JPH10330315A - New (meth)acrylic acid derivative and thermosetting resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject derivative useful as a raw material for thermosetting resins excellent in adhesiveness of a cured product to a substrate, flexibility, electricity-insulating properties, water resistance, etc., by deriving it from an alicyclic hydroxy compound obtained by hydrogenating an adduct of a phenol to a cyclic terpene compound. SOLUTION: This new (meth)acrylic acid derivative is obtained by deriving it from an aliphatic hydroxy compound (D) which is prepared by hydrogenating an adduct (C) of 1 mole of (A) a cyclic terpene compound (e.g.; paramentene-1) with 1 mole of (B) a phenol (e.g.; phenol). The objective derivative is, e.g. a (meth)acrylic ester of the ingredient D, etc. The ingredient C is obtained by reacting 1 mole of the ingredient A with 0.1-6 mole of the ingredient B in the presence of an acidic catalyst at 20-150 deg.C for 1-10 hours. As the ingredient D, e.g. a compound of formula I (X<1> and X<2> are each H, a 1-5C alkyl or OH), a compound of formula II (X<3> and X<4> are each H, a 1-5C alkyl or OH), etc., are cited.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel (meth) acrylic acid derivative and a curable resin composition containing the same. More specifically, the present invention relates to a novel (meth) acrylic acid derivative excellent in adhesion, flexibility, heat resistance, electric insulation, water resistance, and the like of a cured product to a substrate, and a cured resin composition containing the same.

[0002]

2. Description of the Related Art Conventionally, curable resin compositions which are cured by irradiation with heat or energy rays such as ultraviolet rays and electron beams have been used for a wide range of uses as solventless curable materials. Among them, the energy ray curing type is used for coating and printing of plastics such as resist ink, metal, wood, paper, etc. from various advantages such as energy saving and low-temperature high-speed curing. Further, in recent years, it has begun to attract attention as a semiconductor resist material, particularly for a next-generation argon fluorine excimer laser for ultrafine processing. Various acrylic compounds and methacrylic compounds have been used as curable resin compositions used for such purposes.

For example, poly (meth) acrylates such as 2-ethylhexyl acrylate, lauryl acrylate, phenoxyethyl acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, and polyethylene glycol Alkoxy (meth) acrylates such as diacrylate, oxyethylenated bisphenol A diacrylate, bisphenol A
(Meth) acrylate of type glycidyl ether,
(Meth) of phenol novolak type polyepoxy compound
Various (meth) acrylic compounds such as epoxy acrylates and the like have been used.

[0004] However, these compounds are not necessarily satisfactory in performance such as adhesion of a cured product to a substrate, flexibility, electrical insulation and water resistance.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems in the prior art. In a curable resin composition, the cured product has good adhesion to a substrate, flexibility, electrical insulation, and the like. An object of the present invention is to provide a novel compound for improving performance such as water resistance and a curable resin composition containing the novel compound.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above objects can be achieved, and have reached the present invention. That is, the present invention provides a novel (meth) acrylic acid derivative derived from an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol, and a curable resin composition containing the same. Is provided. Also,
As the cyclic terpene compound, paramenthen-1 or camphene, and as the phenol, phenol is used.
It is desirable that the (meth) acrylic acid derivative be an acrylic ester.

The cyclic terpene compound 1 used in the present invention
The alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of phenols and 1 mol of phenols is an alicyclic hydroxy compound obtained by hydrogenating the unsaturated bond of a 1 mol / 1 mol addition product of a cyclic terpene compound and a phenol compound Examples of the hydroxy compound include, but are not limited to, compounds represented by the following general formula (1) or general formula (2).

[0008]

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In the general formula (1), X1 and X2 are the same or different and represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group. ｝

[0010]

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In the general formula (2), X3 and X4 are the same or different and represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group. ｝

The cyclic terpene compound 1 used in the present invention
The cyclic terpene compound as a raw material for producing an adduct of 1 mol of phenols and 1 mol of phenols may be a monocyclic terpene compound or a bicyclic terpene compound.
Specific examples thereof include the following, but are not limited thereto. However, Campfen,
Paramenten-1 has a relatively large effect on physical properties, which is desirable.

Α-pinene, β-pinene, dipentene, limonene, α-pherandrene, β-pherandrene, α
-Terpinene, β-terpinene, γ-terpinene, terpinolene, 1,8-cineole, 1,4-cineole,
α-terpineol, β-terpineol, γ-terpineol, 4-terpineol, sabinene, camphene, tricyclene, paramentene-1, paramenten-
2, paramenten-3, paramenten-8, paramentadienes, Δ2-carene, Δ3-carene and the like.

Further, these cyclic terpene compounds may be used alone or in combination of two or more.

The cyclic terpene compound 1 used in the present invention
Examples of the phenol, which is the other raw material for producing an adduct of 1 mol of phenol and 1 mol of phenol, include phenol or a phenol compound substituted with an alkyl group having 1 to 5 carbon atoms and / or a hydroxyl group.

Examples of the phenol compound to which an alkyl group having 1 to 5 carbon atoms is added include o-cresol, p-cresol, m-cresol, 2,6-xylenol, 2,4
Xylenol, propylphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol,
o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,6-xylenol, p
-Compounds such as phenylphenol, but are not limited to these compounds.

Examples of the phenol compound having a substituted hydroxyl group include compounds such as catechol, resorcin, hydroquinone, and pyrogallol, but are not limited to these compounds.

In addition to the above phenols, compounds such as p-methoxyphenol, m-methoxyphenol, bisphenol A, bisphenol F, and naphthol can be used. These phenols can be used alone or in combination of two or more.

The method for producing an adduct of 1 mol of cyclic terpene compound and 1 mol of phenol used in the present invention is, for example, 0.1 to 6 mol, preferably 0 to 6 mol of phenol per 1 mol of cyclic terpene compound. It is obtained by reacting at a temperature of 20 to 150 ° C. for 1 to 10 hours in the presence of an acidic catalyst using 0.5 to 4 mol. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boron trifluoride or a complex thereof, a cation exchange resin, a heteropolyacid, and activated clay. At this time, a reaction solvent may not be used, but a solvent such as an aromatic hydrocarbon, an alcohol, or an ether may be used.

The alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol used in the present invention is obtained by mixing 1 mol of the cyclic terpene compound obtained by the above method with 1 mol of the cyclic terpene compound. One mole of the phenol adduct can be obtained by hydrogenating unsaturated bonds in the presence of a hydrogenation catalyst.

The hydrogenation method is not particularly limited. For example, noble metals such as palladium, ruthenium and rhodium or those obtained by supporting them on a carrier such as activated carbon, activated alumina and diatomaceous earth are used as catalysts. Method. At this time, it is possible to use a batch method in which the reaction is performed while the powdery catalyst is suspended and stirred, or a continuous method using a reaction tower filled with the shaped catalyst. Absent.

When the reaction is of a batch type, the amount of the catalyst used is 0.1 to 50% by weight, preferably 0.2 to 20% by weight, based on the adduct as a raw material. When the amount of the catalyst is less than 0.1% by weight, the rate of the hydrogenation reaction is slow, while the amount of the catalyst is 5%.
Exceeding 0% by weight is not preferred because the catalytic effect does not increase.

The reaction solvent may not be used, but usually, chain or cyclic alcohols, ethers, esters and saturated hydrocarbons are used. As the reaction solvent,
For example, methanol, ethanol, n-propanol,
Isopropanol, butanol, propyl ether, ethyl acetate, butyl acetate, hexane, cyclohexane, etc.

The reaction temperature of the hydrogenation reaction is not particularly limited, but is usually 20 to 250 ° C, preferably 50 to 200 ° C.
It is. If the reaction temperature is lower than 20 ° C., the rate of hydrogenation is reduced, while if it exceeds 250 ° C., the decomposition of hydride may increase.

Here, 1 mol of the cyclic terpene compound represented by the general formula (1) and the phenol 1
As a specific example of the alicyclic hydroxy compound obtained by hydrogenating a molar adduct, a hydroxy compound having a paramenthane skeleton is shown in the following structural formula (1). Further, as a specific example of the alicyclic hydroxy compound used in the present invention represented by the general formula (2), a hydroxy compound having a bornane skeleton is shown in the following structural formula (2).

[0026]

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[0027]

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The (meth) acrylic acid derivative derived from an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol according to the present invention is obtained by acid substitution of a (meth) acrylic compound. A compound in which a group is reacted with a hydroxyl group or a functional group of a hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol, or a compound containing a functional group derived from the hydroxy compound Can be mentioned.

For example, an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol to form an ester group by introducing a (meth) acryl group into the hydroxyl group, or this hydroxyl group Is reacted with a compound having another functional group, and a compound into which a (meth) acryl group is further introduced.

For example, (1) (meth) acrylic acid ester of an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol (2) 1 mol of a cyclic terpene compound and a phenol Alkoxy (meth) acrylate of alicyclic hydroxy compound obtained by hydrogenating 1 mol of adduct (3) Alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of cyclic terpene compound and 1 mol of phenols Epoxy acrylate of compound (4) Urethane acrylate of an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol. However, it is not limited to these compounds.
Among the above (meth) acrylates, (1) a hydroxy compound (meth) acrylate obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol is preferably used.

The (meth) acrylic acid ester of an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol is an ester of the alicyclic hydroxy compound with (meth) acrylic acid. An esterification reaction with an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol with (meth) acrylic acid, transesterification with (meth) acrylic acid ester It can be produced by a reaction, a condensation reaction with (meth) acrylic acid chloride, or the like.

Alkoxy (meth) acrylic acid of an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol is obtained by mixing the alicyclic hydroxy compound with ethylene oxide, propylene oxide or the like. An ester compound obtained by reacting (meth) acrylic acid with a reaction product of an alkylene chlorohydrin such as alkoxide or ethylene chlorohydrin, for example, by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol. It can be produced by an esterification reaction of the resulting alicyclic hydroxy compound with an alkoxide reactant with (meth) acrylic acid, a transesterification reaction with (meth) acrylic acid ester, a condensation reaction with (meth) acrylic chloride, and the like.

The epoxy acrylate of an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol is used as a reaction product of the alicyclic hydroxy compound with epichlorohydrin or the like.
An esterified product obtained by reacting acrylic acid.For example, a hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol and an epichlorohydrin are subjected to a condensation reaction to form an epoxy compound.
It can be produced by an addition reaction with (meth) acrylic acid.

The urethane acrylate of an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol is used as a reaction product of the alicyclic hydroxy compound and a diisocyanate compound.
Compounds obtained by reacting a hydroxyl-containing ester of acrylic acid are exemplified. For example, an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol is subjected to an addition reaction with a diisocyanate, followed by an addition reaction of an alkylene glycol monoester (meth) acrylate. Can be manufactured.

The diisocyanate compound used here includes, for example, tolylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate and the like.

The alkylene glycol (meth) acrylate monoester is a monoester of alkylene glycol and (meth) acrylic acid. For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate and the like can be mentioned.

The novel (meth) acrylic acid derivative derived from an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of the cyclic terpene compound thus obtained and 1 mol of a phenol is a monomer of an acrylic polymer. Available as an ingredient. Applications include adhesives, paints, inks, building materials, lighting, glass fiber reinforced resins,
Anti-corrosion, optical lens, optical fiber coating, UV /
EB curable resin, resist, fiber, fiber improver, leather,
Paper processing, rubber, signs, displays, vehicles / aircraft / ships, electric / mechanical parts, sundries, greenhouses, aquariums, etc.

The novel (meth) acrylic acid derivative of the present invention is a compound comprising a monofunctional (meth) acrylic acid derivative. When the monofunctional novel (meth) acrylic acid derivative of the present invention is used as a reactive monomer, it is used as a function-imparting agent because of its low polymerizability as compared with the polyfunctional derivative, and is usually polyfunctional (meth) acrylic acid. Used in combination with derivatives.

At this time, the polyfunctional (meth) acrylic acid derivative to be used in combination is, for example, a polyvalent (meth) acrylic acid such as 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, etc. Alkoxy (meth) acrylates such as esters, polyethylene glycol diacrylate, oxyethylenated bisphenol A diacrylate, and the (meth) of bisphenol A glycidyl ether
Examples include, but are not limited to, acrylic acid esters and epoxy acrylates such as (meth) acrylate of a phenol novolak type polyepoxy compound.

The curable resin composition of the present invention comprises a novel (meth) acrylic acid derivative derived from an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of the cyclic terpene compound and 1 mol of a phenol. It is characterized by containing, and can improve the performance such as adhesion, flexibility, electrical insulation, and water resistance of the cured product to the substrate.

Novel (meth) acrylic acid derivative derived from an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol used in the curable resin composition of the present invention Alicyclic hydroxy compounds obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol, a (meth) acrylate, an alkoxy (meth) acrylate, an epoxy acrylate, a urethane acrylate or the like are used alone Or two or more of them can be used in combination.

A (meth) acrylic acid derivative derived from an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of the cyclic terpene compound and 1 mol of a phenol used in the curable resin composition of the present invention. Is 2% by weight or more, preferably 5% by weight or more, based on the composition. If it is less than 2% by weight, the performance such as the adhesion of the cured product cannot be satisfied.

Further, a (meth) acrylic acid ester derived from an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of the cyclic terpene compound and 1 mol of the phenol to the curable resin composition of the present invention. And other (meth) acrylic compounds can be used in combination with the (meth) acrylic acid ester, the epoxy acrylate, and the urethane acrylate.

Other (meth) acrylic compounds include, for example, polyester acrylates produced by subjecting a polyester obtained by a reaction between a polyhydric alcohol such as ethylene glycol and a polybasic acid such as phthalic acid to (meth) acrylication. Bisphenol A type epoxy resin, novolak type epoxy resin or alicyclic type epoxy resin is obtained by esterifying the epoxy group of the epoxy group with (meth) acrylic acid or diisocyanate compound such as diphenylmethane diisocyanate. Urethane acrylate obtained by reacting an acrylate having a hydroxy group such as acrylate, and further, polyether acrylate, melamine acrylate, alkyd acrylate, silicon acrylate and the like. It is, but is not limited thereto.

The amount of these other (meth) acrylic compounds used is less than 80% by weight, preferably 6% by weight, based on the composition.
Less than 0% by weight. If it exceeds 80% by weight, the performance such as the adhesion of the cured product cannot be satisfied.

Acrylic and methacrylic compounds derived from an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol are reacted with an acrylic or methacrylic group. In general, the reactivity of the acryl group is higher than that of the methacryl group due to its reactivity with energy rays and its usefulness is greater. Both an acrylic compound and a methacrylic compound can be used in the curable resin composition of the present invention, but the acrylic compound is more preferably used for the above reasons.

An initiator is usually added to the curable resin composition of the present invention to accelerate the curing reaction. For example, a radical initiator is used for a curing reaction by thermal energy. Examples of the radical initiator include benzoyl peroxide, acetyl peroxide, and di-t
-Butyl peroxide, t-butyl peroxylaurate, dicumyl peroxide, α, α'-bis-t-butylperoxy-p-diisopropylbenzene, 2,
5-dimethyl-2,5-di-tert-butylperoxyperoxyhexane, 2,5-di-tert-butylperoxyhexyne, t-butylperoxybenzoate, n-butyl-4,4-bis-tert-butylperoxy Valate, p
Organic peroxides such as -menthane hydroperoxide and t-butylcumyl peroxide, azobisisobutyronitrile, 2,2'-azobis (2,4,4-trismethylvaleronitrile), 2,2'-azobis ( Examples thereof include, but are not limited to, azobis compounds such as 2-cyclopropylpropionitrile).

A photoinitiator is used for a curing reaction by energy rays. As the photoinitiator, for example,
Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, benzoin phenyl ether,
2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, Michler's ketone, 4-dialkylaminoacetophenone, 2-phenylthioacetophenone, benzyl, benzyldimethylketal, benzoylbenzoate, anthraquinone, 2-ethylanthraquinone, naphthoquinone, , 4-Diisopropylthioxanthone, azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, benzoyl peroxide, di-t-butyl peroxide, diphenyl disulfide, tetramethylthiuram monosulfide, Tetraethyl thiuram disulfide, benzophenone, bivaloin ethyl ether, dibenzyl sulfide, cinnamoyl chloride, dimethyl diphenylene disulfide, Examples include, but are not limited to, dibenzothiazole disulfide.

The amount of the radical initiator or photoinitiator used is at least 0.01% by weight based on the weight of the curable resin composition.
5% by weight or less, preferably 0.05% by weight or more, 3%
It is as follows. If it is less than 0.01% by weight, the curing speed is too low to be practical. On the other hand, if it exceeds 5% by weight, the effect of improving the curing speed can no longer be obtained, and the performance of the cured film is undesirably reduced.

A sensitizer can be added to the curable resin composition by energy rays of the present invention for the purpose of enhancing the effect of the photoinitiator. The sensitizer alone is not activated by irradiation with energy rays, but when used together with a photoinitiator, it is more effective than the photoinitiator alone.
For example, triethylamine, triethylenetetramine,
n-butylamine, di-n-butylamine, tri-n-
Examples include, but are not limited to, butylphosphine, allylthiourea, s-benzylisothiuronium-p-toluenesulfinate, diethylaminoethyl methacrylate, and the like.

The amount of the sensitizer to be used is 0.01% by weight or more and 5% by weight or less, preferably 0.05% by weight or more and 3% or less based on the curable resin composition. If it is less than 0.01% by weight, the curing speed is too low to be practical. On the other hand, if it exceeds 5% by weight, the effect of improving the sensitizer can no longer be obtained, and the performance of the cured film is undesirably reduced.

In the curable resin composition of the present invention, a polymerizable diluent can be used for the purpose of lowering the viscosity and improving workability in practical use. For example, 2-ethylhexyl acrylate, ethoxydiethylene glycol acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate Acrylate,
Examples include, but are not limited to, neopentyl glycol diacrylate hydroxypivalate, polyethylene glycol diacrylate, bis (acryloxyethyl) bisphenol A, trimethylolpropane triacrylate, pentaerythritol triacrylate, and the like.

The amount of the polymerizable diluent used is at most 70% by weight, preferably at most 50% by weight, based on the energy ray-curable resin composition. If it exceeds 70% by weight, the cured product is inferior in practical performance, which is not preferable.

In the present invention, if necessary, components such as an inorganic filler, a leveling agent, a coloring agent such as a pigment or a dye, an antifoaming agent, an adhesion promoter, a plasticizer, a solvent, and a storage stabilizer may be added. it can.

With respect to the curable resin composition using energy rays of the present invention, the energy rays for irradiating the composition to cause a curing reaction include ultraviolet rays, electron beams, X-rays and the like. As a light source used for ultraviolet irradiation, a solar ray, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc, or the like can be used.

By using the curable resin composition of the present invention, skin irritation is low, and the cured product has good adhesion to a substrate, durability such as abrasion resistance, water resistance and flexibility. Performance is improved. This is considered to be due to the introduction of the cyclic terpene skeleton into the (meth) acrylic compound. That is, a cyclic terpene skeleton such as a menthane skeleton composed of carbon atoms and hydrogen atoms, a pinane skeleton, and a bornane skeleton gives a composition with little skin irritation, and gives durability, water resistance, and flexibility of a cured product. It is considered something.

[0057]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below.
The present invention is not limited to these Examples. In the examples, parts and percentages are by weight unless otherwise specified.

An example of the synthesis of an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol is shown below. Synthesis Example 1 Production Example of Alicyclic Hydroxy Compound 4 equipped with thermometer, stirrer, dropping funnel and cooling tube
After charging 11.3 g (0.12 mol) of phenol and 2 g of a strongly acidic cation exchange resin,
While maintaining the temperature at 0 ° C, Paramenthen-1 was added to 13.8.
g (0.1 mol) was added dropwise over 3 hours, followed by stirring for 3 hours to react. Next, the cation exchange resin was removed from the mixture by filtration, and 30 g of toluene was added to the obtained reaction solution to dissolve the mixture, and the mixture was washed twice with distilled water.
Distillation was carried out under reduced pressure of 5 mmHg, and the boiling point was 138 ° C to 1 ° C.
19.5 g of a 48 ° C. fraction were obtained. Next, the above fraction, 200 ml of 2-propanol, and 1.0 g of a 5% ruthenium-supported alumina catalyst were charged into a 500 ml stainless steel autoclave. Next, this was sealed, and the atmosphere was replaced with nitrogen gas.
It was introduced while applying a pressure of g / cm @ 2. When the temperature was raised to 150 ° C. with stirring, the pressure of hydrogen was adjusted to 40 kg / cm 2, and the reaction was carried out for 10 hours while maintaining the pressure at 40 kg / cm 2 by supplementing the absorbed hydrogen. Thereafter, the mixture was cooled to room temperature, 300 ml of ethanol was added to the obtained suspension, and the catalyst was removed by suction filtration using a Buchner funnel. The filtrate was finally distilled and concentrated at 130 ° C. and a degree of vacuum of 1 mmHg or less for 30 minutes to obtain 19.4 g of a white crystal represented by the structural formula (1). The obtained crystalline product had a melting point of 104 ° C. and a purity by gas chromatography of 92%.

Synthesis Example 2 Preparation of alicyclic hydroxy compound Preparation of alicyclic hydroxy compound The same procedure as in the preparation of the hydroxy compound was carried out except that the terpene compound used as the starting material was changed to 13.6 g of camphene. 2)
17.6 g of a white crystal represented by the formula was obtained. The melting point of the obtained crystal was 125 ° C., and the purity by gas chromatography was 74%.

Example 1 Synthesis of Acrylic Acid Derivative (1) 11.9 g of the hydroxy compound obtained in Synthesis Example 1, 50 g of toluene and 3.9 g of acrylic acid were placed in a reactor equipped with an oil / water separator equipped with a reflux device. , 0.08 g of concentrated sulfuric acid,
0.05 g of hydroquinone was charged and refluxed at 110 ° C. while heating and stirring. The reaction was carried out for 10 hours while removing generated water with an oil-water separator. Next, the reaction oil was washed with water and distilled under reduced pressure to distill off toluene and unreacted substances to obtain a slightly yellow liquid as a residue. Next, the residue was purified by column chromatography to obtain 9.6 g of a colorless semi-solid substance. It was identified as an acrylate of a hydroxy compound represented by the structural formula (1) by 1HNMR, C13NMR analysis and IR analysis.

Example 2 Synthesis of acrylic acid derivative (2) 11.8 g of the hydroxy compound obtained in Synthesis Example 2, 50 g of toluene and 3.9 g of acrylic acid were placed in a reactor equipped with an oil-water separator equipped with a reflux device. , 0.08 g of concentrated sulfuric acid,
0.05 g of hydroquinone was charged and operated in the same manner as in Example 1 to obtain 9.4 g of a colorless semi-solid acrylate of a hydroxy compound represented by the structural formula (2).

Examples 3 and 4 The acrylic acid derivatives obtained in Examples 1 and 2 were used to prepare UV-curable solder resist ink compositions having the formulations shown in Table 1. This composition was uniformly kneaded with three rolls, printed on a polyimide substrate flexible copper-clad laminate using a 300-mesh polyester screen plate, and subjected to 1,000 mJ / square at a distance of 15 cm under a 80 W / cm high-pressure mercury lamp. It was cured with an integrated light quantity of cm.
The cured product is adhered, flexible, electrically insulating,
The water resistance was evaluated. Table 2 shows the measurement results of various properties of the obtained resist film.

Evaluation Method <Adhesiveness> Cross-cutting cellophane tape peeling test of resist film (JIS D0202) <Flexibility> Judgment by the number of times of bending until crack generation by 180 ° outer folding inner folding test (MIT test) did. (Diameter = 4 mmφ) <Electrical Insulation Resistance> The insulation resistance value of a comb-shaped electrode (JISZ-3197) formed by an etching method was measured. <Water resistance> The test piece was placed in boiling water for 100 hours, and the change in weight was measured as the water absorption (%).

Comparative Example 1 Examples 3 and 4 except that 2-ethylhexyl acrylate was used in place of the acrylate used in Examples 3 and 4.
The composition was cured in the same manner as described above to obtain a resist film. Table 2 shows the measurement results of various properties of the obtained resist film.

[0065]

[Table 1]

[0066]

[Table 2]

Table 2 shows that the cured product using the acrylic acid derivative used in the present invention had improved adhesion, flexibility, electrical insulation and water resistance.

[0068]

The novel (meth) acrylic acid derivative of the present invention is an industrially useful compound, and the curable resin composition containing the compound is useful for plastics such as resist inks, metals, and the like.
It is suitable for the purpose of improving adhesion, flexibility, electrical insulation, water resistance, and the like by being used for painting or printing of wood, paper, and the like.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Takahiro Nishiguchi 1080 Yasuhake Chemical Co., Ltd., Takagicho, Fuchu City, Hiroshima Prefecture

Claims (7)

[Claims] 1. A novel (meth) acrylic acid derivative derived from an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol. 2. The (meth) acrylic acid ester of an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol compound. Novel (meth) acrylic acid derivative. 3. A curable resin composition containing a novel (meth) acrylic acid derivative derived from an alicyclic hydroxy compound obtained by hydrogenating an adduct of 1 mol of a cyclic terpene compound and 1 mol of a phenol. 4. The method according to claim 1, wherein the cyclic terpene compound is paramenthen-
1. The novel (meth) acrylic acid derivative according to claim 1, wherein the phenol is phenol and the acrylic acid derivative is an acrylic ester. 5. The novel (meth) acrylic acid derivative according to claim 1, wherein the cyclic terpene compound is camphene, the phenol is phenol, and the acrylic acid derivative is an acrylic ester. 6. The method according to claim 1, wherein the cyclic terpene compound is paramenthen-
The curable resin composition according to claim 3, wherein the phenol is phenol and the acrylic acid derivative is an acrylate. 7. The curable resin composition according to claim 3, wherein the cyclic terpene compound is camphene, the phenol is phenol, and the acrylic acid derivative is an acrylate.