JP2002105168A - Epoxyacrylate resin and resin composition containing the resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable or thermosetting resin whose hardened product can satisfy performances such as hardness and heat resistance at high levels, and a method for manufacturing the same. SOLUTION: An epoxyacrylate resin (I) expressed by general formula (I) wherein, X is a unit shown by formula (Ia) [in the formula (Ia), R is H or a 1-5C normal or branched alkyl]; and n is an integer from 0 to 20}.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel epoxy acrylate resin having light and thermosetting properties, a method for producing the resin, and a photocurable resin composition and a thermosetting composition containing the resin. Furthermore, the present invention relates to a molded article having excellent heat resistance and a high refractive index, which is obtained by using the resin composition.

[0002]

2. Description of the Related Art Epoxy acrylate resins have been widely used as functional polymer materials. For example, this resin has been used in the fields of photosensitive materials, optical materials, dental materials, various polymer crosslinking agents, and the like. However, acrylic resins generally have insufficient heat resistance and weather resistance, and are insufficient, for example, in fields requiring a high level of heat resistance.

On the other hand, various resins have been proposed. For example, JP-A-8-278629 discloses an epoxy resin having a fluorene skeleton. JP-A-3-205417, JP-A-4-292611, JP-A-5-32807, and JP-A-7-205.
No. 48424 discloses an epoxy acrylate resin having a fluorene skeleton represented by the following formula (IV):

[0004]

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(Where R ¹ is H or a lower alkyl group,
R ² is H or CH _3, and n is an integer of 0 to 20).

[0006] Such a resin is characterized in that its cured product is relatively excellent in heat resistance. Although the above-mentioned problems can be solved to some extent by using these resins, it cannot be said that the required performance at the current high level can be sufficiently satisfied.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems. It is an object of the present invention to provide a cured product having a high hardness and a high level of heat resistance. Another object of the present invention is to provide a photocurable or thermosetting resin, a method for producing the resin, and a composition containing the resin. Another object of the present invention is to provide a molded article obtained by curing such a resin composition.

[0008]

The epoxy acrylate resin (I) of the present invention is represented by the following general formula:

[0009]

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Here, X is a unit represented by the following formula (Ia):

[0011]

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R is a hydrogen atom or a C1-5 linear or branched alkyl group, and n is an integer from 0 to 20.

The epoxy acrylate resin (I) of the present invention
Comprises the following steps: bisphenylphenol fluorene compound (II) represented by the following general formula:

[0014]

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(Where R is a hydrogen atom or a C1-5 linear or branched alkyl group) with epichlorohydrin to give a bisphenylphenol fluorene type epoxy compound (III):

[0016]

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(Where X is a unit represented by the following formula (IIIa):

[0018]

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R is a hydrogen atom or a C1-5 linear or branched alkyl group, and n is an integer from 0 to 20); and the bisphenylphenol fluorene type epoxy compound (III) has an acrylic acid Reacting.

The photocurable resin composition of the present invention contains the epoxy acrylate resin (I).

In a preferred embodiment, the photocurable resin composition further contains a photocurable acrylate compound other than the epoxy acrylate resin (I), and the total amount of the photocurable components in the composition. Based on the epoxy acrylate resin (I) in a proportion of 30 to 90% by weight and the photocurable acrylate compound in a proportion of 70 to 10% by weight.

In a preferred embodiment, the photocurable resin composition further contains a photopolymerization initiator, and the photopolymerization initiator is used in an amount of 100 parts by weight of the total amount of the photocurable components in the composition. It is contained at a ratio of 1 to 10 parts by weight with respect to the weight.

The present invention includes a molded product obtained by curing the above-mentioned photocurable resin composition by irradiating it with light.

The thermosetting resin composition of the present invention contains the above epoxy acrylate resin (I).

[0025] In a preferred embodiment, the thermosetting resin composition further contains a thermosetting acrylate compound other than the epoxy acrylate resin (I), and the total amount of the thermosetting components in the composition. Based on the epoxy acrylate resin (I) in a proportion of 30 to 90% by weight and the thermosetting acrylate compound in a proportion of 70 to 10% by weight.

The present invention includes a molded article obtained by thermosetting the above thermosetting resin composition.

[0027]

DETAILED DESCRIPTION OF THE INVENTION The epoxy acrylate resin (I) of the present invention is represented by the following general formula:

[0028]

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Here, X is a unit represented by the general formula (Ia),

[0030]

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R represents a hydrogen atom or a C1-5 linear or branched alkyl group, and n represents an integer of 0 to 20.

The epoxy acrylate resin (bisphenylphenol fluorene type epoxy acrylate resin) (I) is produced, for example, as follows.

First, a substituted or unsubstituted bisphenylphenol fluorene compound (II):

[0034]

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When epichlorohydrin is acted on (where R is a hydrogen atom or a C1-5 linear or branched alkyl group), a bisphenylphenol fluorene type epoxy compound (III) is obtained:

[0036]

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(Where X is a unit represented by the following formula (IIIa):

[0038]

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R is a hydrogen atom or a C1-5 linear or branched alkyl group, and n is an integer from 0 to 20). By reacting this with acrylic acid, a bisphenylphenol fluorene type epoxy acrylate resin (I) is synthesized.

The reaction of the above bisphenylphenol fluorene compound (II) with epichlorohydrin is usually carried out in 5
The reaction is performed in a temperature range of 0 to 120 ° C. for 3 to 10 hours. Similarly, the reaction with acrylic acid is carried out in a temperature range of 50 to 120 ° C. by using an appropriate solvent if necessary.
Performed for 30 hours. Examples of the solvent that can be used include:
Methyl cellosolve acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl-1
-Alkylene monoalkyl ether acetates such as acetate, and ketones such as methyl ethyl ketone and methyl amyl ketone. Of these, propylene glycol monomethyl ether acetate and 3-methoxybutyl-1-acetate are preferred.

The molecular weight and the acid value of the epoxy acrylate resin (I) are substantially controlled by changing the above reaction conditions to control the reaction and changing the number of n in the formula (I). It is possible. The value of n is set to 0 to 20 depending on the reaction conditions.

The photocurable resin composition and the thermosetting resin composition of the present invention both contain an epoxy acrylate resin (I). This epoxy acrylate resin (I) can be used alone or as a mixture of two or more.

When the composition of the present invention is a photocurable resin composition, the composition comprises a thermosetting resin composition in addition to the epoxy acrylate resin (I). In some cases, a radical initiator may be included. Further, these compositions include a light or thermosetting acrylate compound other than the epoxy acrylate resin (I),
Various additives and the like may be contained.

The photopolymerization initiator that can be contained in the photocurable resin composition of the present invention is the photopolymerization initiator of the epoxy acrylate resin (I) and, if necessary, the photocurable acrylate compound. And / or a compound having a sensitizing effect. Such photoinitiators include, for example, the following compounds: acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert. Acetophenones such as -butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone and p, p'-bisdimethylaminobenzophenone; benzyl, benzoin,
Benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether and benzoin isobutyl ether; sulfur compounds such as benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone; -Ethylanthraquinone, octamethylanthraquinone, 1,2
-Anthraquinones such as benzanthraquinone, 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide; and 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, −
Thiol compounds such as mercaptobenzothiazole.

One of these compounds may be used alone, or two or more of them may be used in combination. In addition, a compound which does not act as a photopolymerization initiator by itself, but can be used in combination with the above compound, can increase the ability of the photopolymerization initiator. Such compounds include:
For example, a tertiary amine such as triethanolamine, which is effective when used in combination with benzophenone, can be mentioned.

Examples of the radical initiator that can be contained in the thermosetting resin composition include ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and the like. A radical initiator such as a percarbonate-based or azobis-based initiator is used. In particular, a diacyl peroxide-based or azobis-based radical initiator is suitable, and for example, benzoyl peroxide, α, α'-azobis (isobutyronitrile) and the like are widely used.

The photo- or heat-curable acrylate compound other than the epoxy acrylate resin (I) is blended within a predetermined range as a viscosity modifier or a photo-crosslinking agent depending on the physical properties required of the composition. . Examples of the acrylate compound include monovalent acrylates having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; and ethylene glycol di (meth) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri ( (Meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Can be exemplified dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, a polyvalent (meth) acrylates such as glycerol (meth) acrylate.

One of these compounds can be used alone, or two or more of them can be used in combination.

As the additives that can be contained in the composition of the present invention, a thermal polymerization inhibitor, an adhesion aid, an antifoaming agent, a surfactant, a plasticizer, and the like are used according to the intended use of the composition. .

Among these, examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and phenothiazine.

When the composition obtained is applied to a substrate, the cohesive rib is added for the purpose of improving the adhesion to the substrate. As the adhesion aid, a silane compound (functional silane coupling agent) having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group is preferably used. Specific examples of such a functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ -Glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

Examples of the antifoaming agent include silicone-based defoaming agents,
Fluorine-based and acrylic-based compounds are exemplified.

The surfactant is added for the purpose of facilitating the application of the obtained composition and improving the flatness of the obtained coating film. Examples of the surfactant include silicone-based, fluorine-based, and acrylic-based compounds. Specifically, for example, BM-1000
[BM Heme Company]; MegaFac F142D, F17
2, F173 and F183 [manufactured by Dainippon Ink and Chemicals, Inc.]; Florad FC-135, FC-17
0C, Florado FC-430 and FC-431
[Sumitomo 3M Ltd.]; Surflon S-112,
S-113, S-131, S-141 and S
-145 [manufactured by Asahi Glass Co., Ltd.]; SH-28PA, SH-
190, SH-193, SZ-6032, SF-842
8, DC-57 and DC-190 [Toray Silicone
Co., Ltd.].

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl and the like.

As light (including radiation) used for photocuring the photocurable composition of the present invention, visible light, ultraviolet light, electron beam, X-ray, α-ray, β-ray, γ-ray and the like are used. Is done. Ultraviolet rays are preferred in terms of economy and efficiency. For UV irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an arc lamp, a xenon lamp, or the like is used.

In addition, if necessary, the composition of the present invention may contain various solvents. Examples of such a solvent include the following solvents: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether; Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol monobutyl ether; alkylene glycol monoalkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol methyl ether acetate and 3-methoxybutyl-1-acetate Aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone;
And ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, 3- Methyl methoxypropionate,
Esters such as ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or as a mixture of two or more.

The composition of the present invention is formed into a molded product according to the purpose. This molded article may be a product of a desired shape formed of a cured product of the composition itself, or a coating film formed of a cured product of the composition formed on a substrate.

For example, the epoxy acrylate resin (I) and, if necessary, a light or thermosetting acrylate compound other than the epoxy acrylate resin (I), a photopolymerization initiator (in the case of a photocurable resin composition) By mixing a radical initiator (in the case of a thermosetting resin composition) and various additives, or dispersing or dissolving in a suitable solvent, a photocurable or thermosetting resin composition can be obtained. . For example, a cured composition can be formed on a substrate by applying and drying a liquid composition containing a solvent on the substrate, and then irradiating or heating with light. Alternatively, the photocurable or thermosetting composition is heated and melted, if necessary, poured into a predetermined mold and irradiated with light or heated to obtain a molded article having a desired shape.

A molded article (including a coating film) formed from the composition of the present invention has high hardness, extremely excellent heat resistance, and high refractive index.

The composition of the present invention is specifically, for example,
It is useful as various coating agents, especially as coating agents requiring high hardness and heat resistance. In addition, the composition of the present invention is specifically used for a resist ink material for a color filter; a material for a protective film of an electronic component (for example, a liquid crystal display device including a color filter, an integrated circuit device, a solid-state imaging device, etc.). Material for forming protective film); Material for forming interlayer insulating and / or planarizing film; Solder resist used for manufacturing printed wiring board; or Photosensitive suitable for forming columnar spacers that can be used instead of bead spacers in liquid crystal display devices Composition is preferably used. Further, the composition of the present invention comprises a material for various optical components (lens, LED, plastic film, substrate, optical disk, etc.); a coating agent for forming a protective film on the optical component; an adhesive for optical components (adhesive for optical fiber) Etc.); a coating agent for producing a polarizing plate; suitably used as a raw material of a photosensitive resin composition for hologram recording.

[0061]

The present invention will be specifically described below based on examples and comparative examples. In the following, “parts” indicates “parts by weight”.

Example 1 (1) Synthesis of bisphenylphenol fluorene type epoxy compound (III) 502 g of a bisphenylphenol fluorene compound (R = H) represented by the formula (II) was added to epichlorohydrin 1
It was dissolved in 850 g. To this, 0.3 g of benzyltriethylammonium chloride was added, and under reduced pressure (150 m
mHg), 40% aqueous sodium hydroxide solution 2 at 70 ° C.
00 g was added dropwise over 3 hours. During that time, generated water was removed from the system by azeotropic distillation with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the completion of the dropwise addition, the reaction was continued for another 30 minutes. Thereafter, salts formed by filtration were removed, and after further washing with water, epilorhydrin was distilled off to obtain 512 g of a bisphenylphenol fluorene type epoxy compound (III) (R = H; content of the compound of n = 0: 95%). . The epoxy equivalent of this resin is 3
It was 12.

(2) Synthesis of epoxy acrylate resin (I) In a 500 ml four-necked flask, 312 g of the above bisphenylphenol fluorene type epoxy resin (III)
(Epoxy equivalent 312), 450 mg of triethylbenzylammonium chloride, 100 mg of 2,6-diisobutylphenol, 72.0 g of acrylic acid, and 500 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and stirred.
90 to 10 while blowing air at a rate of 25 ml / min.
Heated at 0 ° C. Although this mixture was cloudy, the temperature was gradually raised as it was and heated to 120 ° C. to obtain a solution in which the contents were completely dissolved. This gradually became a transparent and viscous solution, but stirring was continued as it was, and the acid value was measured over time. Heating and stirring were continued until the acid value was less than 2.0 mgKOH / g. It took 20 hours for the acid value to reach the target. After completion of the reaction, PGM
The EA was distilled off, and the mixture was cooled to room temperature, and was converted to a colorless and transparent compound of the formula (I)
A bisphenylphenol fluorene type epoxy acrylate resin represented by the following formula was obtained (R = H; content of the compound where n = 0: 85%).

Further, this was dried under reduced pressure at 30 ° C. for one day and night to obtain a target sample of bisphenylphenol fluorene type epoxy acrylate resin (I).

(3) Analysis results The above sample was purified by washing with hexane, and R = H, n = 0.
Was obtained and the structure was determined. Next, the analysis results are shown.

(3.1) Melting point 74-80 ° C. (3.2) ¹ H-NMR (solvent: CDCl ₃ , internal standard: TMS) Peak in FIG. 1 ppm q 1.64 2H a 3.88-4.022 Hb 4.04-4.15 2H c 4.15-4.25 2H d 5.82-5.85 2H e 6.07-6.14 2H f 6.38-6.43 2H g 6.79-6.80 2H h 7.09-7.11 2H i, j, k, l, m, n 7.22-7.40 16H o 7.40-7.44 2H p 7.73-7.77 2H (3.3) IR (KBr) 1,720 cm ^-1 (ester group; C = O) 1,620 cm ^-1 (vinyl group; C = C) 3,070 cm ^-1 (benzene ring; CH) (3.4) MS m / n = 758 (m ⁺ )

(4) Preparation of Photocurable Composition and Performance Evaluation (4.1) Photosensitivity To 39 parts by weight of the bisphenylphenol fluorene type epoxy acrylate resin (I) obtained in the above section (2),
1 part by weight of Michler's ketone was added and mixed as a photopolymerization initiator, and 60 parts by weight of PGMEA was further added and dissolved. The obtained mixture was applied on a glass substrate by a spin coater so that the film thickness after drying was 50 μm.

The coating film was exposed using an ultra-high pressure mercury lamp to cure the coating film. The amount of light at this time is 30
It was 0 mJ / cm ² .

(4.2) Heat Resistance The cured film obtained above was subjected to thermogravimetric analysis (TG).
The onset of weight loss was 288 ° C.

(4.3) Optical Characteristics The refractive index of the cured film was measured with an Abbe refractometer. The refractive index was 1.625.

From these results, it is understood that the epoxy acrylate resin of the present invention has high sensitivity, and the cured coating film has high heat resistance and refractive index.

Comparative Example 1 (1) Synthesis of epoxy compound (VI) 350 g of bisphenolfluorene represented by formula (V)
Was dissolved in 1850 g of epichlorohydrin.

[0073]

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To this, 0.3 g of benzyltriethylammonium chloride was added, and under reduced pressure (150 mmHg),
200 g of 40% aqueous sodium hydroxide solution at 70 ° C.
It was dropped over time. During that time, generated water was removed from the system by azeotropic distillation with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the completion of the dropwise addition, the reaction was continued for another 30 minutes. Thereafter, salts produced by filtration were removed, and after washing with water, epilorhydrin was distilled off. 420 g of bisphenol fluorene type epoxy resin (VI)
Got:

[0075]

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Here, X ¹ is a unit represented by the following formula (VIa):

[0077]

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The content ratio of the compound where n = 0 was 95%. The epoxy equivalent of this resin was 231.

(2) Epoxy acrylate resin (VII)
In a 500 ml four-necked flask, 231 g of a bisphenolfluorene-type epoxy resin represented by the formula (VI) (epoxy equivalent 231), 450 mg of triethylbenzylammonium chloride, 100 mg of 2,6-diisobutylphenol and 72.0 g of acrylic acid, Further, 500 g of PGMEA was charged as a solvent and stirred, and air was blown at a rate of 25 ml / min.
Heated at ° C. Although this mixture was cloudy, the temperature was gradually raised as it was and heated to 120 ° C. to obtain a liquid in which the resin was completely melted. This gradually became a transparent and viscous liquid, but stirring was continued as it was, and the acid value was measured over time. Heating and stirring were continued until the acid value was less than 2.0 mgKOH / g. It took 12 hours for the acid value to reach the target. After completion of the reaction, PGM
EA was distilled off, and the mixture was cooled to room temperature.
A bisphenol fluorene type epoxy acrylate resin represented by I) was obtained (content ratio of compound where n = 0: 8)
8%).

[0080]

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Here, X ¹ is a unit represented by the following formula (VIIa):

[0082]

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N is an integer from 0 to 20.

This was dried under reduced pressure at 30 ° C. for one day and night to obtain a sample of the desired bisphenol fluorene type epoxy acrylate resin (VII).

Example 2 30 parts by weight of the above epoxy acrylate resin (I), dipentaerythritol hexaacrylate (DPHA) 2
0 parts by weight and 1 part by weight of Michler's ketone were dissolved in methyl ethyl ketone to obtain a solution having a solid concentration of 50% by weight. The thickness of the epoxy acrylate composition solution after drying on a glass substrate surface using a bar coater is 5 μm.
And dried at 100 ° C. for 5 minutes. Next, light of 300 mJ / cm ² was irradiated with a high-pressure mercury lamp (400 W) to cure the coating film.

The surface properties of the obtained coating film were measured according to the following test methods. Table 1 shows the results.

(1) Abrasion Resistance (Scratch Resistance) The steel wool was rubbed by reciprocating 30 times while the coating film surface on the substrate was lightly pressed with # 1000 steel wool. The degree of scratches on the coating film surface was determined according to the following criteria, and the abrasion resistance was evaluated. ：: no scratches △: scratches but gloss is maintained ×: countless scratches and loss of gloss

(2) Adhesion The adhesion was evaluated by a cross-cut peel test according to JIS-Z-1552.

(3) Pencil hardness The pencil hardness was measured according to JIS-K-5400.

Example 3 A sample was prepared and evaluated under the same conditions as in Example 2 except that dipentaerythritol hexaacrylate was changed to trimethylolpropane triacrylate (TMATA).

Example 4 A sample was prepared under the same conditions as in Example 2 except that dipentaerythritol hexaacrylate was changed to pentaerythritol tetraacrylate (PETA).
An evaluation was performed.

Comparative Example 2 A sample was prepared and evaluated under the same conditions as in Example 2 except that the epoxy acrylate resin (I) was changed to the epoxy acrylate resin (VII).

[0093]

[Table 1]

Example 5 Epoxy acrylate resin (I) 9 obtained in Example 1
9 parts by weight were heated and melted to obtain a liquid, 1 part by weight of benzoyl peroxide as a radical initiator was added thereto, mixed, and poured into a Teflon (registered trademark) mold. This is 100
Heated in oven at 30 ° C. for 30 minutes, then at 170 ° C. for 1 hour and heat cured. The following items were evaluated using the obtained molded body. (1) Flexural strength: Measured according to ASTM D-790. (2) Pencil hardness: Measured according to JIS-K-5400. (3) Heat distortion temperature (HDT): Measured according to ASTM D-648. (4) Visible light transmittance: spectrophotometer (U-Made by Hitachi, Ltd.)
2000) in the range of 800 to 380 nm. (5) Refractive index: measured with an Abbe refractometer.

Table 2 shows the evaluation results. Example 6 to be described later
Table 2 also shows the results of Comparative Example 8 and Comparative Example 3.

Example 6 Epoxy acrylate resin (I) 3 obtained in Example 1
3 parts by weight, 33 parts by weight of dipentaerythritol hexaacrylate (DPHA), 33 parts by weight of pentaerythritol triacrylate (PETA), and 1 part by weight of benzoyl peroxide as a radical initiator were thoroughly mixed,
The resulting mixture was poured into a Teflon mold. This is placed in an oven at 100 ° C. for 30 minutes, then at 170 ° C. for 1 minute.
Heated for an hour and heat cured. About the obtained molded body,
The same evaluation as in Example 5 was performed.

Example 7 Epoxy acrylate resin (I) 6 obtained in Example 1
6 parts by weight, 2-hydroxyethyl methacrylate (2-
(HEMA) 33 parts by weight and 1 part by weight of benzoyl peroxide as a radical initiator were thoroughly mixed, and the resulting mixture was poured into a Teflon mold. This is heated in an oven at 100 ° C. for 30 minutes, then at 170 ° C. for 1 hour,
Heat cured. The same evaluation as in Example 5 was performed on the obtained molded body.

Example 8 Epoxy acrylate resin (I) 4 obtained in Example 1
9.5 parts by weight, 49.5 parts by weight of ethylene glycol dimethacrylate (EG-DMA), and 1 part by weight of benzoyl peroxide as a radical initiator were thoroughly mixed, and the resulting mixture was poured into a Teflon mold. Was. This one
Heating was performed in an oven at 00 ° C. for 30 minutes, then at 170 ° C. for 1 hour, and heat-cured. The same evaluation as in Example 5 was performed on the obtained molded body.

Comparative Example 3 Epoxy acrylate resin (VII) obtained in Comparative Example 1
99 parts by weight and 1 part by weight of benzoyl peroxide as a radical initiator were thoroughly mixed, and the resulting mixture was poured into a Teflon mold. Put this in a 100 ° C oven
The mixture was heated for 0 minutes and then at 170 ° C. for 1 hour to be thermally cured. The same evaluation as in Example 5 was performed on the obtained molded body.

[0100]

[Table 2]

[0101]

As described above, according to the present invention, a novel epoxy acrylate resin having photocurable and thermosetting properties and a method for producing the resin are provided. A cured product obtained from the composition containing the resin (for example, a molded article itself or a coating film formed on a substrate) has high hardness, extremely excellent heat resistance, and further has a high refractive index. .

Accordingly, the composition of the present invention is useful, for example, as various coating agents, particularly, coating agents requiring high hardness and heat resistance. In addition, it is used as a resist ink for forming a printed wiring board, a material for forming an interlayer insulating film of a laminated substrate, a material for forming a protective film for an image sensor, a solder resist, a plating resist, and a protective film for a color filter. Furthermore, the composition of the present invention utilizes the fact that the cured product has a high refractive index and good adhesion to a substrate, and is used as a molding material for optical products, a coating agent for optical materials, and an adhesive. Used as such.

[Brief description of the drawings]

FIG. 1 shows the epoxy acrylate resin of the present invention.
^{It is a 1} H-NMR chart.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Kei Kitano 236 Nakai, Tatsuno-cho, Tatsuno-shi, Hyogo Nagase Kasei Kogyo Co., Ltd. Harima Plant F-term (reference) QA23 QA24 QB19 QB20 SA01 SA04 SA05 SA06 SA07 SA21 SA25 SA27 SA31 SA36 SA41 SA51 SA54 SA63 SA64 SA76 SA78 SA79 SA83 UA01 WA02 WA06 4J027 AC02 AC06 AE01 AE02 BA08 BA10 BA20 BA25 BA28 CB04 CB10 CC05 CD07 CD08 AD09 JA09

Claims (9)

[Claims] 1. An epoxy acrylate resin (I) represented by the following general formula: Here, X is a unit represented by the following formula (Ia): R is a hydrogen atom or a C1-5 linear or branched alkyl group, and n is an integer from 0 to 20. 2. The method for producing an epoxy acrylate resin (I) according to claim 1, wherein the bisphenylphenol fluorene compound (II) represented by the following general formula: (Where R is a hydrogen atom or a C1-5 linear or branched alkyl group) with epichlorohydrin to give a bisphenylphenol fluorene type epoxy compound (III): (Where X is a unit represented by the following formula (IIIa): R is a hydrogen atom or a C1-5 linear or branched alkyl group, and n is an integer from 0 to 20); and reacting the bisphenylphenol fluorene type epoxy compound (III) with acrylic acid A method comprising: 3. A photocurable resin composition containing the epoxy acrylate resin (I) according to claim 1. 4. The composition further contains a photocurable acrylate compound other than the epoxy acrylate resin (I), and the epoxy acrylate resin (I) is 30% based on the total amount of the photocurable components in the composition. The composition according to claim 3, wherein the composition comprises about 90% by weight and the photocurable acrylate compound in a proportion of 70% to 10% by weight. 5. The composition further comprises a photopolymerization initiator, wherein the photopolymerization initiator has a total amount of 100 parts of a photocurable component in the composition.
The composition according to claim 3, wherein the composition is contained in a ratio of 1 to 10 parts by weight based on parts by weight. 6. A molded article obtained by curing the photocurable resin composition according to any one of claims 3 to 5 by irradiating the composition with light. 7. A thermosetting resin composition containing the epoxy acrylate resin (I) represented by the general formula of claim 1. 8. The composition further contains a thermosetting acrylate compound other than the epoxy acrylate resin (I), and the epoxy acrylate resin (I) is 30% based on the total amount of the thermosetting components in the composition. 8. The composition according to claim 7, wherein the composition comprises about 90% by weight and the thermosetting acrylate compound in a proportion of 70% to 10% by weight. 9. A molded product obtained by thermosetting the thermosetting resin composition according to claim 7 or 8.