WO2012108305A1

WO2012108305A1 - Epoxy acrylate, acrylic curable composition, cured product and manufacturing processes therefor

Info

Publication number: WO2012108305A1
Application number: PCT/JP2012/052205
Authority: WO
Inventors: 篤彦片山; スレスタ・二ランジャン・クマール
Original assignee: 新日鐵化学株式会社
Priority date: 2011-02-10
Filing date: 2012-02-01
Publication date: 2012-08-16
Also published as: JP5758923B2; JPWO2012108305A1; TW201245141A; TWI507392B

Abstract

Provided are: an epoxy acrylate which exhibits excellent heat resistance and low thermal expansion and is useful for solder resist resins, electroless plating resist resins, hard coat materials, UV-curable coating materials, substitute materials for glass, color filters for liquid crystal displays, and so on; an acrylic composition; and a cured product. The epoxy acrylate is represented by general formula (1) [wherein Z is C_1-6 alkyl; a is a number of 0 to 4; and n is an integer of 2 to 3]. The epoxy acrylate can be obtained by reacting an epoxycyclohexane compound with acrylic acid or methacrylic acid.

Description

Epoxy acrylate, acrylic curable composition, cured product and method for producing the same

The present invention relates to a novel epoxy acrylate, an acrylic curable composition, a cured product, and a production method thereof excellent in heat resistance, fluidity, toughness, photosensitivity, chemical resistance, hardness, transparency, and weather resistance. is there. This epoxy acrylate has high heat resistance, toughness, chemical resistance, hardness, transparency, weather resistance, etc. by polymerizing itself or copolymerizing with compounds having various unsaturated bonds. A molecular material can be given, and it can be used for various applications such as paints, laminates and adhesives. In addition, by using a photo-curable resin composition or a thermosetting resin composition, a solder resist resin, an electroless plating resist resin, a hard coat material, a UV curable paint, a glass substitute material, or even a liquid crystal color It is also suitably used as a protective film for filters and the like.

Epoxy acrylate resins obtained by reaction of epoxy compounds with acrylic acid are widely used as various functional polymer materials such as photosensitive materials and crosslinking agents. Since this resin has a hydroxyl group in the molecule, it is excellent in solvent solubility, heat resistance and the like (Non-Patent Document 1). In particular, in a resin obtained by curing 2-hydroxy-2-phenylethyl acrylate, which is an epoxy acrylate derived from epoxyethylbenzene, which is an epoxyphenyl compound in which an epoxy group is directly bonded to benzene, an epoxy acrylate resin having a general glycidyl ether group Compared with the above, since it does not have a flexible oxymethylene moiety, excellent heat resistance and low thermal expansion are expected by suppressing the molecular motion of the cured product. Furthermore, it is excellent in heat resistance, moisture resistance, chemical resistance, etc. by copolymerization with compounds having various unsaturated bonds (Patent Document 1) and crosslinking with a compound capable of reacting with a hydroxyl group such as isocyanate (Patent Document 2). Give a high polymer material.

However, the role of 2-hydroxy-2-phenylethyl acrylate, which is the only disclosed example of epoxy acrylate derived from epoxyethylbenzene, is exclusively a reaction diluent and a cross-linking agent, and the role of epoxy acrylate itself for the purpose of improving the physical properties of the resin. There was no focus on improvement.

Furthermore, since epoxy acrylate derived from epoxyethylbenzene is an aromatic compound, it is considered that transparency and weather resistance are insufficient for application to the field of optical components.

JP 52-129735 A JP-A-9-59535

Therefore, the object of the present invention is excellent in heat resistance, low thermal expansion, transparency, and weather resistance, and is a resin for solder resist or resin for electroless plating resist, hard coat material, UV curable paint, glass substitute material, liquid crystal It is to provide an epoxy acrylate, an acrylic composition and a cured product useful for a color filter and the like. In particular, it is to provide an acrylic resin composition and a cured product useful as an optical material.

In light of the actual situation in the prior art described above, the present inventors have excellent heat resistance, low thermal expansion, high refractive index, transparency, weather resistance, solder resist resin or electroless plating resist resin, hard coat As a result of earnest research to obtain acrylic resins useful for materials, UV curable paints, glass substitute materials, liquid crystal color filters, etc., epoxy acrylate obtained by reacting an epoxy cyclohexane compound with an unsaturated carboxylic acid is used as an epoxy acrylate. By using it, it has been found that the above problems can be solved, and the present invention has been completed.

That is, the present invention relates to an epoxy acrylate represented by the following general formula (1).

(However, X represents a hydrogen atom or a methyl group. Z represents a C1-C6 alkyl group, all of which may be the same or different. N represents a number from 2 to 3. a represents a number from 0 to 4. Indicates the number.)

Moreover, this invention relates to the epoxy acrylate which contains the epoxy acrylate represented by the said General formula (1) as a main component, and contains the epoxy acrylate represented by the following General formula (2) as a subcomponent.

However, A is an ester bond-containing group represented by Formula (3), and B is an ester bond-containing group represented by Formula (3) or Formula (4). b represents an integer of 1 to 2. Z, X, and a have the same meaning as in general formula (1).

The present invention also relates to an acrylic curable composition comprising the above epoxy acrylate and a polymerization initiator. Moreover, this invention relates to the acrylic resin hardened | cured material characterized by shape-hardening this acrylic curable composition.

The present invention also relates to a method for producing the above epoxy acrylate, characterized by reacting the epoxycyclohexane compound represented by the general formula (5) with acrylic acid or methacrylic acid.

(However, Z, a and n have the same meaning as in general formula (1).)

Further, the present invention is an acrylic curable composition or an acrylic resin cured product, wherein the acrylic curable composition or the acrylic resin cured product is for an optical material.

Triepoxy methacrylate cyclohexane ¹ H -NMR spectrum is shown.

First, the epoxy acrylate of the present invention will be described.

The epoxy acrylate of the present invention is represented by the above general formula (1). Here, X represents a hydrogen atom or a methyl group. Z represents a C1-C6 alkyl group, and all may be the same or different. n represents an integer of 2 to 3. a represents an integer of 0 to 4. However, n + a does not exceed 6.

The epoxy acrylate represented by the general formula (1) is obtained by reacting the epoxycyclohexane compound represented by the general formula (5) with an unsaturated carboxylic acid (meaning including acrylic acid, methacrylic acid, or both). It can be produced by acrylated. Therefore, the kind of Z comes from the structure of the epoxycyclohexane compound used as a raw material. Z is a C1 to C6 alkyl group, and a is an integer of 0 to 4, preferably 0 to 1, from the viewpoint of the availability of the epoxycyclohexane compound and the properties of the resulting epoxy acrylate.

The epoxycyclohexane compound represented by the general formula (5) can have a structure in which two epoxyethyl groups are substituted on the cyclohexane skeleton (disubstituted product) or a structure in which three epoxyethyl groups are substituted (trisubstituted product). The isomers of the di-substituted product include 1,2-di-substituted product (o-isomer), 1,3-di-substituted product (m-isomer) and 1,4-di-substituted product (p-isomer). Tri-substituted isomers include 1,2,3-tri-substituted, 1,2,4-tri-substituted, and 1,3,5-tri-substituted. As an epoxycyclohexane compound used in the production method of the present invention, a mixture of these isomers (may be a di-substituted product, a tri-substituted product or a mixture of a di-substituted product and a tri-substituted product). In the case of a mixture of isomers, those having a high content of m-isomer and p-isomer are preferable from the viewpoint of both heat resistance and low viscosity, and are 90% by weight or more, preferably 95% by weight or more. -Those containing the body are preferably used. Further, from the viewpoint of heat resistance of the cured acrylic resin, a tri-substituted product is preferable, and a 1,2,4-tri-substituted product is particularly preferable.

The epoxy acrylate of the present invention can be produced by reacting an epoxycyclohexane compound with an unsaturated carboxylic acid. In this reaction, the epoxy group of the epoxycyclohexane compound is ring-opened to form an ester bond with the unsaturated carboxylic acid. This ring-opening occurs from both α-position and β-position, but the epoxy acrylate (α-adduct) of the above general formula (1) opened at the α-position is a main component, and the above-described general formula opened at the β-position. The epoxy acrylate (β adduct) of (2) is a subcomponent. There are two types of epoxy acrylates of general formula (2). That is, both A and B in the general formula (2) are ester bond-containing groups (β adducts) represented by the formula (3), and A in the general formula (2) is the formula (3). In some cases, a part or all of B is an ester bond-containing group (α adduct) represented by the formula (4). The former is called a full β adduct, the latter is called a half β adduct, and both are collectively called a β adduct. The production rate of the total β-adduct is sufficiently lower than that of the half-β-adduct. In addition, when both A and B in General formula (2) are ester bond containing groups ((alpha) adduct) represented by Formula (3), it becomes the same as General formula (1).

In the above production method, the production ratio of α-adduct and β-adduct is usually 100 / 0.01 to 100/70, preferably 100 / 0.1 to 100/50 in molar ratio. Therefore, in the above production method, an epoxy acrylate containing both the α-adduct and β-adduct of the present invention is usually obtained. When distinguishing an epoxy acrylate containing both an α-adduct and a β-adduct from an epoxy acrylate comprising only the epoxy acrylate of the general formula (1), the former is called an epoxy acrylate composition, and the latter is a general formula (1). This is called epoxy acrylate. Especially when it is not necessary to distinguish, both are called epoxy acrylate.
The epoxy acrylate of the general formula (1) can be separated from the epoxy acrylate composition by a known method. In addition, including as a main component means containing 60% or more, preferably 70% or more, and a subcomponent may contain 40% or less, preferably 30% or less.

In the above production method, an epoxy acrylate containing the epoxy acrylate represented by the general formulas (1) and (2) is obtained. Since these epoxy acrylates are all cyclohexane ring compounds, there are chair-type and ship-type isomers, and since there are cis, trans isomers, or optical isomers, the main component and subcomponents are: A mixture containing these isomers may also be used. Since the epoxy acrylates represented by the general formulas (1) and (2) obtained by the above production method are both epoxy acrylates, the epoxy acrylates represented by the general formulas (1) and (2) are included. Even if it is a composition, it is also called epoxy acrylate.

The epoxy acrylate of the present invention can be produced by reacting an epoxycyclohexane compound and an unsaturated carboxylic acid at 50 to 200 ° C. for 1 to 50 hours in the presence of a catalyst and a polymerization inhibitor as necessary.

The raw material charge ratio of the epoxycyclohexane compound and the unsaturated carboxylic acid is preferably a reaction ratio of 100/5 to 5/100, preferably 100/10 to 10/100, as the molar ratio of the epoxycyclohexane compound and the unsaturated carboxylic acid. .

Examples of the catalyst that can be used in this case include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, tertiary amines such as triethylamine and benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, imidazole, and the like. Compounds, phosphines such as triphenylphosphine, and phosphonium salts such as tetra-n-butylphosphonium tetraphenylborate. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used varies depending on the catalyst used, but is preferably 0.01 to 100 mol, more preferably 0.1 to 80 mol, based on 100 mol of the epoxycyclohexane compound.

As the polymerization inhibitor that can be used in carrying out the reaction, known polymerization inhibitors may be used as polymerization inhibitors for vinyl compounds. For example, amines such as phenothiazine, methoxyphenothiazine, hindered amine, phenol, methoxyphenol, hydroquinone, t- Phenols such as butylcatechol, butylhydroxytoluene, cresol and the like can be mentioned, and phenols are preferable. These polymerization inhibitors may be used alone or in combination of two or more. The amount of the polymerization inhibitor used varies depending on the catalyst used, but is preferably 0.001 to 10 mol, more preferably 0.01 to 1 mol, per 100 mol of the epoxycyclohexane compound.

In carrying out the reaction, an organic solvent may be used as necessary. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as MIBK and MEK, and the like. The amount of the solvent used is usually 50 to 5000 parts by weight, preferably 100 to 2000 parts by weight, based on 100 parts by weight of the total weight of the epoxycyclohexane compound and the unsaturated carboxylic acid.

When performing the reaction, air or oxygen may be introduced as necessary. From the viewpoint of controlling the reaction, air is preferably introduced.

The epoxy acrylate obtained by the reaction is a mixture containing the epoxy acrylate of the general formula (1) as a main component and an isomer such as the epoxy acrylate of the general formula (2) as a minor component, or a mixture having a different n number. Will be. When these mixtures are used as resin raw materials, they can be used as they are as epoxy acrylates. When used as a raw material for organic chemicals, it can be purified or separated by recrystallization or the like.

As the epoxycyclohexane compound, a vinylcyclohexyl compound epoxidized with a peroxide can be used. Since epichlorohydrin is not used, the resulting compound has a low chlorine content. As the peroxide, a peracid, hydrogen peroxide, or an organic peroxide obtained by a usual method can be used.

The acrylic curable composition of the present invention includes the epoxy acrylate of the general formula (1) or the epoxy acrylate composition containing the epoxy acrylate as a main component and a polymerization initiator.

The polymerization initiator may be a known polymerization initiator as a polymerization initiator for a vinyl compound, and is cured by irradiation with an active energy ray such as an ultraviolet ray or an electron beam or by applying a radical polymerization initiator.

When curing by ultraviolet irradiation, a photopolymerization initiator is added. Although it does not specifically limit as a photoinitiator, The normal photoinitiator of the type which generate | occur | produces a radical by being excited by ultraviolet irradiation is mentioned, Specifically, as a suitable initiator, Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin-iso-propyl ether, α-methylbenzoin, α-hydroxyisobutylphenone, benzophenone, p-methylbenzophenone, p-chlorobenzophenone, p-diethylaminobenzophenone, etc. Examples include benzophenones, acetophenone, 9,10-anthraquinone, 1-chloroanthraquinone, anthraquinones such as 2-chloroanthraquinone, and sulfur-containing compounds such as diphenyl disulfide and tetramethylthiuram disulfide.

These photopolymerization initiators are used alone or in admixture of two or more, and the blending amount is recommended to be about 0.1 to 10% by weight with respect to the total amount of polymerizable compounds.

Further, a photosensitizer may be added in order to accelerate the photopolymerization reaction by the photopolymerization initiator.

The photosensitizer is not particularly limited. Specifically, tertiary amines such as triethylamine and triethanolamine, alkylphosphines such as triphenylphosphine, thioethers such as thiodiglycol, and the like. The blending amount thereof is about 0.01 to 5% by weight with respect to the total amount of the polymerizable compound (referring to the above-mentioned epoxy acrylate or epoxy acrylate composition and other polymerizable monomer added if necessary). Recommended.

As the ultraviolet light source, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is used.

When curing with an electron beam, it is not necessary to use a photopolymerization initiator or a photosensitizer, and a general-purpose electron beam generator may usually irradiate an electron beam with a dose of about 1 to 20 megarads.

The radical polymerization initiator used for radical polymerization of the acrylic curable composition according to the present invention is not particularly limited, and specific examples thereof include benzoyl peroxide, diisopropyl peroxycarbonate, lauroyl peroxide, and the like. Azo compounds such as peroxide and azobisisobutyronitrile are exemplified, and these polymerization initiators may be used alone or in combination of two or more. As the polymerization initiator, it is preferable to use one for thermosetting and one for photocuring depending on the application.

The amount of these polymerization initiators used varies depending on the polymerization inhibitor used, but is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight based on the total amount of the polymerizable compounds. is there. However, since this mixing ratio varies greatly depending on the type of curing agent used, it is necessary to appropriately determine the optimum conditions.

In addition to the epoxy acrylate of the general formula (1) or the above-mentioned epoxy acrylate composition containing this as a main component, the acrylic curable composition of the present invention may contain other polymerizable monomers by heat or light as necessary. Can be added. However, it is preferable that the polymerizable component contains a total of 50 wt% or more of the epoxy acrylate of the general formula (1) or the epoxy acrylate composition containing the same as the main component. The other polymerizable monomer may be a known heat or light polymerizable monomer, and various acrylate compounds exemplified below may be used alone or in combination of two or more, and used together as a curable component.

Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, butyl (meth) acrylate, iso-butyl (meth) acrylate, n-hexyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Examples include acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, and 2,3-dibromopropyl (meth) acrylate. It is.

Bifunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. , Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, propanediol di (meth) acrylate, glycerin di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bis (oxymethyl) tricyclo [5.2.2.02,5] decane di (meth) acrylate, cyclohexanediol di (meth) ) Acrylate, bis [(meth) acryloxymethyl] cyclohexane, acetal diacrylate of trimethylolpropane and pivalaldehyde, neopentyl glycol ester diacrylate of hydroxypivalic acid, bisphenol A-di (meth) acrylate, bisphenol A Examples thereof include di (meth) acrylates of alkylene oxide adducts.

Examples of tri- to tetrafunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. The

Acrylic polymerizable oligomers include epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polybutadiene oligomer (meth) acrylate, polyamide-type (meth) acryl oligomer, melamine (meth) acrylate, cyclopentadiene Examples include oligomeric (meth) acrylates and silicone oligomer (meth) acrylates.

In addition to the above acrylate monomers, other polymerizable monomers, for example, vinyl compounds such as styrene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, vinyl ether, acrolein, α-olefins such as ethylene and butadiene, etc. Can be used in combination as appropriate. These heat or light polymerizable monomers may be used alone or in combination of two or more. As the polymerizable monomer by heat or light, it is preferable to use either a thermally polymerizable monomer or a photopolymerizable monomer depending on the application.

Other components such as fillers, fibers, coupling agents, flame retardants, mold release agents, and foaming agents can be added to the acrylic curable composition of the present invention as necessary. Examples of the filler include polyethylene powder, polypropylene powder, quartz, silica, silicate, calcium carbonate, magnesium carbonate, gypsum, bentonite, fluorite, titanium dioxide, carbon black, graphite, iron oxide, aluminum powder, iron Examples of fibers such as powder, talc, mica, kaolin clay, and the like include cellulose fiber, glass fiber, carbon fiber, and aramid fiber. Examples of the coupling agent include a silane coupling agent and a titanium coupling agent. Examples of the flame retardant include brominated bisphenol A, antimony trioxide, and phosphorus compounds. Examples of the mold release agent include stearates, silicones, waxes and the like. Examples of the blowing agent include CFC, dichloroethane, butane, pentane, dinitropentamethylenetetramine, p-toluenesulfonyl hydrazide, or CFC, dichloroethane, butane, pentane and the like. Vinyl chloride-vinylidene chloride copolymer and styrene- (meth) Examples thereof include expandable thermoplastic resin particles filled in an acrylic ester copolymer shell. *

The acrylic curable composition of the present invention can be easily made into a cured acrylic resin by a method similar to a conventionally known method. For example, the epoxy acrylate or epoxy acrylate composition of the present invention, a polymerization initiator, if necessary, a polymerizable monomer by heat or light and other additives are made uniform by using an extruder, a kneader, a roll or the like, if necessary. To obtain an acrylic resin composition, melted and then molded using a casting or transfer molding machine, and further heated to 80 to 200 ° C. to obtain a cured product. Can do.

In addition, a prepreg obtained by dissolving the acrylic curable composition of the present invention in a solvent, impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and drying by heating is hot-pressed. It can be molded to obtain a cured product. For example, the epoxy acrylate or epoxy acrylate composition of the present invention, a polymerization initiator and other additives are heated and stirred until uniform, impregnated into a glass cloth, heated and semi-dried, and the solvent is removed. A glass cloth laminate can be produced by heating and pressing at a temperature of 80 to 200 ° C. for 1 hour or more. *

Specific examples of the dilution solvent that can be used in this case include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, and the like, and the amount used is based on the total weight of the acrylic curable composition and the dilution solvent. It is 10 to 70% by weight, preferably 15 to 65% by weight.

Since the cured product thus obtained has high heat resistance, toughness, chemical resistance and hardness, the cured acrylic resin of the present invention can be used in a wide range of fields such as optical resins. Specifically, it is also suitably used as a protective film for solder resist resins or electroless plating resist resins, hard coat materials, UV curable paints, glass substitute materials, and liquid crystal color filters. In particular, it is excellent as an optical material such as a lens, a prism, a color filter, or a protective film thereof.

Next, in order to further clarify the characteristics of the present invention, an example will be given and described in detail. In the text, “part” and “%” all indicate weight standards. *

Example 1
A 300 ml glass three-necked flask equipped with a condenser, a thermometer, and an air blowing tube was charged with 10.51 g (50 mmol) of 1,2,4-triepoxyethylcyclohexane, 18.01 g (250 mmol) of acrylic acid, and benzyltriethylammonium chloride. 0.23 g (1 mmol), 0.055 g (0.25 mmol) of dibutylhydroxytoluene and 100 ml of toluene were added, and the mixture was heated and stirred at 80 ° C. while introducing air, and reacted for 24 hours. After the reaction, the mixture was cooled to room temperature and washed with 100 ml of distilled water three times. The toluene layer was separated and the toluene was distilled off, followed by purification with a silica gel column using ethyl acetate + hexane (4: 6) as a developing solution. A colorless transparent viscous liquid triepoxy acrylate cyclohexane (13.00 g, yield 61%) was obtained. It was confirmed by GC analysis that this triepoxy acrylate cyclohexane was mainly composed of an epoxy acrylate having a of 0, X of H, and n of 3 in the general formula (1). The ¹ H-NMR spectrum of this triepoxyacrylate cyclohexane is shown in FIG.

Comparative Example 1
In a 500 ml glass three-necked flask equipped with a cooling tube, a thermometer, and an air blowing tube, 50.00 g (416 mmol) of styrene oxide, 29.98 g (416 mmol) of acrylic acid, 1.09 g (4.16 mmol) of triphenylphosphine, 4-Tertiary butyl catechol (0.346 g, 2.08 mmol) and toluene (100 ml) were added, and the mixture was heated and stirred at 60 ° C. while introducing air, and reacted for 24 hours. After the reaction, the mixture was cooled to room temperature and washed with 100 ml of distilled water three times. The toluene layer was separated and the toluene was distilled off, followed by purification with a silica gel column using ethyl acetate + chloroform (2: 8) as a developing solution. A colorless and transparent liquid epoxy acrylate benzene (54.37 g, yield 68%) was obtained.

Example 2
100 parts by weight of the triepoxy acrylate cyclohexane obtained in Example 1 and 5 parts by weight of Irgacure 184 [manufactured by Ciba Specialty Chemicals Co., Ltd .; trade name] as a polymerization initiator were kneaded to prepare a composition. . It is coated on a glass plate or an aluminum pan, covered with a release PET film, and cured by irradiating it with ultraviolet rays so that the energy dose becomes 600 mJ / cm ² using a high-pressure mercury lamp, and a film-like cured product is obtained. It was.
Next, the obtained cured product was used as a sample, and the pencil hardness, glass transition point, and thermal expansion coefficient (α1) were analyzed by the following method. The results are shown in Table 1.

(Pencil hardness)
The coating film cured to 10 to 20 μm on the glass plate was measured under a load of 1 kg based on JISK5600, and indicated by the hardness of the hardest pencil without scratches.

(Glass transition point; Tg, thermal expansion coefficient; α1)
A sample adjusted to a length of 20 mm, a width of 5 mm, and a thickness of 0.1 mm was measured with a thermomechanical analyzer (TMA / SS) manufactured by SII NanoTechnology Co., Ltd. under a nitrogen atmosphere in a temperature rising rate of 7 ° C Calculated under the condition of minutes.

(YI value)
A film having a thickness of 50 μm was used as a sample and evaluated according to JIS K7373.

(Total light transmittance; Tt)
A film having a thickness of 50 μm was used as a sample and evaluated according to JIS K7361-1.

Comparative Example 2
A film-like cured product was obtained from the epoxy acrylate benzene obtained in Comparative Example 1 under the same conditions as in Experimental Example 2.
Next, the pencil hardness, glass transition point, and thermal expansion coefficient (α1) of the obtained cured product were analyzed under the same conditions as in Example 2. The results are shown in Table 1.

Industrial applicability

The epoxy acrylate of the present invention is superior in heat resistance, low thermal expansion, high refractive index, transparency, and weather resistance as compared with conventional epoxy acrylate, and is a resin for solder resist or resin for electroless plating resist, hard coat Epoxy acrylates, acrylic compositions and cured products useful for optical resins such as materials, UV curable paints, glass substitute materials, and liquid crystal color filters can be provided.

Claims

Epoxy acrylate represented by the following general formula (1).

(However, X represents a hydrogen atom or a methyl group. Z represents a C1-C6 alkyl group, all may be the same or different. N represents an integer of 2 to 3, and a represents an integer of 0 to 4. Indicates an integer.)
The epoxy acrylate according to claim 1, comprising an epoxy acrylate represented by the general formula (1) and an epoxy acrylate represented by the following general formula (2) as subcomponents.

(However, Z represents a C1-C6 alkyl group, all of which may be the same or different. A is an ester bond-containing group represented by the formula (3), and B is a group represented by the formula (3) or the formula ( 4) An ester bond-containing group represented by 4), wherein X represents a hydrogen atom or a methyl group, a represents an integer of 0 to 4, and b represents an integer of 1 to 2.
An acrylic curable composition comprising the epoxy acrylate according to claim 1 and a polymerization initiator. *
An acrylic curable composition comprising the epoxy acrylate according to claim 2 and a polymerization initiator. *
A cured acrylic resin obtained by molding and curing the acrylic curable composition according to claim 3 or 4.
The method for producing an epoxy acrylate according to claim 1, wherein an epoxycyclohexane compound represented by the following general formula (5) is reacted with acrylic acid or methacrylic acid.

(Wherein Z represents a C1-C6 alkyl group, all of which may be the same or different. A represents a number from 0 to 4, and n represents a number from 2 to 3.)
The epoxy acrylate production method according to claim 2, wherein an epoxycyclohexane compound represented by the following general formula (5) is reacted with acrylic acid or methacrylic acid.

(Wherein Z represents a C1-C6 alkyl group, all of which may be the same or different. A represents a number from 0 to 4, and n represents a number from 2 to 3.)
The acrylic curable composition according to claim 3 or 4, wherein the acrylic curable composition is for an optical material.
A cured acrylic resin according to claim 5, wherein the cured acrylic resin is for an optical material.