0.8 to 1.5 mol, and preferably 0.9 to 1.5 mol, per 1 mol of the hydroxyl group of the aromatic compound (A). More preferably 3 mol. It is preferable that the addition amount of the basic compound is 0.8 mol or more because the ring closure reaction in step 1b can proceed favorably. On the other hand, when the amount of the basic compound added is 1.5 mol or less, it is preferable because side reactions can be prevented or suppressed. When a basic compound is used in step 1a, it is preferable to use the above amount including the amount used in step 1a.

The reaction temperature in step 1b is preferably 30 to 120°C, more preferably 25 to 80°C. The reaction time is preferably 0.5 to 4 hours, more preferably 1 to 3 hours.

After performing the step 1b, the reaction product obtained can be purified, etc., if necessary.

Examples of the cyclic compound (a1) include, but are not limited to, compounds represented by the following structural formulas.

In the formula, each R is independently a hydrogen atom or a methyl group, and each R ¹ is independently a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen is any atom, m is 0 or an integer of 1-4, and n is 0 or an integer of 1-3.

In the formula, each R is independently a hydrogen atom or a methyl group, and each R ¹ is independently a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen is any atom, and m is 0 or an integer of 1-6.

In the formula, each R is independently a hydrogen atom or a methyl group, and each R ¹ is independently a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen is any atom, and m is 0 or an integer of 1-8.

In the formula, each R is independently a hydrogen atom or a methyl group, and each R ¹ is independently a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, a halogen each R ² is independently a hydrogen atom or a methyl group; and m is 0 or an integer of 1-8.

The cyclic compound (a1) may be contained alone or in combination of two or more.

The content of the cyclic compound (a1) has a low viscosity, and an epoxy (meth)acrylate resin capable of forming a cured product having excellent elasticity is obtained. , preferably 0.040 to 0.115 mol, particularly preferably 0.050 to 0.115 mol, most preferably 0.070 to 0.115 mol. In addition, when the content of the cyclic compound is within this range, the effect of suppressing crystallization is enhanced. In addition, in this specification, "the content of a cyclic compound" is the value measured by the method as described in an Example. Moreover, when two or more kinds of cyclic compounds are included, the "content of cyclic compounds" is the total content thereof.

The content of the cyclic compound (a1) can be controlled by appropriately adjusting the charging ratio of raw materials, catalyst, solvent type and reaction conditions in the reaction with the epihalohydrin (B) or the ring closure step.

The step 2 is a reaction between the epoxy resin (I) obtained in the step 1 and the unsaturated monobasic acid (C). The reaction ratio is such that the obtained epoxy (meth)acrylate resin has an epoxy group and a (meth)acryloyl group, and a low-viscosity epoxy (meth)acrylate resin is obtained, so the epoxy resin (I) has The number of moles of acid groups of the unsaturated monobasic acid (C) per 1 mole of epoxy groups is preferably in the range of 0.25 to 0.75. The reaction of step 2 can be carried out, for example, in the presence of a suitable esterification catalyst, with heating and stirring at a temperature of about 80 to 140°C. Moreover, the reaction of the step 2 may be carried out in an organic solvent, if necessary.

The epoxy equivalent weight of the solid content of the epoxy resin (I) is preferably in the range of 150 to 1000 g/equivalent so that a low-viscosity epoxy (meth)acrylate resin can be obtained.

Examples of the esterification catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine; amine compounds such as triethylamine, tributylamine and dimethylbenzylamine; 2-methylimidazole, 2-heptadecylimidazole, 2-ethyl -4-methylimidazole, 1-benzyl-2-methylimidazole, 1-isobutyl-2-methylimidazole and other imidazole compounds. These esterification catalysts can be used alone or in combination of two or more.

As the organic solvent, the same organic solvent as described above can be used, and the organic solvent can be used alone or in combination of two or more. Further, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, since the reaction efficiency is improved.

Since the epoxy (meth)acrylate resin of the present invention has a polymerizable (meth)acryloyl group in its molecular structure, it can be used as a curable resin composition by adding a photopolymerization initiator, for example. .

As for the photopolymerization initiator, an appropriate one may be selected and used according to the type of active energy ray to be irradiated. Further, it may be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound and a nitrile compound. Specific examples of photopolymerization initiators include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino) -2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkylphenone photoinitiators; 2,4,6-trimethylbenzoyl-diphenyl- acylphosphine oxide-based photopolymerization initiators such as phosphine oxide; intramolecular hydrogen abstraction type photopolymerization initiators such as benzophenone compounds; Each of these may be used alone, or two or more of them may be used in combination.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2- Hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1- one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, and the like.

Commercially available products of the other photopolymerization initiators include, for example, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", and "Omnirad-379". , "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", " Omnirad-754”, “Omnirad-784”, “Omnirad-500”, “Omnirad-81” (manufactured by IGM), “Kayacure-DETX”, “Kayacure-MBP”, “Kayacure-DMBI”, “Kayacure-EPA ”, “Kayacure-OA” (manufactured by Nippon Kayaku Co., Ltd.), “Vicure-10”, “Vicure-55” (manufactured by Stouffer Chemical), “Trigonal P1” (manufactured by Akzo), “Sunray 1000” ( Sands), "Deep" (Upjohn), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (Ward Blenkinsop), "Runtecure-1104" (Runtec company) and the like. These photopolymerization initiators can be used alone or in combination of two or more.

The amount of the photopolymerization initiator added is, for example, preferably in the range of 0.05 to 15% by mass with respect to the total of components other than the solvent of the curable resin composition, and in the range of 0.1 to 10% by mass. is more preferable.

The curable resin composition of the present invention may contain resin components other than the epoxy (meth)acrylate resin described above. Examples of the other resin components include epoxy resins and various (meth)acrylate monomers.

Examples of the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, Bisphenol novolak type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Reactive epoxy resins, biphenylaralkyl-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, dihydroxybenzene-type epoxy resins, trihydroxybenzene-type epoxy resins, and the like can be mentioned. These epoxy resins can be used alone or in combination of two or more.

The various (meth)acrylate monomers are not particularly limited as long as they have a (meth)acryloyl group. Examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, ) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate and other aliphatic mono (meth) acrylate compounds; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate , adamantyl mono (meth) acrylate and other alicyclic mono (meth) acrylate compounds; glycidyl (meth) acrylate, tetrahydrofurfuryl acrylate and other heterocyclic mono (meth) acrylate compounds; benzyl (meth) acrylate, phenyl (meth) ) acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate , benzylbenzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate, etc. Mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds: In the molecular structure of the various mono (meth) acrylate monomers (poly ) (poly)oxyalkylene-modified mono(meth)acrylate compounds introduced with polyoxyalkylene chains such as oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains; Lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di( Aliphatic di(meth)acrylate compounds such as meth)acrylate and neopentyl glycol di(meth)acrylate; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth) Alicyclic di(meth)acrylates such as acrylates, dicyclopentanyl di(meth)acrylates, and tricyclodecanedimethanol di(meth)acrylates rate compounds; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; ) A polyoxyalkylene-modified di(meth)acrylate compound into which a (poly)oxyalkylene chain such as an oxypropylene chain or (poly)oxytetramethylene chain is introduced; ) Lactone-modified di(meth)acrylate compounds having a lactone structure; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; the aliphatic tri(meth)acrylate compounds A (poly)oxyalkylene-modified tri(meth)acrylate compound in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, (poly)oxypropylene chain, or (poly)oxytetramethylene chain is introduced into the molecular structure of; Lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure is introduced into the molecular structure of the aliphatic tri(meth)acrylate compound; pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipenta A tetrafunctional or higher aliphatic poly(meth)acrylate compound such as erythritol hexa(meth)acrylate; (poly)oxyethylene chain, (poly)oxypropylene chain, ( Tetrafunctional or higher (poly)oxyalkylene-modified poly(meth)acrylate compound introduced with a (poly)oxyalkylene chain such as a poly(poly)oxytetramethylene chain; in the molecular structure of the aliphatic poly(meth)acrylate compound (poly ) Tetra- or higher-functional lactone-modified poly(meth)acrylate compounds into which a lactone structure is introduced; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, Hydroxyl group-containing (meth)acrylate such as dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, etc. Acrylate compound; a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, (poly)oxypropylene chain, or (poly)oxytetramethylene chain introduced into the molecular structure of the hydroxyl group-containing (meth)acrylate compound (poly ) oxyalkylene modified product; lactone modified product in which a (poly)lactone structure is introduced into the molecular structure of the hydroxyl group-containing (meth)acrylate compound; 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis (Acryloyloxymethyl) isocyanate group-containing (meth)acrylate compounds such as ethyl isocyanate; ) Epoxy group-containing (meth)acrylate compounds such as acrylate monomers, mono(meth)acrylates of diglycidyl ether compounds of droxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether is mentioned. The various (meth)acrylate monomers can be used alone or in combination of two or more.

In addition, the curable resin composition of the present invention may optionally contain a cured product, a curing accelerator, an organic solvent, inorganic fine particles or polymer fine particles, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a flame retardant, Various additives such as storage stabilizers can also be contained.

The curing agent is not particularly limited as long as it has a functional group capable of reacting with the epoxy group in the epoxy (meth)acrylate resin. Examples include polybasic acid, polybasic acid anhydride, and unsaturated monobasic Examples include acids, amine compounds, amide compounds, and the like.

Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid. , tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2 .2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1, 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid and the like. As the polybasic acid, for example, a copolymer of a conjugated diene-based vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used. These polybasic acids can be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydro phthalic anhydride, methylhexahydrophthalic anhydride, octenyl succinic anhydride, tetrapropenyl succinic anhydride and the like. These polybasic acid anhydrides can be used alone or in combination of two or more.

As the unsaturated monobasic acid, the same unsaturated monobasic acid (C) as described above can be used, and the unsaturated monobasic acid can be used alone or in combination of two or more. can.

Examples of the amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complexes, guanidine derivatives and the like. These amine compounds can be used alone or in combination of two or more.

Examples of amide-based compounds include dicyandiamide and polyamide resins synthesized from dimers of linolenic acid and ethylenediamine. These amide compounds can be used alone or in combination of two or more.

The curing accelerator accelerates the curing reaction, and examples thereof include phosphorus compounds, amine compounds, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. These curing accelerators can be used alone or in combination of two or more. Moreover, the amount of the curing accelerator to be added is preferably in the range of 0.01 to 10% by mass based on the solid content of the curable resin composition.

As the organic solvent, the same organic solvent as described above can be used, and these organic solvents can be used alone or in combination of two or more.

The cured product of the present invention can be obtained by irradiating the curable resin composition with an active energy ray. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, the irradiation may be performed in an atmosphere of an inert gas such as nitrogen gas or in an air atmosphere in order to efficiently perform the curing reaction using the ultraviolet rays.

An ultraviolet lamp is generally used as a source of ultraviolet light from the viewpoint of practicality and economy. Specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.

The integrated amount of active energy rays is not particularly limited, but is preferably 10 to 5,000 mJ/cm ² , more preferably 50 to 1,000 mJ/cm ² . It is preferable that the integrated amount of light is within the above range because the generation of uncured portions can be prevented or suppressed.

The irradiation with the active energy ray may be performed in one step, or may be performed in two or more steps.

The article of the present invention has a coating film made of the cured product. Examples of the articles include mobile phones, home electric appliances, automotive interior and exterior materials, plastic moldings such as OA equipment, semiconductor devices, display devices, imaging devices, and the like.

The present invention will be described in more detail below with examples and comparative examples.

In the examples, the weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) under the following conditions.

<GPC measurement conditions>
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,
Column: Guard column "HXL-L" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: "GPC-8020 model II version 4.10" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40°C
Developing solvent Tetrahydrofuran
Flow rate 1.0 ml/min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of "GPC-8020 Model II Version 4.10".

(Polystyrene used)
"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
Sample: A 1.0% by mass tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (50 μl).

In this example, ¹³ C-NMR was measured under the following conditions.

< ¹³ C-NMR measurement conditions>
Device: JNM-ECA500 manufactured by JEOL Ltd.
Measurement mode: Decoupling with reverse gate Solvent: Deuterated dimethyl sulfoxide Pulse angle: 30° pulse Sample concentration: 30 wt%
Accumulation times: 4000 times Chemical shift standard: Peak of dimethyl sulfoxide: 39.5 ppm

In the examples of the present application, the content X (mol) of the cyclic compound in the epoxy resin was calculated by the following formula.

In the above formula, X is the cyclic compound content (mol) per 100 g of the epoxy resin, (A) is the cyclic compound (mol) per 1 mol of the aromatic ring, and (B) is the epoxy group per 1 mol of the aromatic ring ( mol) and (C) is the epoxy equivalent weight (g/equivalent).

(Synthesis Example 1: Synthesis of epoxy resin (1))
Step 1a
165 g (1.50 mol) of catechol and 1388 g (15 mol) of epichlorohydrin were added to a flask equipped with a thermometer, dropping funnel, condenser, nitrogen inlet tube and stirrer, and the temperature was raised to 50°C. Then, 11.2 g (0.06 mol) of benzyltrimethylammonium chloride was added and stirred at 50° C. for 15 hours.

Step 1b
1000 mL of distilled water was poured into the reaction liquid obtained in the step 1a, and the mixture was stirred, left to stand, and then the upper layer was removed. 318 g of a 48% sodium hydroxide aqueous solution was added dropwise over 2.5 hours, and the mixture was stirred for 1 hour.

400 mL of distilled water was poured into the resulting solution and left to stand. The lower layer of saline was removed, and epichlorohydrin was recovered by distillation at 120°C. Then, 566 g of methyl isobutyl ketone (hereinafter abbreviated as "MIBK") and 167 g of water were sequentially added and washed with water at 80°C. After removing the washing water of the lower layer, dehydration and filtration were performed, and MIBK was desolvated at 150° C. to produce epoxy resin (1). In addition, when the obtained epoxy resin was visually observed, it was found to be liquid.

This epoxy resin (1) had an epoxy equivalent weight of 138 g/equivalent and a viscosity at 25° C. of 190 mPa·s. In the present invention, the epoxy equivalent is a value measured according to JIS K 7236:2009, and the viscosity is a value measured with "TV-22" manufactured by Toki Sangyo Co., Ltd.

In addition, the cyclic compound content (mol) per 100 g of this epoxy resin (1) is expressed in the above formula, where (A) is an aromatic ring corresponding to the ipso position of catechol near 130 to 150 ppm in ¹³ C-NMR measurement. and the peak derived from the cyclic compound near 60 ppm. It was calculated from the integral ratio of peaks derived from nearby epoxy groups. As a result, the content of the cyclic compound was 0.071 mol/100 g. The results of ¹³ C-NMR measurement [chart] are shown in FIG.

(Synthesis Example 2: Synthesis of epoxy resin (2))
Epoxy resin in the same manner as in Synthesis Example 1 except that 165 g (1.50 mol) of catechol in step (1) of Synthesis Example 1 was changed to 126 g (1.00 mol) of pyrogallol, 566 g of MIBK was changed to 500 g, and 167 g of water was changed to 147 g. (2) was produced. In addition, when the obtained epoxy resin was visually observed, it was found to be liquid. This epoxy resin (2) has an epoxy equivalent weight of 128 g/equivalent and a viscosity at 25° C. of 3100 mPa.s. was s. Moreover, the cyclic compound content per 100 g of this epoxy resin (2) was 0.086 mol/100 g. The result of ¹³ C-NMR measurement [chart] is shown in FIG.

(Synthesis Example 3: Synthesis of epoxy resin (3))
An epoxy resin was produced according to the Experimental section described in Non-Patent Document (Tetrahedron, 2013, 69, 1345-1353). 126 g (1.00 mol) of 1,2,3-trihydroxybenzene and 1111 g (12 mol) of epichlorohydrin were placed in a flask equipped with a thermometer, a dropping funnel, a condenser, a nitrogen inlet tube, and a stirrer, and heated to 100°C. The temperature was raised to 11.4 g (0.05 mol) of benzyltriethylammonium chloride was added thereto, and the mixture was heated and stirred at 100° C. for 1 hour. After that, the temperature was lowered to 30° C., 780 g of a 20% NaOH aqueous solution was added dropwise over 2.5 hours, and the mixture was stirred for 1 hour and allowed to stand still. After that, the same operation as in Synthesis Example 1 was performed to produce an epoxy resin (3). In addition, when the obtained epoxy resin was visually observed, it was found to be liquid.

The epoxy equivalent of this epoxy resin (3) was 184 g/equivalent, and the viscosity at 25° C. was 53300 mPa·s. Moreover, the content of the cyclic compound per 100 g of this epoxy resin (3) was 0.120 mol/100 g.

(Synthesis Example 4: Synthesis of epoxy resin (4))
Epoxy resin (4) was produced by purifying the epoxy resin produced in Synthesis Example 3 by recrystallization using MIBK as a good solvent and hexane as a poor solvent. The epoxy equivalent of this epoxy resin (4) was 107 g/equivalent. Moreover, the cyclic compound content per 100 g of this epoxy resin (4) was 0.039 mol/100 g. The viscosity could not be measured because the obtained epoxy resin (4) was solid.

(Example 1: Preparation of epoxy acrylate resin (1))
Into a flask equipped with a thermometer, stirrer, and reflux condenser, 24 g butyl acetate, 138 g epoxy resin (1), 0.2 g dibutylhydroxytoluene, 0.1 g methoquinone, 72 g acrylic acid and 1.1 g triphenylphosphine. and reacted at 100° C. for 20 hours while blowing air to obtain the desired epoxy acrylate resin (1). This epoxy acrylate resin (1) had a solid weight average molecular weight of 870, an epoxy equivalent of 25790 g/equivalent, and a viscosity at 25° C. of 38 Pa·s. Further, the number of moles of acrylic acid per 1 mole of epoxy groups possessed by the epoxy resin (1) was 1.0.

(Example 2: Preparation of epoxy acrylate resin (2))
In a flask equipped with a thermometer, stirrer, and reflux condenser, 22 g butyl acetate, 128 g epoxy resin (2), 0.2 g dibutylhydroxytoluene, 0.1 g methoquinone, 72 g acrylic acid, and 1.0 g triphenylphosphine. and reacted at 100° C. for 20 hours while blowing air to obtain the desired epoxy acrylate resin (2). This epoxy acrylate resin (2
) had a weight average molecular weight of 910, an epoxy equivalent of 12580 g/equivalent, and a viscosity at 25° C. of 65 Pa·s. Further, the number of moles of acrylic acid per 1 mole of epoxy groups possessed by the epoxy resin (2) was 1.0.

(Example 3: Preparation of epoxy acrylate resin (3))
Into a flask equipped with a thermometer, stirrer, and reflux condenser, 19 g butyl acetate, 138 g epoxy resin (1), 0.1 g dibutylhydroxytoluene, 0.1 g methoquinone, 36 g acrylic acid and 0.1 g triphenylphosphine. Then, an esterification reaction was carried out at 80° C. for 20 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH/g or less, 0.1 part by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain the desired epoxy acrylate resin (3). The epoxy acrylate resin (3) had a solid weight average molecular weight of 510, an epoxy equivalent of 491 g/equivalent, and a viscosity at 25° C. of 730 mPa·s. Further, the number of moles of acrylic acid per 1 mole of epoxy groups possessed by the epoxy resin (1) was 0.5.

(Example 4: Preparation of epoxy acrylate resin (4))
In a flask equipped with a thermometer, stirrer, and reflux condenser, 18 g butyl acetate, 128 g epoxy resin (2), 0.1 g dibutylhydroxytoluene, 0.1 g methoquinone, 36 g acrylic acid, and 0.1 g triphenylphosphine. Then, an esterification reaction was carried out at 80° C. for 20 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH/g or less, 0.1 part by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain the desired epoxy acrylate resin (4). This epoxy acrylate resin (4) had a solid weight average molecular weight of 550, an epoxy equivalent of 521 g/equivalent, and a viscosity at 25° C. of 10 Pa·s. Further, the number of moles of acrylic acid per 1 mole of epoxy groups possessed by the epoxy resin (2) was 0.5.

(Example 5: Preparation of epoxy acrylate resin (5))
In a flask equipped with a thermometer, stirrer, and reflux condenser, 24 g butyl acetate, 184 g epoxy resin (3), 0.1 g dibutylhydroxytoluene, 0.1 g methoquinone, 36 g acrylic acid, and 0.1 g triphenylphosphine. Then, an esterification reaction was carried out at 80° C. for 20 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH/g or less, 0.1 part by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain the desired epoxy acrylate resin (5). The epoxy acrylate resin (5) had a solid weight average molecular weight of 610, an epoxy equivalent of 632 g/equivalent, and a viscosity at 25° C. of 103 Pa·s. Further, the number of moles of acrylic acid per 1 mole of epoxy groups possessed by the epoxy resin (3) was 0.5.

(Example 6: Preparation of epoxy acrylate resin (6))
In a flask equipped with a thermometer, stirrer, and reflux condenser, 16 g butyl acetate, 107 g epoxy resin (4), 0.1 g dibutylhydroxytoluene, 0.1 g methoquinone, 36 g acrylic acid, and 0.1 g triphenylphosphine. Then, an esterification reaction was carried out at 80° C. for 20 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH/g or less, 0.1 part by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain the desired epoxy acrylate resin (6). This epoxy acrylate resin (6) had a solid weight average molecular weight of 530, an epoxy equivalent of 482 g/equivalent, and a viscosity at 25° C. of 207 Pa·s. Further, the number of moles of acrylic acid per 1 mole of epoxy groups possessed by the epoxy resin (4) was 0.5.

(Example 7: Preparation of epoxy acrylate resin (7))
In a flask equipped with a thermometer, stirrer, and reflux condenser, 128 g of epoxy resin (2), 0.1 g of dibutylhydroxytoluene, 0.1 g of methoquinone, 36 g of acrylic acid, 0.1 g of triphenylphosphine are added and air is added. The esterification reaction was carried out at 80° C. for 20 hours while blowing in. Then, after confirming that the acid value was 1 mgKOH/g or less, 0.1 part by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain the desired epoxy acrylate resin (7). The epoxy acrylate resin (7) had a solid weight average molecular weight of 570, an epoxy equivalent of 541 g/equivalent, and a viscosity at 25° C. of 150 Pa·s. Further, the number of moles of acrylic acid per 1 mole of epoxy groups possessed by the epoxy resin (2) was 0.5.

(Example 8: Preparation of epoxy acrylate resin (8))
In a flask equipped with a thermometer, stirrer, and reflux condenser, 16 g butyl acetate, 128 g epoxy resin (2), 0.1 g dibutylhydroxytoluene, 0.1 g methoquinone, 14 g acrylic acid, and 0.1 g triphenylphosphine. Then, an esterification reaction was carried out at 80° C. for 20 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH/g or less, 0.1 part by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain the desired epoxy acrylate resin (8). The epoxy acrylate resin (8) had a weight average molecular weight of 500, an epoxy equivalent of 269 g/equivalent, and a viscosity of 2 Pa·s at 25°C. Further, the number of moles of acrylic acid per 1 mole of epoxy groups possessed by the epoxy resin (2) was 0.2.

(Example 9: Preparation of epoxy acrylate resin (9))
Into a flask equipped with a thermometer, stirrer, and reflux condenser, 17 g butyl acetate, 128 g epoxy resin (2), 0.1 g dibutylhydroxytoluene, 0.1 g methoquinone, 22 g acrylic acid, and 0.1 g triphenylphosphine. Then, an esterification reaction was carried out at 80° C. for 20 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH/g or less, 0.1 part by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain the desired epoxy acrylate resin (8). This epoxy acrylate resin (9) had a solid weight average molecular weight of 520, an epoxy equivalent of 303 g/equivalent, and a viscosity at 25° C. of 5 Pa·s. Further, the number of moles of acrylic acid per 1 mole of epoxy groups possessed by the epoxy resin (2) was 0.3.

(Example 10: Preparation of epoxy acrylate resin (10))
In a flask equipped with a thermometer, stirrer, and reflux condenser, 20 g butyl acetate, 128 g epoxy resin (2), 0.1 g dibutylhydroxytoluene, 0.1 g methoquinone, 50 g acrylic acid, and 0.1 g triphenylphosphine. Then, an esterification reaction was carried out at 80° C. for 20 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH/g or less, 0.1 part by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain the desired epoxy acrylate resin (10). This epoxy acrylate resin (10) had a weight average molecular weight of 710, an epoxy equivalent of 781 g/equivalent, and a viscosity of 20 Pa·s at 25°C. Further, the number of moles of acrylic acid per 1 mole of epoxy groups possessed by the epoxy resin (2) was 0.7.

(Comparative Example 1: Preparation of epoxy acrylate resin (C1))
A flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 151 g of phenyl glycidyl ether (“Denacol EX-141” manufactured by Nagase Chemtex Co., Ltd., epoxy equivalent: 151 g/equivalent), 0.2 g of dibutylhydroxytoluene, and methoquinone. 0.1 g of acrylic acid, 73 g of acrylic acid and 1.1 g of triphenylphosphine were added and reacted at 120° C. for 8 hours while blowing air to obtain the desired epoxy acrylate resin (C1). This epoxy acrylate resin (C1) had a solid weight average molecular weight of 470, an epoxy equivalent of 31590 g/equivalent, and a viscosity at 25° C. of 750 mPa·s.

(Comparative Example 2: Preparation of epoxy acrylate resin (C2))
A flask equipped with a thermometer, stirrer and reflux condenser was charged with 18 g of butyl acetate, 129 g of resorcinol-type epoxy resin ("ERISYS RDGE-H" manufactured by CVC Thermoset Specialties, epoxy equivalent: 129 g/equivalent), and 0.2 g of dibutylhydroxytoluene. 1 g, 0.1 g of methoquinone, 36 g of acrylic acid and 0.1 g of triphenylphosphine were added, and an esterification reaction was carried out at 80° C. for 20 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH/g or less, 0.1 part by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain the desired epoxy acrylate resin composition (C2). . This epoxy acrylate resin (C2) had a solid weight average molecular weight of 890, an epoxy equivalent of 565 g/equivalent, and a viscosity at 25° C. of 3 Pa·s.

(Comparative Example 3: Preparation of epoxy acrylate resin (C3))
A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 151 g of phenylglycidyl ether ("Denacol EX-141" manufactured by Nagase Chemtex Co., Ltd., epoxy equivalent: 151 g/equivalent), 0.1 g of dibutylhydroxytoluene, and methoquinone. 0.1 g, 36 g of acrylic acid and 0.1 g of triphenylphosphine were added, and an esterification reaction was carried out at 80° C. for 20 hours while blowing air. Then, after confirming that the acid value was 1 mgKOH/g or less, 0.1 part by mass of oxalic acid was added and stirred at 70°C for 3 hours to obtain the desired epoxy acrylate resin composition (C3). . This epoxy acrylate resin (C3) had a solid weight average molecular weight of 440, an epoxy equivalent of 387 g/equivalent, and a viscosity at 25° C. of 60 mPa·s.

(Example 11: Preparation of curable resin composition (1))
80 parts by mass of the epoxy acrylate resin (1) obtained in Example 1, 20 parts by mass of EO-modified diacrylate of bisphenol A (“Miramaer M240” manufactured by Miwon Specialty Chemical Co., Ltd.) and a photopolymerization initiator (manufactured by IGM Co., Ltd.) as an acrylate monomer 2.0 parts by mass of "Omnirad-184") and kneaded by a roll mill to obtain a curable resin composition (1).

(Examples 12 to 20: Preparation of curable resin compositions (2) to (10))
Curability was determined in the same manner as in Example 11, except that the epoxy acrylate resins (2) to (10) obtained in Examples 2 to 10 were used instead of the epoxy acrylate resin (1) used in Example 11. Resin compositions (2) to (10) were obtained.

(Comparative Examples 4 to 6: Preparation of curable resin compositions (C4) to (C6))
A curable resin was prepared in the same manner as in Example 11, except that the epoxy acrylate resins (C1) to (C3) obtained in Comparative Examples 1 to 3 were used instead of the epoxy acrylate resin (1) used in Example 11. Compositions (C4) to (C6) were obtained.

The following evaluations were performed using the curable resin compositions (1) to (10) and (C4) to (C6) obtained in the above examples and comparative examples.

[Curability evaluation method]
The curable resin compositions (1) to (10) obtained in Examples and the curable resin compositions (C4) to (C6) obtained in Comparative Examples were coated on a glass substrate using an applicator. It was applied so as to have a thickness of 50 μm. Then, using a high-pressure mercury lamp, ultraviolet rays were irradiated to obtain a cured coating film. The surface of the obtained cured coating film was touched with a finger, and the minimum value of the integrated amount of light when the tack disappeared was evaluated according to the following criteria.

A: Cured at an integrated amount of light of 300 mJ/cm ² or less.
B: Cured at an integrated light quantity of more than 300 mJ/cm ² and less than or equal to 400 mJ/cm ² .
C: Cured at an integrated amount of light of more than 400 mJ/cm ² and less than or equal to 500 mJ/cm ² .
D: Cured at an integrated amount of light exceeding 500 mJ/cm ² and not more than 600 mJ/cm ² .
E: Curing did not occur even when the cumulative amount of light exceeded 600 mJ/cm ² .

[Method for measuring elasticity]
Elasticity measurements were based on tensile tests.
<Preparation of test piece>
The curable resin compositions obtained in Examples and Comparative Examples were applied on glass with a 50 μm applicator and dried at 80° C. for 30 minutes. After irradiating ultraviolet rays of 1000 mJ/cm ² using a metal halide lamp, it was heated at 160° C. for 1 hour. The cured product was separated from the glass to obtain a test piece (cured product).

<Tensile test>
The test piece was cut into a size of 10 mm x 80 mm, and a tensile test was performed on the test piece under the following measurement conditions using a precision universal testing machine Autograph "AG-IS" manufactured by Shimadzu Corporation. The elastic modulus (MPa) until the test piece breaks was measured and evaluated according to the following criteria.

Measurement conditions: temperature 23° C., humidity 50%, distance between gauge lines 20 mm, distance between fulcrums 20 mm, tensile speed 10 mm/min.

The compositions and evaluation results of the curable resin compositions (1) to (10) prepared in Examples 11 to 20 and the curable resin compositions (C4) to (C6) prepared in Comparative Examples 4 to 6 are shown in Table 1. show.

"Acrylate monomer" in Table 1 indicates EO-modified diacrylate of bisphenol A ("Miramaer M240" manufactured by Miwon Specialty Chemical Co.).

"Photopolymerization initiator" in Table 1 indicates "Omnirad-184" manufactured by IGM.

Examples 11 to 20 shown in Table 1 are examples of curable resin compositions using the epoxy acrylate resin of the present invention. It was confirmed that the epoxy acrylate resin of the present invention has a low viscosity, and the curable resin composition containing it has excellent curability and excellent elasticity in the cured product.

On the other hand, Comparative Examples 4 to 6 are examples of curable resin compositions that do not use the epoxy acrylate resin of the present invention. It was confirmed that this curable resin composition had insufficient curability and remarkably insufficient elasticity in the cured product.

Claims (10)

an aromatic compound (A) having a hydroxyl group;
epihalohydrin (B);
an unsaturated monobasic acid (C);
is an epoxy (meth)acrylate resin having as an essential reaction raw material,
The aromatic compound (A) has at least two hydroxyl groups as substituents on the aromatic ring, and at least two of the hydroxyl groups of the aromatic compound (A) are positioned ortho to each other , , 2-dihydroxybenzene and 1,2,3-trihydroxybenzene, at least one selected from the group consisting of
an intermediate reaction product of the aromatic compound (A) and the epihalohydrin (B);
An epoxy (meth)acrylate resin which is a reactant with the unsaturated monobasic acid (C) . The epoxy (meth)acrylate resin according to claim 1 , wherein the intermediate reaction product contains a cyclic compound (a1) having a cyclic structure containing two adjacent oxygen atoms derived from the aromatic compound (A) as constituent atoms. . 3. The epoxy (meth)acrylate resin according to claim 2 , wherein the content of said cyclic compound (a1) is in the range of 0.040 to 0.115 mol per 100 g of said intermediate reaction product. The epoxy (meta- ) acrylate resins. The epoxy (meth)acrylate resin according to Claim 1, which has an epoxy group and a (meth)acryloyl group. A curable resin composition comprising the epoxy (meth)acrylate resin according to any one of claims 1 to 5 and a photopolymerization initiator. 7. The curable resin composition according to claim 6 , further containing an organic solvent. 7. The curable resin composition according to claim 6 , further comprising a (meth)acrylate monomer. A cured product, which is a cured reaction product of the curable resin composition according to any one of claims 6 to 8 . An article comprising a coating film comprising the cured product according to claim 9 .

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