JP2002121258A - Method for producing energy ray-curable resin and energy ray-curable resin composition for resist - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an energy ray-curable resin which is used for resists, has an excellent basic performance, and has good toughness as a physical property. SOLUTION: The method for producing the energy ray-curable resin is characterized by reacting an acid anhydride with a hydroxyl group-containing modified epoxy acrylate compound obtained by reacting an epoxy resin with an unsaturated monocarboxylic acid and a dibasic acid anhydride in a specific range. The resin composition comprises the energy ray-curable resin and an epoxy group- having compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an energy ray-curable resin having excellent curing properties and an energy ray-curable resin composition for a resist, and more particularly, to an energy ray such as an ultraviolet ray or an electron beam. Highly sensitive, developable with alkaline aqueous solution, has excellent heat resistance, hardness, elongation, and electrical characteristics of the cured film, protective film for color filter layer and electronic device, permanent resist mask such as solder resist for printed wiring board, The present invention relates to a method for producing an energy ray-curable resin and an energy ray-curable resin composition for a resist, which are optimal for applications such as an insulating layer of a wiring board and a build-up material.

[0002]

2. Description of the Related Art Epoxy acrylate resins, also called unsaturated epoxy ester resins or vinyl ester resins, are superior in heat resistance, chemical resistance, adhesion, and mechanical properties to other acrylic oligomers. Widely used as structural materials, solder resists for wiring boards, and the like.

[0003] In particular, as for the solder resist, as the amount of substrate information increases, it is expected that the pattern becomes finer, and a solder resist formed by a photoengraving method is used. As this method, there is a method of developing the unexposed portion ink with a solvent or a dilute alkaline liquid. However, dilute alkaline liquid development is mainly used due to cost and pollution problems of the solvent.

[0004] These dilute alkali developable solder resists are mainly composed of a so-called acid pendant epoxy acrylate resin in which a carboxyl group is pendant by reacting an acid anhydride with a hydroxyl group of an epoxy acrylate resin.

[0005] A method for producing the resin, a composition using the resin,
And the coating method is described in JP-A-61-243869 and JP-A-63-258975, etc.
These resin systems are based on acid pendant epoxy acrylates, especially novolak epoxy. This novolak epoxy acrylate has a greater degree of branching than its structure and is excellent in heat resistance and the like, but has a disadvantage of being brittle in physical properties.

Further, JP-A-5-339356 discloses a composition mainly composed of a compound obtained by reacting a hydroxyl group of a bisphenol type epoxy (containing fluorene) acrylate with an acid anhydride. At this time, when synthesizing the epoxy acrylate, the ratio of the number of moles of the epoxy group of the epoxy resin to the number of moles of the (meth) acrylic acid is equivalent,
That is, the reaction of the acid anhydride is performed by the reaction with the secondary hydroxyl group of the epoxy acrylate in both the half esterification and the esterification. Generally, the reactivity of esterification of secondary hydroxyl groups is poor, and it is difficult to directly esterify a carboxyl group formed from the ring-opening reaction of an acid anhydride with a secondary hydroxyl group. There is a need. Since these catalysts remain in the system, the pot life becomes extremely short when a curing agent is added, especially when a thermosetting epoxy resin is added, and the physical properties such as electrical properties due to the mixing of ionic substances Causes a decrease in

In Japanese Patent Application Laid-Open No. 11-21327, a compound obtained by reacting an epoxy resin with a monocarboxylic acid having two or more acryloyl groups per molecule and acrylic acid is reacted with a dibasic acid anhydride. A technique for improving the sensitivity and the like by using a photocurable resin obtained by the above method has been disclosed. However, the introduction of such an acrylate can achieve high sensitivity, but has a disadvantage in that the physical properties are brittle.

[0008]

SUMMARY OF THE INVENTION In view of the above-mentioned various problems, the present invention provides a method for manufacturing even under mild conditions such as a reduction in the amount of use of a halogen ion catalyst or the use of a non-halogen catalyst. Energy ray-curable resin that is capable of reducing ionic substances remaining in the coating film, is excellent in basic performance as a resist composition, and can greatly improve physical properties such as toughness. And a method for producing the same, and an energy ray-curable resin composition for a resist.

[0009]

Means for Solving the Problems The present inventors have used an unsaturated monocarboxylic acid, an epoxy resin and a dibasic acid anhydride, and the number of moles of the epoxy group of the epoxy resin is set to be equal to that of the unsaturated monocarboxylic acid. It is charged at a ratio close to the sum of the number of moles of the acid and the number of moles of the carboxylic acid of the dibasic anhydride, and
Hydroxyl-containing epoxy acrylate compounds having a structure in which the number of moles of the unsaturated monocarboxylic acid and the number of moles of the carboxylic acid of the dibasic anhydride are obtained using a specific molar ratio are basically obtained by reacting the epoxy group with the carboxylic acid. It is possible to reduce strong base catalysts such as halogen-based catalysts, etc., and to change to non-halogen-based catalysts, and to obtain energy rays having a structure obtained by reacting this acrylate compound with an acid anhydride. The present inventors have found that a resist resin composition containing a curable resin compound satisfies the required performance, and have completed the present invention.

More specifically, in the reaction of the epoxy acrylate, the unsaturated monocarboxylic acid (a2) and the dibasic acid anhydride (a3) are reacted with the epoxy resin (a1) to obtain the unsaturated monocarboxylic acid (a2). ) Reacts with the epoxy group of the epoxy resin (a1), and at this time, a hydroxyl group is generated by a ring opening reaction of the epoxy group. Also, the hydroxyl group originally contained in the epoxy resin (a1), or the epoxy resin (a1) and the unsaturated carboxylic acid (a2)
And / or any of the hydroxyl groups and the dibasic acid anhydride (a3) react by ring-opening esterification to form a carboxyl group from the dibasic acid anhydride (a3) I do. The carboxyl group generated at that time further reacts with the epoxy group of the epoxy resin remaining in the system to perform molecular growth.

In such a series of reactions, the epoxy group of the epoxy resin (a1) and the unsaturated monocarboxylic acid (a
The respective molar ratios n _a1 , n _a2 and n _a3 of 2) and the dibasic acid anhydride (a3) are set to 0.9 n _a1 <n _a2 + n _a3 <1.1 n
By performing the reaction at a specific molar ratio of _a1 and 1.0 < _na2 / _na3 <5.0, it is possible to accurately produce a resin capable of satisfying the physical properties required for the resist. They have found and completed the present invention. Therefore, in the production method according to the present invention, the dibasic acid anhydride (a3)
Plays a role as a chain extender for epoxy acrylate, and it is possible to use a relatively low molecular weight epoxy resin as a starting material in order to carry out this chain extension reaction.

The production of general epoxy resins is carried out by a dehydrochlorination reaction between various phenolic compounds and epichlorohydrin. In the production of high-molecular epoxy resins, high-purity epoxy resins are used in the ring closing and washing steps during the epichlorohydrin reaction. It is difficult to produce a resin. Therefore, the resin contains hydrolyzable chlorine, a hydroxyl group component that could not be ring-closed, and the like, and the cured resist film contains an ionic substance, which causes a problem in physical properties. For these reasons, epoxy resin starting materials used for resists are preferably low-molecular-weight epoxy resins because of their higher purity. However, epoxy acrylates synthesized from low molecular weight epoxy resins are difficult to use because they cause tack (adhesion) after solvent drying. Tackability after solvent drying affects the adhesion, dirt or workability of a negative film used during exposure to ultraviolet rays or the like, and is an important performance.

In the present invention, even with the use of such a low-molecular epoxy resin, it is possible to overcome such a problem by passing through a chain extension reaction with a dibasic acid anhydride (a3). In addition, it has been found that since the molecular structure grows linearly compared to epoxy acrylates using a general novolak type epoxy as a starting material, the physical properties after curing are also good, and a large effect is exhibited particularly in terms of toughness. The present invention has been completed.

Further, since this chain extension reaction is carried out by ring-opening esterification of the dibasic acid anhydride (a3) and reaction between the generated carboxyl group and epoxy group, it can be produced under mild conditions. is there. This has further advantages because the side reaction can be suppressed and reproducibility can be achieved without using a catalyst having a stronger activity.

That is, the present invention relates to [1] an epoxy resin
(a1), unsaturated monocarboxylic acid (a2) and dibasic anhydride
(a3) is reacted with the following formulas (1) and (2) in a ratio that satisfies both of the following formulas (1) and (2) to react with a hydroxyl group-containing modified epoxy acrylate compound (A) and an acid anhydride (B). it is intended to provide a method of manufacturing a radiation-curable resin, _{wherein, 0.9n a1 <n a2 + n} a3 <1.1n a1 (1) 1.0 <n a2 / n a3 <5.0 (2) (where n _a1 is the number of moles of all epoxy groups in (a1), n _a2 is the number of moles of all carboxyl groups in (a2),
_na3 represents the number of moles of the acid anhydride compound in (a3)),
The present invention also provides the energy of [1], wherein the reaction of the epoxy resin (a1) with the unsaturated monocarboxylic acid (a2) and the dibasic anhydride (a3) is carried out in the presence of a non-halogen catalyst. It is intended to provide a method for producing a line-curable resin,
The present invention also provides a method for producing an energy ray-curable resin according to [1] or [2], wherein the [3] non-halogen-based catalyst is a phosphorus-based catalyst.
[4] The method for producing an energy ray-curable resin according to [1], [2] or [3], wherein the unsaturated carboxylic acid (a2) is acrylic acid and / or methacrylic acid. In the present invention, the [5] epoxy resin (a1) has an epoxy equivalent of 90 to 400 g / equivalent (g /
eq) bisphenol A type epoxy resin and / or
Or epoxy equivalent 90 to 400 g / equivalent (g / eq)
[1] to the bisphenol F type epoxy resin
[4] The present invention provides a method for producing the energy ray-curable resin according to any one of [4] and [6].
It is characterized by comprising an energy ray-curable resin (I) obtained by the production method according to any one of [1] to [5] and a compound (II) having an epoxy group in a molecule. And an energy ray-curable resin composition for a resist.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

As the epoxy resin (a1) used in the present invention, any resin having two or more epoxy groups in the molecule can be used. Representative examples of such epoxy resins include bisphenol-type epoxy resins such as bisphenol A, bisphenol F, and bisphenol S; various novolak-type epoxy resins such as bisphenol novolak, cresol novolac, phenol novolac, and xylenol novolac; dicyclopentadiene Modified epoxy resin, naphthol having a naphthalene skeleton, binaphthol, an epoxy resin having a naphthalene skeleton obtained by epoxidizing these naphthols and novolaks thereof; a glycidyl ester type resin of a polycarboxylic acid, a linear aliphatic epoxy resin; Alicyclic epoxy resin, triglycidyl isocyanurate and derivatives thereof; unsaturated glycidyl group-containing unsaturated resins such as polyglycidyl (meth) acrylate and glycidyl (meth) acrylate; It can be mentioned copolymers of mer with other unsaturated monomers, the desired performance requirements, may use these epoxy resins alone or may be used in combination of two or more.

As a more preferred epoxy resin in the present invention, an epoxy resin having two epoxy groups is preferred in terms of molecular weight control and physical properties. As such an epoxy resin having two epoxy groups, a bisphenol-type epoxy resin represented by the following general formula can be suitably used. General formula (3)

Embedded image (Wherein R1, R2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X is a single bond _{or, -CO -, - SO 2 -} , -
_{C (CF 3) 2 -,} - Si (CH 3) 2 -, - CH 2 -, -
It represents C (CH ₃ ) ₂ —, —O—, or the following structural formula (4), and n is an integer of 0 to 10. ) Structural formula (4)

Embedded image

More preferred are bisphenol A type epoxy resin and bisphenol F type epoxy resin,
Above all, the epoxy equivalent of these epoxy resins is 90 to
Those having a range of 400 g / equivalent (g / eq) are particularly preferable in view of reproducibility during synthesis, developability, and cured physical properties.

The unsaturated monocarboxylic acid used in the present invention
As (a2), acrylic acid and / or methacrylic acid are preferable, or dimer acid or trimer acid thereof can be used. Further, a compound obtained by reacting a compound having an ethylenically unsaturated double bond and a hydroxyl group with an acid anhydride can be used. One or more unsaturated monocarboxylic acids (a2) can be used.

Examples of the compound having an ethylenically unsaturated double bond and a hydroxyl group used as a raw material of the unsaturated monocarboxylic acid (a2) include, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl Hydroxyalkyl (meth) acrylates such as (meth) acrylate and hydroxycyclohexyl (meth) acrylate; trimethylolpropane mono (meth) acrylate, trimethylolpropane diacrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) ) Acrylate, pentaerythritol tri (meth)
Esterified with polyols such as acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and (meth) acrylic acid A compound having a hydroxyl group in the molecule of the obtained compound; an epoxy (meth) acrylate obtained by reacting an epoxy compound having an epoxy group in the molecule with (meth) acrylic acid; the above-mentioned hydroxyl group and (meth) acrylate group A compound having a hydroxyl group and a (meth) acrylate group reacted with a cyclic lactone such as ε-caprolactone, and a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran. And the like compounds obtained by reacting.

The unsaturated monocarboxylic acid (a2)
Examples of the acid anhydride used as a raw material include maleic anhydride, phthalic anhydride, succinic anhydride, dodecenyl succinic anhydride, tetrahydrophthalic anhydride, 4-methyl-tetrahydrophthalic anhydride, and 4-methyl-hexahydroanhydride. Examples thereof include phthalic acid, hexahydrophthalic anhydride, trimellitic anhydride, methylnadic anhydride, itaconic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic anhydride.

The dibasic acid anhydride (a3) used in the present invention includes, for example, maleic anhydride, phthalic anhydride, succinic anhydride, dodecenyl succinic anhydride, tetrahydrophthalic anhydride, 4-methyl-tetrahydrophthalic anhydride Acid, 4
-Methyl-hexahydrophthalic anhydride, hexahydrophthalic anhydride and the like.

The production of the hydroxyl group-containing modified epoxy acrylate compound (A) used in the present invention is carried out by using an epoxy resin (a1)
And unsaturated monocarboxylic acid (a2) and dibasic anhydride (a3)
May be reacted simultaneously or sequentially.

The acid group of the dibasic acid anhydride (a3) is ester-bonded to the hydroxyl group formed by reacting the epoxy resin (a1) with the unsaturated monocarboxylic acid (a2) while ring-opening, and A group is formed. The carboxyl group reacts with the remaining epoxy group to form a hydroxyl group and grows.

In the reaction, the epoxy resin (a1), the unsaturated monocarboxylic acid (a2) and the dibasic acid anhydride (a3)
It is essential that both of the following expressions (1) and (2) are satisfied. 0.9n _a1 <n _a2 + n _a3 <1.1n _a1 (1) 1.0 <n _a2 / n _a3 <5.0 (2) (where n _a1 was used in the reaction (a1) The number of moles of all epoxy groups therein, n _a2, was used for the reaction (a
The number of moles of all the carboxyl groups in 2) and n _a3 represent the number of moles of the acid anhydride compound in (a3) used in the reaction. )

The sum of the number of moles of all the carboxyl groups in the unsaturated monocarboxylic acid (a2) and the number of moles of the acid anhydride compound in the dibasic acid anhydride (a3) is the total number of moles of the epoxy resin in the epoxy resin (a1). 0.9 to 1.1 times the number of moles of the group.

The sum of the number of moles of all the carboxyl groups in the unsaturated monocarboxylic acid (a2) and the number of moles of the acid anhydride compound in the dibasic acid anhydride (a3) is equal to the total epoxy number in the epoxy resin (a1). If the number of moles is less than 0.9 times the number of moles of the group, the epoxy group remains even after the completion of the reaction and adversely affects stability and the like. On the other hand, when the ratio is more than 1.1 times, the acid remains and adversely affects odor, stability and the like.

In the above formula (2), the ratio of the number of moles of all the carboxyl groups in the unsaturated monocarboxylic acid (a2) to the number of moles of the dibasic anhydride (a3) (n _a2 / n _a3 )
Is in the range of 1 to 5.

If the ratio of (n _a2 / n _a3 ) is less than 1, the acrylate functional group concentration of the epoxy acrylate will be low, causing problems in terms of sensitivity, resolution, and physical properties of the coating film. Also, the ratio of (n _a2 / n _a3 ) is 5
If it is larger, molecular growth is not sufficiently performed, and a problem occurs in tackiness after the solvent is temporarily dried. The ratio of (n _a2 / n _a3 ) is particularly preferably 2.0 <n _a2 / n _a3 <4.0.

The reaction can be carried out at a temperature in the range of 70 ° C. to 170 ° C., and particularly preferably in the range of 80 ° C. to 160 ° C. in terms of reduction of side reactions, control of molecular weight distribution, and reaction time. preferable.

At the time of production, a catalyst or a stabilizer may be used as long as the physical properties are not impaired. As the catalyst, a non-halogen catalyst or a small amount of a halogen catalyst in the range of 10 to 3000 ppm can be used.

As the catalyst, a non-halogen catalyst is preferable, for example, tertiary amines such as triethylamine, trisdimethylaminomethylphenol and benzyldimethylamine; and quaternary amines such as trimethylbenzylammonium hydroxide and tetramethylammonium hydroxide. Ammonium salts; imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; nitrogen compounds such as diazabiscycloundecene; triphenylphosphine, tris (methylphenyl) phosphine, tris- (2,6 Phosphines such as -dimethoxyphenyl) phosphine; phosphonium salts such as ethyltriphenylphosphonium hydroxide and tetra-n-butylphosphonium hydroxide; and chromium naphthenate. Various catalysts such as any metal salt can be used. Of these, phosphorus-based catalysts such as phosphines and phosphonium salts are preferred, and phosphines are particularly preferred. The amount used is 10 to 1 with respect to the charged amount.
0000 ppm is a suitable amount.

Examples of the halogen-based catalyst include inorganic catalysts such as sodium hydroxide and lithium hydroxide; diethylamine hydrochloride; and quaternary catalysts such as trimethylbenzylammonium chloride and tetramethylammonium chloride.
And quaternary ammonium salts, and phosphonium salts such as tetra-n-butylphosphonium bromide and ethyltriphenylphosphonium bromide.

As the polymerization inhibitor, for example, hydroquinone, methylhydroquinone, trimethylhydroquinone, tert-butylhydroquinone, 2-6-ditert-butyl-4-methoxyphenol, copper salt, phenothiazine and the like can be used.

Examples of the antioxidant include phosphorous acid,
Phosphites and phosphite diesters can be used.

The hydroxyl group-containing modified epoxy acrylate compound (A) has a number average molecular weight of 1,000 to 20,000 in terms of polystyrene in order to improve tackiness and mechanical properties after solvent drying and to make developability appropriate. Within the range, a polystyrene equivalent weight average molecular weight of 2000-4
It is preferably in the range of 0000.

The desired energy ray-curable resin can be produced by reacting the thus obtained hydroxyl-containing modified epoxy acrylate compound (A) with the acid anhydride (B).

As the acid anhydride (B), for example,
Maleic anhydride, phthalic anhydride, succinic anhydride, dodecenyl succinic anhydride, tetrahydrophthalic anhydride, 4-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride , Methylnadic anhydride, itaconic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride and the like.

The production of the energy ray-curable resin is carried out by, for example, modifying the hydroxyl group-containing modified epoxy acrylate compound (A)
0.15 mol or more, preferably 0.3 to 0.95 mol, of the acid anhydride (B) per 1 mol of the hydroxyl group in
It can be produced by reacting at 30 ° C., preferably 50 to 110 ° C., and performing pendant esterification. Here, the hydroxyl group in the hydroxyl group-containing modified epoxy acrylate compound (A) is the sum of the number of moles of the hydroxyl group contained in the epoxy resin (a1) and the reacted unsaturated monocarboxylic acid (a2). The value obtained by subtracting the number of moles of the dibasic anhydride (a3) from the sum of the number of moles of the hydroxyl group contained in the resin (a1) and the reacted unsaturated monocarboxylic acid (a2) is the number of moles of the hydroxyl group remaining during half esterification. And the carboxylic acid group generated by half-esterification of the dibasic acid anhydride (a3) reacts with the remaining epoxy group to form a hydroxyl group. Therefore, the number of moles of the dibasic acid anhydride (a3) is Further, it is an amount generated as a hydroxyl group.) At this time, the acid value is preferably in the range of 30 to 120 KOHmg / g, and particularly preferably in the range of 40 to 100 KOHmg / g in terms of developability and cured physical properties.

The reaction end point between the hydroxyl group in the hydroxyl group-containing modified epoxy acrylate compound (A) and the acid anhydride (B) is as follows:
Infrared spectrum 1770cm ^{- 1} and 1850cm
It is possible to confirm by an acid anhydride peak of ^-1 disappeared.

The molecular weight of the energy ray-curable resin (I) obtained by such a production method is determined to be a number average molecular weight in terms of polystyrene in order to improve tackiness and mechanical properties after drying the solvent and to make developability suitable. 1500 to 20
It is preferable that the weight average molecular weight is in the range of 2,500 to 40,000 in terms of polystyrene.

Further, the compound (II) having an epoxy group in the molecule, which can react with a carboxyl group in the energy ray-curable resin (I) after pattern formation by exposure to ultraviolet light and development, is present in the composition. Further, an energy ray-curable resin composition having improved mechanical properties, heat resistance properties, and the like can be obtained.

Compound (II) having an epoxy group in the molecule
Is not particularly limited, but an epoxy compound having two or more epoxy groups in one molecule is preferable, and typical examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, Phenol novolak type epoxy resin, cresol novolak type epoxy resin, glycidyl ester type epoxy resin of polyvalent carboxylic acid, alicyclic epoxy resin,
Examples include triglycidyl isocyanurate resin, dicyclopentadiene modified epoxy resin, epoxy resin having a naphthalene skeleton, epoxy resin derived from xylenol, phenol aralkyl epoxy resin, naphthalene aralkyl epoxy resin, and other Xyloc type epoxy resins.

The epoxy compound (II) having an epoxy group in the molecule may be used alone or as a mixture of two or more. Although there is no particular limitation on the range of use, 5 to 3 parts by weight per 100 parts by weight of the solid content of the energy ray-curable resin composition.
The amount is preferably 00 parts by weight, and particularly preferably 10 to 100 parts by weight.

Further, as long as the effects of the present invention are not impaired,
For accelerating the reaction, an epoxy curing accelerator can be added.

Examples of the epoxy curing accelerator include various epoxy curing accelerators such as amine compounds, imidazole compounds, dialkyl ureas, carboxylic acids, phenols, and compounds containing a methylol group. These curing accelerators promote the polymerization of energy ray-curable components by post-heating the coating film, and
Various physical properties of the resist film can also be improved through a reaction between the epoxy compound and a carboxyl group in the energy ray-curable resin composition and a reaction between the epoxy compounds.

In the energy ray-curable resin composition of the present invention, a photopolymerization initiator and a photosensitizer can be used when curing by irradiation with ultraviolet rays.

As the photopolymerization initiator, various photopolymerization initiators can be used, for example, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ester, alkoxyacetophenone, benzophenone and benzophenone derivatives, benzoylbenzoic acid Alkyl, bis (4-dialkylaminophenyl) ketone, benzyl and benzyl derivatives, benzoin and benzoin derivatives, benzoin alkyl ether, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, 2,4,6- Trimethylbenzoyl diphenoylphosphine oxide, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholinopropane-
1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, acetophenone,
2,2-dimethoxy-2-phenylacetophenone, 2,
2-diethoxy-2-phenylacetophenone, 1,1
Acetophenones such as dichloroacetophenone,
Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-aluminanthraquinone, 2,4-dimethylthioxanthone, 2,
Thioxanthones such as 4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; and xanthones.

The amount of the photopolymerization initiator is usually 0.2 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the solid content of the energy ray-curable resin composition. is there. Such photopolymerization initiators can be used alone or in combination of two or more.

The energy ray-curable resin composition for a resist according to the present invention may be used in combination with other photopolymerizable compounds for the purpose of improving the physical properties of the cured film, improving the curability, and improving the coating suitability. it can. The photopolymerizable compound used is
There is no particular limitation, and various photopolymerizable vinyl monomers and oligomers can be used.
-Hydroxyethyl (meth) acrylate, β-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, β-hydroxyethyl (meth) acryloyl phosphate, dimethylaminoethyl (meth)
Acrylate, diethylaminoethyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate
Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or tris (2- (meth) acryloyloxyethyl) Isocyanurates, mono-, di-, tri- or higher polyester (meth) acrylate compounds of polybasic acids and hydroxyalkyl (meth) acrylates, or bisphenol-type epoxy (meth) acrylates, novolak-type epoxy (meth) ) Monomers having ethylenically unsaturated double bonds, such as acrylates or urethane acrylates;
Oligomers.

In the present invention, an organic solvent can be used for improving the stirring efficiency in synthesizing the resin, reducing the viscosity, improving the handleability and the suitability for application.

Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; toluene,
Aromatic hydrocarbons such as xylene; cellosolves such as cellosolve and butyl cellosolve; carbitols such as carbitol and butyl carbitol; ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate and ethyl carbitol acetate And butyl carbitol acetate and other ether solvents and acetates derived from propylene glycol.

The above photopolymerizable compounds and / or organic solvents are used alone or as a mixture of two or more. The preferred range of the amount is 5 to 3 parts by weight based on 100 parts by weight of the solid content of the energy ray-curable flame-retardant resin.
The amount is preferably 00 parts by weight, more preferably 10 to 200 parts by weight.

The energy ray-curable resin composition for a resist of the present invention may further contain various fillers such as barium sulfate, silicon oxide, talc, clay and calcium carbonate, phthalocyanine blue, phthalocyanine green, Various coloring pigments such as titanium and carbon black, an antifoaming agent, an adhesion-imparting agent, a leveling agent, a slip agent and the like may be added.

The energy ray-curable resin composition for a resist of the present invention can form a coating film by being applied to various substrates. As the base material, for example, there is a printed wiring board, etc., on which the present composition is applied over the entire surface by a screen printing method, a roll coater method or a curtain coater method, a spray coater, a spin coater, etc., and irradiated with energy rays. After the necessary portions are cured, the unexposed portions are dissolved away with a dilute aqueous alkali solution, and further subjected to post-curing by heat, whereby a target film can be formed. When a solvent or the like is contained, the solvent may be dried before the irradiation with the energy beam.

The energy beam referred to in the present invention is an electron beam,
α-rays, γ-rays, X-rays, neutron rays or ultraviolet rays,
It is a general term for ionizing radiation and light.

When an ultraviolet ray is used as a light source for irradiating an energy ray, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp or a metal halide lamp is suitable. Can be used as energy rays.

[0059]

Next, the present invention will be described by way of examples and application examples.
More specifically, in the following, parts and%
All are by weight unless otherwise specified.

Example 1 A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 428 parts of ethyl carbitol acetate, and a bisphenol A type epoxy resin (epoxy equivalent 188 g /
eq; Epicron 85 manufactured by Dainippon Ink and Chemicals, Inc.
0) After dissolving 1128 parts, adding 1 part of hydroquinone as a polymerization inhibitor, adding 288 parts of acrylic acid, 296 parts of phthalic anhydride, and 5 parts of triphenylphosphine, and blowing at air at 120 ° C. for 12 hours. An esterification reaction was performed. At this time, the acid value of the system was 0.5 KOH-mg / g, and the epoxy equivalent was 18,600 g / eq. Thereafter, 687.2 parts of ethyl carbitol acetate and 552 parts of tetrahydrophthalic anhydride were added and reacted at 100 ° C. for 5 hours.
An energy ray-curable resin (X-1) was obtained. The acid value at this time was 60.6 KOH-mg / g (solid content 90.5 KOH-mg / g).
g).

Example 2 Into the same experimental apparatus as in Example 1, 402.5 parts of ethyl carbitol acetate were put, and 1026 parts of bisphenol F (epoxy equivalent: 171 g / eq; Epicron 830 manufactured by Dainippon Ink and Chemicals, Inc.) was dissolved. Then, after adding 1 part of hydroquinone as a polymerization inhibitor, 288 parts of acrylic acid,
296 parts of phthalic anhydride and 5 parts of triphenylphosphine were added, and an esterification reaction was performed at 120 ° C. for 12 hours while blowing air. At this time, the acid value of the system is 0.7 KOH
-mg / g, epoxy equivalent was 17,200 g / eq. Thereafter, 646.2 parts of ethyl carbitol acetate and 519.2 parts of tetrahydrophthalic anhydride were added and reacted at 100 ° C. for 5 hours to obtain an energy ray-curable resin (X-2). The acid value at this time was 60.4 KOH-mg / g (solid content 9
0.2 KOH-mg / g).

Example 3 Into the same experimental apparatus as in Example 1, 410 parts of ethyl carbitol acetate were placed, and 564 parts of a bisphenol A type epoxy resin (epoxy equivalent: 188 g / eq; Epicron 850 manufactured by Dainippon Ink and Chemicals, Inc.) was added. Dicyclopentadiene-modified epoxy resin (Epoxy equivalent: 264 g / eq; Epicron HP7200 manufactured by Dainippon Ink and Chemicals, Inc.)
Was dissolved, and 1 part of hydroquinone was added as a polymerization inhibitor. Then, 288 parts of acrylic acid and 2 parts of phthalic anhydride were added.
96 parts and 5 parts of triphenylphosphine were added, and an esterification reaction was performed at 120 ° C. for 12 hours while blowing air. At this time, the acid value of the system was 0.2 KOH-mg / g, and the epoxy equivalent was 15,200 g / eq. Thereafter, 757.8 parts of ethyl carbitol acetate and 528.9 parts of tetrahydrophthalic anhydride were added and reacted at 100 ° C. for 5 hours.
An energy ray-curable resin (X-3) was obtained. The acid value at this time was 58.5 KOH-mg / g (solid content 90.0 KOH-mg / g).
g).

Example 4 A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 420 parts of ethyl carbitol acetate, and a bisphenol A type epoxy resin (epoxy equivalent: 188 g /
eq; Epicron 85 manufactured by Dainippon Ink and Chemicals, Inc.
0) 1128 parts were dissolved, 1 part of hydroquinone was added as a polymerization inhibitor, and then 324 parts of acrylic acid, 228 parts of tetrahydrophthalic anhydride and 5 parts of triphenylphosphine were added. A time esterification reaction was performed. At this time, the acid value of the system is 0.5K
OH-mg / g, epoxy equivalent was 15,600 g / eq.
Thereafter, 655 parts of ethyl carbitol acetate and 502.7 parts of tetrahydrophthalic anhydride were added, and the mixture was added at 100 ° C for 5 hours.
The reaction was carried out for an hour to obtain an energy ray-curable resin (X-4). The acid value at this time was 57.2 KOH-mg / g (solid content 8
5.2 KOH-mg / g).

Example 5 In the same experimental apparatus as in Example 1, 507 parts of ethyl carbitol acetate were put, and 1368 parts of bisphenol F (epoxy equivalent: 171 g / eq; Epicron 830 manufactured by Dainippon Ink and Chemicals, Inc.) was dissolved. After adding 1.3 parts of hydroquinone as a polymerization inhibitor, 360 parts of acrylic acid,
300 parts of succinic anhydride and 5 parts of triphenylphosphine were added, and an esterification reaction was performed at 120 ° C. for 12 hours while blowing air. At this time, the acid value of the system is 0.7 KOH
-mg / g and epoxy equivalent was 19500 g / eq. Thereafter, 887 parts of ethyl carbitol acetate and 561 parts of tetrahydrophthalic anhydride were added and reacted at 100 ° C. for 5 hours to obtain an energy ray-curable resin (X-5). The acid value at this time was 52 KOH-mg / g (solid content 80.0 KOH-mg / g).
g).

Comparative Example 1 A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 428 parts of ethyl carbitol acetate, and a bisphenol A type epoxy resin (epoxy equivalent: 188 g /
eq; Epicron 85 manufactured by Dainippon Ink and Chemicals, Inc.
0) Dissolve 376 parts, add 0.5 part of hydroquinone as a polymerization inhibitor, add 144 parts of acrylic acid, 2 parts of triphenylphosphine, and blow 1
The esterification reaction was performed at 20 ° C. for 12 hours. At this time, the acid value of the system was 0.5 KOH-mg / g, and the epoxy equivalent was 3860.
It was 0 g / eq. Thereafter, 229.2 parts of ethyl carbitol acetate and 167.7 parts of tetrahydrophthalic anhydride were used.
The reaction was conducted at 100 ° C. for 5 hours to obtain an energy ray-curable resin (RX-1). The acid value at this time is 67.2 KO
H-mg / g (solids value: 89.5 KOH-mg / g).

Comparative Example 2 A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 356 parts of ethyl carbitol acetate, and a bisphenol A type epoxy resin (epoxy equivalent: 640 g /
eq; Epicron 205 manufactured by Dainippon Ink and Chemicals, Inc.
5) After dissolving 1280 parts and adding 1.3 parts of hydroquinone as a polymerization inhibitor, 144 parts of acrylic acid and 5 parts of triphenylphosphine were added, and while blowing air,
The esterification reaction was performed at 120 ° C. for 12 hours. At this time,
The acid value of the system was 0.5 KOH-mg / g, and the epoxy equivalent was 511.
It was 00 g / eq. Thereafter, 423.2 parts of ethyl carbitol acetate, 394.
One part was added and reacted at 100 ° C. for 5 hours to obtain an energy ray-curable resin (RX-2). The acid value at this time was 56.3.
KOH-mg / g (solid content: 80.5 KOH-mg / g)

Comparative Example 3 A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 356 parts of ethyl carbitol acetate, and a bisphenol A type epoxy resin (epoxy equivalent: 640 g /
eq; Epicron 205 manufactured by Dainippon Ink and Chemicals, Inc.
5) After dissolving 1280 parts and adding 1 part of hydroquinone as a polymerization inhibitor, 288 parts of acrylic acid and 5 parts of triphenylphosphine were added, and while blowing air, 1 part was added.
The temperature was raised to 20 ° C. to carry out the reaction, but the gel was formed in about 6 hours.

Comparative Example 4 A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 71.5 parts of ethyl carbitol acetate.
Cresol novolak type epoxy resin (epoxy equivalent 2
14 g / eq; 214 parts of Epicron N-665 manufactured by Dainippon Ink and Chemicals, Inc. were dissolved, 0.5 part of hydroquinone was added as a polymerization inhibitor, and 72 parts of acrylic acid and 2 parts of triphenylphosphine were added. The esterification reaction was performed at 120 ° C. for 12 hours while blowing air. At this time, the acid value of the system was 0.5 KOH-mg / g and the epoxy equivalent was 1
It was 2200 g / eq. Thereafter, 127.5 parts of ethyl carbitol acetate, tetrahydrophthalic anhydride 8
3.6 parts were added and reacted at 100 ° C. for 5 hours to obtain an energy ray-curable resin (RX-4). The acid value at this time is 5
4.3 KOH-mg / g (solid content: 83.6 KOH-mg / g).

Comparative Example 5 A flask equipped with a thermometer, a stirrer and a reflux condenser was charged with a bisphenol A type epoxy resin (epoxy equivalent: 1).
88 g / eq; 188 parts of Epicron 850 manufactured by Dainippon Ink and Chemicals, Inc. were dissolved, and 2,6-
After adding 0.1 part of diisobutylphenol, 72 parts of acrylic acid and 0.45 part of triethylbenzylammonium chloride are added.
The esterification reaction was performed at 10 ° C. for 10 hours. At this time, the acid value of the system was 0.5 KOH-mg / g, and the epoxy equivalent was 23200 g / e.
q. Then, ethyl carbitol acetate 2
33.8 parts, 38 parts of tetrahydrophthalic anhydride, 80.5 parts of benzophenonetetracarboxylic dianhydride and 1 part of tetraethylammonium bromide were added, and reacted at 115 ° C. for 5 hours to obtain an energy ray-curable resin (RX- 5) was obtained. The acid value at this time was 55.9 KOH-mg / g (solid content 8
6KOH-mg / g).

Comparative Example 6 A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 460.7 parts of ethyl carbitol acetate, and a cresol novolak type epoxy resin (epoxy equivalent: 214 g / eq; Dainippon Ink and Chemicals, Ltd.) After dissolving 430 parts of Epicron N-665 manufactured by Co., Ltd. and adding 0.5 parts of hydroquinone as a polymerization inhibitor, acrylic acid 11
5.2 parts and 159.2 parts of pentaerythritol triacrylate / succinic anhydride adduct were charged, 3 parts of triphenylphosphine was added, and
The esterification reaction was performed at 0 ° C. for 12 hours. At this time, the acid value of the system was 8.3 KOH-mg / g, and the epoxy equivalent was 9800 g / g.
eq. Then, 60 parts of succinic anhydride and 91.2 parts of tetrahydrophthalic anhydride were added and reacted at 80 ° C. for 4 hours to obtain an energy ray-curable resin (RX-6).
At this time, the acid value was 52 KOH-mg / g (solid content 80 KOH-mg / g).
g).

Tables 1 and 2 show the characteristic values of the resins obtained in the examples and comparative examples.

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

[Table 3]

Footnotes to Tables 1 to 3 (a1): Epoxy resin. The numerical values in the table are the number of moles of the epoxy group charged. (a2): unsaturated carboxylic acid. The numbers in the table are the number of moles of carboxylic acid charged. (a3): dibasic acid anhydride. The numbers in the table are the moles of acid anhydride charged. (B): acid anhydride. The numbers in the table are the moles of the acid anhydride. BPA1: Bisphenol A type epoxy resin. Epoxy equivalent 188 g / equivalent (g / eq.) BPA2: bisphenol A type epoxy resin. Epoxy equivalent 640 g / equivalent (g / eq.) ECN: Cresol novolak type epoxy resin. Epoxy equivalent 214 g / equivalent (g / eq.) BPF1: Bisphenol F type epoxy resin. Epoxy equivalent 171 g / equivalent (g / eq) DCPD: dicyclopentadiene-modified epoxy resin. Epoxy equivalent 264 g / equivalent (g / eq) AA: acrylic acid PAN: phthalic anhydride THPA: tetrahydrophthalic anhydride SAN: succinic anhydride PETA-SA: reaction product of pentaerythritol triacrylate and succinic anhydride BPDAn: benzophenone tetracarboxylic acid Dianhydride. (n _a2 + n _a3 ) / n _a1 : Relational expression derived from equation (1). The value of the relationship (n _a2 + n _a3 ) / n _a1 is in the range of 0.9 to 1.1. n _a2 / n _a3 : Relational expression derived from Expression (2). claims that the value of n _a2 / n _a3 relationship is in 1.0 to 5.0. Acid value: KOHmg / g Molecular weight: GPC (MILLENNIUM32-J SYSTEM THF solvent at 40 ° C, manufactured by WATERS) The number average molecular weight and the weight average molecular weight were calculated by measuring the molecular weight distribution in terms of polystyrene.

Preparation of active energy ray-curable composition for resist Examples 6 to 10 and Comparative Examples 4 and 5 Using the resins obtained from Examples 1 to 5 and Comparative Examples 1 to 6, the following resist inks were prepared. A composition was prepared. Solid content of each sample (resin samples of Examples 1 to 5 and Comparative Examples 1 to 6) 45 parts Cresol novolak type epoxy resin (EE214) 10 parts Dipentaerythritol hexaacrylate 4 parts Irgacure 907 (Ciba Geigy, photopolymerization initiator) 6 parts Barium sulfate 34.5 parts Phthalocyanine green 0.5 parts

<Evaluation Method> With respect to the samples (resins) obtained from Examples 1 to 5 and Comparative Example, the prepared resist ink compositions were coated and evaluated by the following methods.

(1) Coating method Each resist ink composition was applied to a glass epoxy substrate by 100
Solid printing was performed on a mesh screen, and the thickness of the coating film that had been forcibly dried was about 40 μm. Evaluation result is 3rd
It is as shown in the table. A substrate was prepared on a tin plate only for preparing a sample of mechanical properties.

(2) Drying property to touch 1 The coating film immediately after drying at 80 ° C. for 30 minutes was evaluated for tackiness when touching the coating. ：: no tack △: slight tack ×: tacky

(3) Drying to the touch 2 Drying at 80 ° C. for 30 minutes, and then irradiating with ultraviolet rays under the above conditions, peeling off the step tablet for sensitivity evaluation (Step tablet No. 2 manufactured by Kodak). The tack was evaluated according to the following criteria. ：: The step tablet can be easily peeled off without tackiness. Δ: Slightly tacky, step tablet caught, but peelable. X: There is tackiness, and the ink adheres to the step tablet and is difficult to peel off.

(4) Developability The screen-printed sample was left in a dryer at 80 ° C. for 30 minutes to evaporate the solvent, immersed in a 1% aqueous sodium carbonate solution at 30 ° C. for 60 seconds, and remained on the substrate. Was evaluated according to the following criteria. ：: No coating film remained on the substrate. Δ: Part of the coating film on the substrate remains. ×: The coating film on the substrate did not dissolve and almost remained.

(5) Sensitivity Measurement of Resist Ink The screen-printed sample was left in an oven at 80 ° C. for 30 minutes to evaporate the solvent, and a step tablet N was formed on the coating film.
o.2 (manufactured by Kodak Co., Ltd.) and using a high-pressure mercury lamp, 125 mj / cm ² , 250 mj / cm ² , 50
After irradiation with ultraviolet rays of 0 mj / cm ^2, the film was immersed in a 1% aqueous sodium carbonate solution at 30 ° C. for 60 seconds, and evaluated by a step tablet method. The numbers in the table indicate the number of steps of the step tablet, and the larger the number, the better the curability (sensitivity). One or more stages in the irradiation conditions of 125mj / cm ^2, 3 or more stages under the conditions of 250mj / cm ^2, 500m
Under the condition of j / cm ² , 5 or more steps were judged to be acceptable.

(6) Resolution The screen-printed sample was left in an oven at 80 ° C. for 30 minutes to evaporate the solvent, and a photomask: PCW
UGRA82 (manufactured by UGRA) was placed thereon, and irradiated with 500 mj / cm ² ultraviolet rays using a high-pressure mercury lamp.
It was immersed in a 1% aqueous solution of sodium carbonate at 0 ° C. for 60 seconds, and evaluated by the minimum value of the remaining line width and the dissolved line width.

(7) Stability test when drying solvent (drying control width) A tin plate (test piece) coated with ink was left in a dryer at 90 ° C. for 30 minutes, 40 minutes and 50 minutes to evaporate the solvent. Then, the film was immersed in a 1% aqueous solution of sodium carbonate at 30 ° C. for 60 seconds and developed, and the stability of the solvent when dried was visually determined. ：: No coating film remained on the substrate. Δ: Part of the coating film on the substrate remains. ×: The coating film on the substrate did not dissolve and almost remained.

(8) Mechanical Properties After the tin plate (test piece) coated with the ink was dried in a dryer at 90 ° C. for 30 minutes, ultraviolet rays were irradiated at 500 mj / c.
m ² irradiation, and curing was further performed at 150 ° C. for 1 hour. This sample was cut into strips 1 cm wide and 7 cm long, and a tensile test was performed. The ambient temperature was 53 RH% at 23 ° C.
The distance between the chucks is 10 mm, and the pulling speed is 10 mm / m
Measurements were made in.

[0086]

[Table 4]

[0087]

[Table 5]

The units of the breaking strength and the elastic modulus in the mechanical properties in the table are MPa, and the units of the breaking elongation are%.

Table 3 shows the evaluation results of the resist compositions prepared using the carboxylic acid group-containing epoxy acrylate resins X-1 to X-5 synthesized in Examples 1 to 5.
Table 4 shows the evaluation results of the epoxy acrylate resins synthesized in Comparative Examples 1 to 6 in which the compositions were adjusted to have the same composition. In addition, since the resin in Comparative Example 3 was gelled, the composition could not be evaluated. Table 3 shows that the compositions of the examples were dry to the touch and all the compositions showed good results. In addition, good results were also obtained regarding the developability.
Further, the sensitivity was at an acceptable level. The resolution was as good as 20 μm. Also, with respect to the drying control width, a result that development for 50 minutes or more was possible was obtained. Regarding the mechanical properties, all the compositions have elongations of 5% or more, and the breaking strength and the elastic modulus are also acceptable. On the other hand, in Comparative Example 4 in Table 4, the dryness to the touch and the mechanical properties, particularly the elongation at break, are poor, and there is a problem in use. In Comparative Examples 5 and 7, the pattern was not formed because of poor developability. In Comparative Examples 6 and 8, the dryness to the touch was inferior, the elongation at break was low, and the material was brittle and easily broken.

[0090]

The method for producing an energy ray-curable resin and the energy ray-curable resin composition for a resist according to the present invention can be stably produced from the above results, and can be used as an energy ray-curable resin composition for a resist. In the evaluation results of tackiness, developability, stability test during solvent drying,
In terms of sensitivity, resolution, mechanical properties, and the like, all the results were superior to the comparative example. Therefore, it is clear that the production method of the present invention and the composition containing the structure obtained by the production method exhibit excellent performance.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AB15 AB17 AC01 AD01 BC74 CC17 FA17 4J036 AB17 AD08 AD20 AE05 AF06 AF08 AF15 AG03 AJ08 AK11 CA21 DB14 DB20 DB21 DB22 EA09 HA01 JA10

Claims (6)

[Claims] 1. An epoxy resin (a1), an unsaturated monocarboxylic acid (a2) and a dibasic acid anhydride (a3) are reacted in a ratio satisfying any of the following formulas (1) and (2). A method for producing an energy ray-curable resin, comprising reacting a hydroxyl group-containing modified epoxy acrylate compound (A) obtained as described above with an acid anhydride (B). 0.9n _a1 <n _a2 + n _a3 <1.1n _a1 (1) 1.0 <n _a2 / n _a3 <5.0 (2) (where n _a1 is the total epoxy group in (a1) And n _a2 is the number of moles of all carboxyl groups in (a2),
_na3 represents the number of moles of the acid anhydride compound in (a3). ) 2. The energy ray-curable type according to claim 1, wherein the reaction between the epoxy resin (a1), the unsaturated monocarboxylic acid (a2) and the dibasic acid anhydride (a3) is carried out in the presence of a non-halogen catalyst. Method of manufacturing resin. 3. The method for producing an energy ray-curable resin according to claim 1, wherein the non-halogen-based catalyst is a phosphorus-based catalyst. 4. The method for producing an energy ray-curable resin according to claim 1, wherein the unsaturated carboxylic acid (a2) is acrylic acid and / or methacrylic acid. 5. A bisphenol A type epoxy resin having an epoxy equivalent of 90 to 400 g / equivalent (g / eq) and / or an epoxy equivalent of 90 to 400 g / eq.
The method for producing an energy ray-curable resin according to any one of claims 1 to 4, wherein the epoxy resin is a bisphenol F type epoxy resin having a weight of 400 g / equivalent (g / eq). 6. An energy ray-curable resin (I) obtained by the production method according to claim 1;
An energy ray-curable resin composition for a resist, comprising a compound (II) having an epoxy group in a molecule.