JPH0297517A - Active energy ray-curable resin composition - Google Patents

Abstract

PURPOSE:To prepare a compsn. laminatable in a desired pattern on metal, glass, ceramics or plastics, by compounding a graft copolymer, an esterified epoxy resin, a monomer and a polymerization initiator, each being respectively specified. CONSTITUTION:A resin compsn. is prepd. by compounding a graft copolymer wherein a branched chain having structural units derived from a monomer, e.g., of the formula (wherein R<1> is H, etc.) is attached to a main chain having a structural unit derived from a monomer such as alkyl methacrylate, a linear polymer having structural units derived from a monomer such as methyl methacrylate, cyclohexyl methacrylate, etc., a resin prepd. by partially esterifying the epoxy groups of an epoxy resin contg. a compd. having at least two epoxy groups in its molecule with an unsatd. carboxylic acid, an ethylenycally unsatd. monomer and a polymerization initiator which generates a Lewis acid by active energy ray radiation.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a resin composition that is cured by irradiation with active energy rays such as ultraviolet rays and electron beams, and particularly relates to a copper-clad laminate for printed wiring boards. The present invention relates to an active energy ray-enriched resin composition that can be laminated onto metals, glass, ceramics, plastic films, etc. in a desired pattern.

(Prior Art) In recent years, active energy ray-curable resin compositions have been widely used as paints, inks, sealing materials, resist materials, protective film materials, pattern forming materials, and the like. For example, an active energy ray-curable resin composition used as a protective coating film for printed wiring boards or a resist material for forming wiring patterns thereof is a dry film containing a polymer substance having film-forming ability. Film resist (
Known examples include RISTON (trade name: manufactured by DuPont Japan Limited), thick film liquid resists produced by photographic methods (trade name: PROVIMER (trade name: manufactured by Ciba Geigy, etc.)), and the like.

The above-mentioned composition contains a polymeric substance (hereinafter simply referred to as polymeric substance) for imparting properties such as shaping into a film or a dry film, and active energy. The main component is a linear hardening substance. The adhesion of the stiff composition to the support, the developability for pattern formation, the durability as a coating film, the applicability, the drying properties, etc. are greatly influenced by the type and molecular structure of the polymeric substance described in 17. . Therefore, selection of the type of polymeric substance and molecular design have been carried out with the aim of achieving desired levels of the above-mentioned properties.

[Problem to be solved by the invention]

However, even after selecting the type of polymer material and designing the molecule as described above, conventional active energy ray-curable resin compositions still have insufficient adhesion properties to various supports. It had not reached that point.

To solve this problem, it has been proposed to add additives or coupling agents capable of forming complexes with metals, such as heterocyclic compounds, to such resins (Japanese Patent Publication No. 51-1999). 5934, Special public service Sho 58-2403
5 etc.). However, over a long period of time, this method
There is a problem in that the above-mentioned additives and the like cause phenomena such as oxidation and corrosion of the composition.

On the other hand, with the aim of obtaining a cured composition that has sufficient adhesion without the addition of such additive aids, a polymer material consisting of a graft co-rfH combination having polar groups in the branch chain was disclosed in Japanese Patent Application Laid-open No. It is disclosed in 61-291619 and the like. The active energy ray-curable resin composition containing the polymer substance (graft copolymer polymer) disclosed therein improves adhesion and further improves the durability of coating S without relying on additives or the like. We were able to achieve this goal. However, these techniques still have the problem that it is difficult to design the molecules of the polymer substances (graft copolymer polymers). That is, in general, while keeping the molecular weight and content of the branch chains constant, the graft copolymer as a whole is synthesized so as to have a desired molecular weight over a wide range (approximately 50,000 to 350,000). This is technically difficult.

In other words, in order to improve the development characteristics during pattern formation, that is, the dissolution rate of the unpolymerized part, the swelling property of the polymerized part, and the resulting sensitivity, pattern sharpness, and controllability of resolution, it is necessary to The average molecular weight of the molecular substance should not be too small.

In graft copolymer polymers, a large number of branch chains with sufficient length to obtain effective adhesion are bonded to a relatively large molecular weight trunk chain to obtain a number average molecular weight that meets the above objectives. This is accompanied by difficulties in the current synthetic techniques due to steric hindrance.

In other words, if the average molecular weight of the polymeric substance is too low,
There are certain limitations on the development characteristics of the pattern-forming material using it, that is, the dissolution rate of the unpolymerized part, the swelling property of the polymerized part, and the resulting sensitivity, pattern sharpness, and resolution adjustment.

The present invention has been made in view of the above-mentioned problems, and its purpose is to provide ultraviolet rays that can be laminated in a desired pattern shape to steel-clad laminates for printed wiring boards, metals, glass, ceramics, plastics, etc. The object of the present invention is to provide a superior resin composition that is cured by (irradiation with) active energy rays such as electron beams.

Another object of the present invention is to provide an active energy ray-curable resin composition that has excellent adhesion to a substrate even without the addition of additives or the like.

Still another object of the present invention is to provide an active energy ray-curable resin composition that has excellent development characteristics during pattern formation.

Another object of the present invention is to provide an excellent active energy ray-curable resin composition whose properties can be easily controlled so as to obtain desired properties in accordance with various uses.

(Means for Solving the Problems) The above object of the present invention is to (A) use a monomer selected from the group consisting of alkyl methacrylate, acrylonitrile and styrene (hereinafter referred to as "monomer ■"); The following general formulas (x) and (y): ) 0=C-0-R' -OH [However, R' represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group, and R2
represents hydrogen, or an alkyl group or acyl group having 1 to 4 carbon atoms which may have a hydroxy group,
R3 is an alkyl group having 2 to 6 carbon atoms, or a halogen-substituted alkyl group, an alkyl group represented by -f CHzh-0 to CH2h- (where 2≦m+n≦6, n≠O, m≠0) Ether group, (however, 2≦m + n=4, n=o or ln"
(including the case of 0) is a phenylalkyl group represented by the following. ] at least one monomer among the seven monomers (hereinafter referred to as "
It is made by adding branch chains that e f the structural position derived from "Monomanor■"), and the number of homogeneous molecules is more than 5,000, and the weight average molecule! (B) methyl methacrylate, ethyl methacrylate, isobutyl methacrylate,
t-Butyl methacrylate, pencil methacrylate, acrylonitrile, isopornyl methacrylate decane acrylate, tricyclodecane methacrylate, tricyclodecaneoxyethyl methacrylate,
One or more monomers selected from the group consisting of monomers consisting of styrene, dimethylaminoethyl methacrylate, and cyclohexyl methacrylate (hereinafter referred to as "monomer ■")
), and has a structural unit derived from the above-mentioned - Noshiro (
It has a structural unit derived from at least one of the monomers represented by X) or (y), and has a number average molecular weight of 50,000 or more and a weight average molecular weight of 35
and (C) at least one compound having two or more epoxy groups in the molecule. A resin partially esterified with an unsaturated carboxylic acid, (D) a monomer having an ethylenically unsaturated bond, and (E)
This is achieved by an active energy ray-curable resin composition comprising a polymerization initiator that generates a Lewis acid upon irradiation with active energy rays.

Below, each component (A) to (E) constituting the composition of the present invention
will be explained in detail.

As mentioned above, one or more types selected from the group consisting of alkyl methacrylate, acrylonitrile, and styrene are used as the main component for the main chain of the graft copolymer polymer (A).

In addition to the monomers represented by Noshiro (X) or (y), the following polar monomers can be used in combination with the monomers used for the branch chain, if necessary.

<I) Acrylic monomer containing amino group or alkylamino group (11) Acrylic or vinyl monomer containing carboxyl group (III) N-vinylpyrrolidone or its derivative (IV) Vinylpyridine or its derivative may also be used as a component in the copolymerization within a range of about 25 mol% or less.

Graft copolymer polymer (A) used in the composition of the present invention
), for example, from 10 to 10 of ``Basics and Applications of Polymer Alloys'' (edited by The Society of Polymer Science, published by Tokyo Kagaku Dojin, 1981).
It can be produced by various conventionally known methods as described on page 35. These methods include:
■Chain transfer method, ■Method using radiation, ■Oxidative polymerization method,
■Ion graft polymerization method, ■Macromonomer method, etc. Using these methods, appropriately select polymerization conditions to obtain a graft copolymer polymer with a 5-number average molecular weight of 5,000 or more and a weight average molecular weight of 50,000 or less using the monomers 1 and 2 exemplified above. Graft copolymer polymer (8) constituting the composition of the present invention can be obtained by polymerization.

It should be noted that among the above-mentioned methods (1) to (2), it is preferable to use method (1) or (2) because the lengths of the chain branches of the copolymer polymer (A) are uniform. In particular, the micro-mono-manor method (2) is a more preferred method.

The linear polymer (B) has at least one of the above-mentioned monomers as a main component, uses at least one of the monomers represented by -Noshiro (x) or (y), and has a number average molecular weight of 50,000 or more. , layer average molecular heat of 350,000 F or more
So that the polymer has a glass transition temperature of 60°C or higher,
It can be obtained by polymerizing using a conventionally known method while appropriately selecting polymerization conditions. In addition, the above-
It is preferable to add the 7-mers represented by Noshiro (x) and (y) in a range of 5 mol % to 30 mol %. If the linear polymer contains more than 30 mol% of this 1,000 mol %, the concentration of polar groups in the cured coating film will increase, and the effect of improving adhesion will not further increase, but the water resistance will increase. This is not desirable because a decrease in Furthermore, if the amount of monomer (1) mixed in the obtained linear polymer is 5 mol % or less, the effect of improving adhesion and acting as a binder for the coating film will be insufficient.

For the purpose of providing a high glass transition temperature and increasing water resistance,
The above-mentioned chemicals include methyl methacrylate,
Isobornyl methacrylate, isobornyl acrylate, tricyclodecane methacrylate, tricyclodecane acrylate and the like give particularly favorable results.

A part of the epoxy groups present in the epoxy resin consisting of a compound containing two or more epoxy groups in one molecule to be contained in the active energy ray-curable resin composition of the present invention is replaced with an unsaturated carboxylic acid. The resin component (C) obtained by esterification (hereinafter abbreviated as half-esterified epoxy resin) is highly sensitive to active energy rays applied to the resin composition of the present invention in the presence of a polymerization initiator (E) described below. In addition, the resin composition of the present invention is applied in liquid form onto various supports made of glass, plastics, ceramics, etc., and then cured to form a cured film. When formed as a dry film or adhered to various supports in the form of a dry film, the cured film made of the resin composition has better adhesion to the support,
It is a component for imparting water resistance, chemical resistance, dimensional stability, etc.

This half-esterified epoxy resin (C) is produced by adding a predetermined amount of unsaturated carboxylic acid to an epoxy resin in the presence or absence of a solvent in the coexistence of an addition catalyst and a polymerization inhibitor at a temperature of 80 to 120°C. It can be obtained by a method in which a part of the epoxy groups present in the epoxy resin is esterified (half-esterified) with a carboxylic acid through a reaction depending on temperature conditions.

Epoxy resins containing one or more compounds containing two or more epoxy groups in one molecule that can be used to form the half-esterified epoxy resin (C) include bisphenol A type, novolac type, and resin. Epoxy resins represented by ring type, bisphenol S, bisphenol F, tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether,
Glycerin triglycidyl ether, pentaerythol triglycidyl ether, ・r-socyanuric acid triglycidyl ether and the following Noshiro (I) (However, R4 is an alkyl group or an oxyalkyl group,
R5 represents (>, K-wing Cf17.+, or an alkyl group) Examples include polyfunctional epoxy resins such as epoxy urethane resins represented by the following formula, and mixtures of one or more of these.

In addition, the following can be mentioned as a specific example of these polyfunctional epoxy resins.

That is, as a bisphenol A type epoxy resin,
For example Epicote 828, 834.871.1001
, +004 (product name, manufactured by Shell Chemical Co., Ltd.), DER33
1-J, 337-J, 661-J, 664-
J, 667-J (manufactured by Dow Chemical Company) and Epicron 800 (trade name, manufactured by Dainippon Ink & Chemicals Company)
Examples of Natoconohorac type epoxy resins include Epicote+52.154, 172, (trade name, manufactured by Shell Chemical Co., Ltd.), Araldite EPN 1138 (trade name,
(manufactured by Ciba Geigy), 431, 438, and 39 (trade name, manufactured by Dow Chemical Company); examples of alicyclic epoxy resins include Araldite GY-175.
, -176, -179=l82, -184, -192
(Product name, manufactured by Ciba Geigy), Chinnox 090
, 09], 092.3 old, 313 (product name, manufactured by Chin■ Co., Ltd.), Syracure (1; YI'1ACLIRE
)6100. 6110. 6200 and ERL 4
090.46] 7.2256.5411 (trade name, manufactured by Union Carbide) etc. Examples of polyglycidyl ethers of aliphatic polyhydric alcohols include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, etc. Glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether 53. 6-hexanesiol diglycidyl ether, glycerin diglycidyl ether, tosomethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 2.2- Dibromoneopentyl glycol diglycidyl ether, etc.; polyhydric glycidyl ethers derived from aromatic polyhydric alcohols include 2 to 1 of alkylene oxide of bisphenol A.
Examples include diglycidyl ether as a 6 mol adduct, diglycidyl ether as a 2 to 16 mol adduct of bisphenol F with alkylene oxide, and diglycidyl ether as a 2 to 16 mol adduct of bisphenol S with alkylene oxide.

As unsaturated carboxylic acids that can be used for half-esterification of a part of the epoxy groups in the epoxy resin (hereinafter referred to as "half-esterification"),
Although a wide variety of acrylic or methacrylic vinyl groups can be used at least at one end of the molecule, in order to impart better curability with activation energy to the resin composition of the present invention. A basic unsaturated carboxylic acid having a carboxyl group at the other end can be suitably used.

Typical examples of such unsaturated carboxylic acids include acrylic acid and methacrylic acid, and monoester compounds obtained by reacting dicarboxylic acids with (meth)acrylic esters having one hydroxyl group can also be used.

The above dicarboxylic acids include phthalic acid, isophthalic acid,
Examples include terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, isosebacic acid, tetrahydrophthalic acid, and anhydrides thereof.

In addition, as the above-mentioned (meth)acrylic acid ester having one hydroxyl group, 2-hydroxypropyl (
meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, hydroxybutyl(meth)acrylate, 5-hydroxybutyl(meth)acrylate and 6-hydroxybutyl(meth)acrylate ) acrylate, etc.

Examples of addition reaction catalysts that can be used in the half-esterification reaction of the epoxy resin include metal halides such as zinc chloride and lithium chloride, sulfide compounds such as dimethyl sulfide and methylphenyl sulfide, and sulfide compounds such as dimethyl sulfoxide and methyl sulfide. Sulfochite compounds such as ethyl sulfoxide, tertiary amine compounds such as N,N-dimethylaniline, pyridine, triethylamine, benzyldimethylamine, and their hydrochlorides or bromates, such as tetramethylammonium chloride, trimethyldodecyl Examples include quaternary ammonium salts such as benzylammonium chloride and triethylbenzylammonium chloride, compounds of sulfonic acids such as para-toluenesulfonic acid, and compounds of mercaptans such as ethyl mercaptan and propyl mercaptan.

Furthermore, examples of polymerization inhibitors that can be used for half-esterifying the epoxy resin include hydroquinone, alkyl- or aryl-substituted hydroquinone, and tertiary hydroquinone.
Butylcatechol, and rogallol, naphthylamine, beta
- Naphthol, cuprous chloride, 2,6-di-tert-butyl-p
-cresol, phenothiazine, N-nitrosodiphenylamine and diF-lobenzene.

In addition, examples of solvents that can be used when carrying out the half-esterification reaction of the epoxy resin described in (g) in the presence of a solvent include toluene, xylene, methyl isobutyl ketone, methyl ethyl ketone, ethyl acetate, butyl acetate, and isobutyl acetate. can be mentioned.

When using an epoxy resin and an unsaturated carboxylic acid in the half-esterification reaction, the ratio of the epoxy group of the epoxy resin to the carboxyl group of the unsaturated carboxylic acid is preferably 1.
:0.3 to l :0.7, more preferably I :
0.45 to 1: Suitably selected to be 0.55.

In other words, if the esterification rate of the epoxy group by unsaturated carboxylic acid in the half-esterified epoxy resin is higher than the above range, active energy rays derived from the epoxy resin that have good chemical resistance and dimensional stability will not be used. It is difficult to obtain effective curable resin compositions for this purpose.

Moreover, if it is lower than the above range, it is difficult to obtain a resin composition based on (meth)acrylic acid ester groups that has sufficient curability with high resolution under the action of active energy rays.

As described above, the active energy ray-curable resin composition of the present invention has the high sensitivity of the half-esterified epoxy resin (C) contained at least as an essential component, and the high sensitivity of the active energy ray-curable resin composition based on the acrylic acid ester group. The resin composition of the present invention is cured by irradiating active energy acid, and then further heated at 80°C or higher for about 10 minutes to 3 hours. The cured film obtained by thermosetting is more effectively provided with good chemical resistance, dimensional stability, etc. derived from the epoxy resin.

The monomer (D) having an ethylenically unsaturated bond used in the resin composition of the present invention refers to It is a component for exhibiting curability and especially for imparting excellent sensitivity to active energy rays, preferably having a boiling point of 100°C or higher under atmospheric pressure, and more preferably having an ethylenically unsaturated bond of 2. It is possible to use various known monomers that have at least one monomer and are cured by irradiation with active energy rays.

Specific examples of such monomers having two or more ethylenically unsaturated bonds include: Acrylic esters, ■ Acrylic esters or methacrylic esters of alkylene oxide adducts of polyhydric alcohols, 〇 Polyesters with a molecular weight of 500 to 3,000 consisting of dibasic acids and dihydric alcohols with acrylic ester groups at the molecular chain ends. Examples include polyester acrylate, and (2) a reaction product of a polyvalent isocyanate and an acrylic acid monomer having a hydroxyl group. Above■
The monomers of ~■ may be urethane-modified products having a urethane bond in the molecule.

Examples of monomers belonging to category (2) include acrylic acid or methacrylic acid esters of polyfunctional epoxy resins used to produce the above-mentioned half-esterified epoxy resin component (C).

Monomers belonging to category (1) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, and polyethylene glycol di(meth)acrylate. Acrylate, pentaerythritol tri(meth)acrylate, etc.6J-L, trade name KAY HachiRAD llX-22
0, HX-620, D-310, D-320, D-33
0%DPHA%R-604, DPCA-20, DPC
A-30, DPCA-60, DPCA-120 (and above,
(manufactured by Nippon Kayaku ■), product name N is ester BPE-200,
BPE-50010PE-1300, A-BPE-4 (
For the above, known products such as those manufactured by Shin Nakamura Kagaku ■ can be used.

As a monomer belonging to ■, the product name is Aronix M-6.
100, M-6200, M-6250, M-6300,
M-6400, M-7100, M-8030, M-80
60, M-8100 (manufactured by Toagosei Kagaku ■), and the like. Items that belong to category (1) and contain polyester urethane bonds include the product name Aronix M-110.
0, Aronix M-1200 (Toagosei Chemical ■
Examples include those known as (manufactured by).

Monomers belonging to category (2) include polyisocyanates and hydroxyl group-containing monomers such as tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and diphenylmethane diisocyanate. Products that react with acrylic monomers include products such as Sumidur N (biuret derivative of hexamethylene diisocyanate), Sumidur L (trimethylolpropane modified product of lylene diisocyanate) (manufactured by Sumidur Urethane ■). ) can be used, such as a reaction product obtained by adding a hydroxyl group-containing (meth)acrylic acid ester to a polyisocyanate compound known as, for example, polyisocyanate compounds. Typical examples of hydroxyl group-containing acrylic monomers mentioned here are (meth)acrylic acid esters, and droxyethyl (meth)acrylate,
Hydroxypropyl (meth)acrylate is preferred.

Further, other hydroxyl group-containing acrylic monomers used in the branch chains of the graft copolymer polymer (A) mentioned above, particularly compounds represented by the general formula (x), can also be used.

In addition to the monomers having two or more ethylenically unsaturated bonds as described above, monomers having only one ethylenically unsaturated bond such as those listed below can also be used. Examples of such monomers having one ethylenically unsaturated bond include carboxyl group-containing unsaturated monomers such as acrylic acid and methacrylic acid; glycidyl group-containing unsaturated monomers such as glycidyl acrylate and glycidyl methacrylate; 02-C8 hydroxyalkyl esters of acrylic acid or methacrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate: polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate , monoesters of acrylic acid or methacrylic acid and polyethylene glycol or polypropylene glycol such as polypropylene glycol monomethacrylate; methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, acrylic acid Octyl, lauryl acrylate, cyclohexyl acrylate,
C1-CI2 alkyl or cycloalkyl of acrylic acid or methacrylate such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, etc. Estelle: Other Thousands
Examples include styrene, vinyltoluene, methylstyrene, vinyl acetate, vinyl chloride, vinyl isobutyl ether, acrylonitrile, acrylamide, methacrylamide, acrylic or methacrylic acid adducts of alkyl glycidyl ethers, vinylpyrrolidone, dicyclopentenyloxyethyl (meth) ) acrylate, ε-caprolactone-modified hydroxyalkyl (meth)acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate;

In any case, by using the above-mentioned monomer having an ethylenically unsaturated bond, sufficient curability with high sensitivity to active energy rays is imparted to the resin composition for forming the cured resin film of the present invention. be done.

The polymerization initiator (E) that generates a Lewis acid upon irradiation with active energy rays is contained in the resin composition of the present invention.
It is a component for curing the above-mentioned half-esterified epoxy resin (C) by the action of the Lewis acid so that the resin composition of the present invention exhibits sufficient curability with high sensitivity to active energy rays, and is preferably For example, the special public service
An aromatic onium salt compound exhibiting photosensitivity containing an element belonging to group VTa as shown in Japanese Patent No. 278, or a photosensor containing an element belonging to group Va as shown in Japanese Patent Publication No. 14279/1986 It is possible to use an aromatic onium salt compound having a photosensitive property, or an aromatic halonium salt having a photosensitivity as disclosed in Japanese Patent Publication No. 14277/1983. Both of these aromatic onium salt compounds or aromatic halonium salts have the property of curing the half-esterified epoxy resin component (C) by releasing a Lewis acid when irradiated with active energy rays. .

The photosensitive aromatic onium salt compound having an element belonging to Group Via or Group Va mentioned above typically has the following formula: [(F6)a(n')b(i(a )cxld” [M
Q, do(e-f)・-(II) (In the above formula, R6 is m organic aromatic groups, R7 is m organic aliphatic groups selected from alkyl groups, cycloalkyl groups, and substituted alkyl groups. , R8 is a polyvalent organic group constituting a heterocyclic or condensed ring structure selected from aliphatic groups and aromatic groups, X is VTa group selected from sulfur, selenium and tellurium, or nitrogen, phosphorus, arsenic, antimony and bismuth an element belonging to Group Va selected from, M represents a metal or metalloid, and Q represents a halogen group,
a is an integer of 0 to 3 if X l) < an element belonging to group Via, an integer of 0 to 4 if X is an element belonging to group Va, b is an integer of 0 to 2, C is X is Via
An integer of 0 or 1 if X is an element belonging to Group Va, an integer of 0 to 2 if X is an element belonging to Group Va, f
is the valence of M and is an integer from 2 to 7, e is an integer greater than f and less than or equal to 8, and the sum of a, b, and C is 3 if X is an element belonging to group VTa, and When is an element belonging to Group Va, compounds represented by 4 and d=ef) can be mentioned.

In addition, as the photosensitive aromatic halonium salt, the following general m;
'-1+, -(III) (in the above formula, R9 is m aromatic organic groups, R10 is a divalent aromatic organic group, X is a halogen group, M is a metal or metalloid, and Q is a halogen group) where g is an integer of 0 or 2 and h is 0 or 1
is an integer in which the sum of g and h is equal to 2 or the valence of X, i is equal to -1, and l is equal to the valence of M 2
-7, and k is an integer greater than 1 and up to 8).

Specific examples of the photosensitive aromatic onium salt compounds containing elements belonging to Group Via or Group Va include, for example, photosensitive aromatic onium salts of elements belonging to Group Vra, such as; Examples include photosensitive aromatic onium salts of elements belonging to Group Va.

Further, as specific examples of photosensitive aromatic halonium salts, for example, the polymerization initiator (D) that releases a Lewis acid as described above.
In addition, we use curing agents such as polyamines, polyamides, acid anhydrides, boron trifluoride-amine complexes, dicyanciamoto, imidazoles, and conoplex of imidazole and metal salts, which are widely known as curing agents for epoxy resins. It may be used as necessary.

The active energy ray-curable resin composition of the present invention is one that is cured by active energy rays, or one that is photopolymerizable as a graft copolymer polymer (A) and/or a linear polymer (B). and when using an active energy ray with a wavelength of 250r+m to 450nffl as the active energy ray, a free radical-generating radical polymerization initiator that can be activated by the action of the active energy ray is added to the resin composition. It is preferable to leave it there.

Specific examples of such radical polymerization initiators include benzyl ether; benzoin alkyl ethers such as benzoin isobutyl ether, benzoin isopropyl ether, benzoin-lobyl ether, benzoin ethyl needle, and benzoin methyl ether; benzophenone; 4.4 '-Bis(N,N-diethylamino)
Benzophenones such as benzophenone and hensifhenone methyl needle; 2-ethylanthraquinone, 2-
Anthraquinones such as tert-butylanthraquinone; xanthones such as 2,4-dimethylthioxanthone and 2,4-diisopropylthioxanthone; 2,2-
Dime, toxic 2-phenylacetophenone, α, α-
Dichloro-4-phenoxyacetophenone, p-te
rt-butyltrichloroacetophenone, p-jer
Acetophenones such as L-butyldichloroacetophenone, 2.2-jetoxyacetophenone, and p-dimethylaminoacetophenone; or hydroxycyclohexylphenyl ketone (manufactured by Irgacure 184 Ciba-Geigy); 1-(4-isopropylphenyl)- 2-
Hydroxy-2-methylpropan-1-one (Darocur 1116 manufactured by MERCK); 2-hydroxy-2-methyl-1-phenyl-propan-1-ono (Darocur 1173 manufactured by Merck ■), etc. are preferably used. It is mentioned as something that can be done. In addition to these radical polymerization initiators, an amino compound may be added as a photopolymerization accelerator.

Examples of amino compounds used as photopolymerization accelerators include ethanolamine, ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, p-
Examples include dimethylaminobenzoic acid n-amyl ester and P-dimethylaminobenzoic acid isoamyl ester.

Next, the above-mentioned graft copolymerized polymer (A), linear polymer (B), half-esterified epoxy resin (C), ethylenically unsaturated The composition ratio of the bond-containing monomer (D) and the polymerization initiator (E) is appropriately determined depending on the purpose.

Specifically, the weight ratio of the graft copolymerized polymer (A) and the linear polymer (B) is (A, ):(B) = 80:2
A range of 0 to 50:50 is desirable. This range is important for the active energy ray-curable resin composition of the present invention to obtain good adhesion based on the graft copolymer polymer and good buttering properties based on the linear polymer.

Half Nisdel epoxy resin (C) and ethylenically unsaturated bond relative to the total amount (Δ) + (B) of graft/copolymer polymer (A) and linear polymer (B)
:1 body (D) (D combination rifta (C) +
(D) 0)7rLm ratio is ((Δ) + (B))
: ((C):(D)) = +00:50~100
:200 is desirable, and the half-esterified epoxy resin (C) and a simple compound having an ethylenically unsaturated bond (D
) is (G): (DJ = 25 cores 5
A range of 75:25 is desirable.

The polymerization initiator (E) is the total amount of the resin (A) + (1(
) ÷ (C+ + (D) for ((8) ÷ ([1)
+ (C) + (D) ): (F,) =+oo:
It is preferable to use the range of t to Ion: 10.

1- When the optical market promotion agent (G) and/or the radical stimulation initiator (F) is used in addition to the polymerization initiator (E), the above (A), (B), The weight ratio of the above (G) or (F) to the total amount of (C) and (D) or [
(A)÷(B)+(C)+(D)]: (F) or (G
) or [(F)+(G)] is 100:1 to 100:10
It is desirable to use it within the range of .

Furthermore, the active energy ray-curable resin composition of the present invention may optionally contain a condensation crosslinking catalyst, a thermal polymerization inhibitor, a coloring agent such as a dye or a pigment, a filler, and a heat stabilizer such as hydroquinone or paramethoxyphenol. Agents, adhesion promoters, plasticizers, extender pigments such as silica and talc, leveling agents that provide coating suitability, and the like may be added.

For example, examples of the condensation crosslinking catalyst include sulfonic acids represented by para-toluenesulfonic acid, carboxylic acids such as formic acid, and the like. Examples of thermal polymerization inhibitors include hydroquinone and its derivatives, paramethoxyphenol, and phenothiazine.7As colorants, oil-soluble dyes and pigments may be added to the extent that they do not substantially prevent the transmission of active energy rays. The filler is 1!1! , increase in film hardness,
Extender pigments, plastic particles, etc., which are commonly used in paints, are used to improve coloring, adhesion, and mechanical strength. Examples of adhesion promoters include silane coupling agents as inorganic surface modifiers, low molecular weight surfactants, and the like.

When using the active energy ray-curable resin composition of the present invention in a molten state or when applying it onto a plastic film, etc., which is a film base material when forming a dry film, the solvent used is alcohol. , glycol ethers, glycol esters, and other hydrophilic solvents. Of course, these hydrophilic solvents are mainly used, and if necessary, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and isobutyl acetate, aromatic hydrocarbons such as toluene and xylene, and their halogen substituted substances .

An appropriate mixture of chlorine-containing aliphatic solvents such as methylene chloride and 1,1.1-trichloroethane may also be used. Incidentally, these solvents can also be used as a developer for the resin composition of the present invention.

Next, the active energy ray-curable resin composition of the present invention obtained by the method explained above can be coated on a support according to a usual method, for example: (1) Coating the cured film on the substrate. When forming, a liquid active energy ray curable resin composition is applied onto the support to form a liquid film. This is followed by evaporation to dryness. The dried coating film is then cured by irradiation with active energy.

(2) When forming a protective cured layer in the shape of a desired pattern on a support, a liquid active energy ray-curable resin composition is applied onto the support to form a liquid coating film. This is followed by evaporation to dryness. The dried layer is then scanned with a laser beam in the desired pattern, and the unexposed areas are covered in steps 1.1. A hardened protective layer in a desired pattern is formed on the support by removing it with a suitable solvent such as trichloroethane.

(3) When forming a protective cured layer in the shape of a desired pattern on a support, a liquid active energy ray-curable resin composition is applied to the liquid film 1.
Apply to form 1Q followed by evaporation drying. A photomask having a pattern with a desired shape through which active energy rays do not pass is placed on the dry film layer, and the photomask is exposed to active energy rays. Then, the unexposed areas are removed with a suitable solvent such as 1.1.1-trichloroethane to form a protective cured layer in the shape of a desired pattern on the support.

(4) When forming a photosensitive dry film and laminating the M dry film on the support t, apply a liquid active energy ray-curable resin to the polyethylene terephthalate film 7 to form a liquid film, and then evaporate it. The polyethylene terephthalate film 7 is dried to obtain a photosensitive dry film. The dry film is laminated to a support by conventional lamination methods to obtain a laminate. The photosensitive dry film laminated on the support is then cured by irradiating it with active energy rays in the same manner as method (1) above.

When it is desired to form a cured photosensitive film into a desired pattern, the dry film laminated on Support-F is treated in the same manner as in method (2) or (3) described above.

When the active energy ray-curable resin composition contains a compound represented by formula (X), the cured film obtained by the methods (1) to (4) in L is further heated at 80°C to 20°C.
It is desirable to carry out condensation hardening by heat treatment at a temperature of 0''C.

Examples of active energy rays used for curing the active energy ray-curable resin composition of the present invention or pattern exposure of the composition include ultraviolet rays and electron beams that have already been widely put into practical use. As an ultraviolet light source, a high-pressure mercury lamp that contains a lot of light with a wavelength of 250 nm to 450 nm,
Examples include ultra-high pressure mercury lamps, metal haley lamps, etc.
The intensity of light in the vicinity of 365 nm at a practically acceptable distance between objects to be irradiated with Ranbu is 1 mif/cm2 to 1
00 mW/cn2 power is preferable. 'The deuteron beam irradiation device is not particularly limited, but 0.5~2GM R
A device having a line performance in the ad range is practically suitable.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples. It should be noted that the present invention is limited to the following examples only.

Using 11M 2-, 80 parts by weight of droxyethyl methacrylate and 20 parts by weight of butyl acrylate, using thiogly9-alic acid as a transfer agent and azobisisobutylnitrile as an initiator, Radical chain transfer polymerization was performed to obtain an oligomer with a carboxy group at the end.

By reacting this oligomer with glycidyl methacrylate, a macromonomer having a methacryloyl group at one end of the molecular chain was obtained.

The number average amount of this macromonomer determined by GPC method was about 3,000. This macromonomer - 30ffiff
1 part by weight and 70 parts by weight of methyl methacrylate were solution polymerized in a methyl cellosolve solvent to obtain a graft copolymer having a weight average molecular weight of about 50,000 and a number average molecular weight of about 12,000.

1113) Methyl methacrylate, isobornyl methacrylate and 2-hydroxyethyl acrylate 70:20:10
A linear acrylic copolymer obtained by polymerizing at a ratio of (molar ratio). The number average molecular weight is approximately 70,000, and the weight average molecular weight is approximately 250,000.

Half ester epoxy C) Epikote 828 (Yuka Shell Epoxy ■ bisphenol A type epoxy resin, epoxy ff1t
a3-193) 50% acrylic ester ethylene
Saturated @, 'D) 1), 2-hydroxyethyl acrylate adduct to diphenylmethane diisocyanate 2), trimethylolpropane triacrylate lil
Bis-[4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluoroantimote [BDS (SbFs) 2] Irgakiure 6 having the following structure
51 (manufactured by Ciba Geigy Aji Co., Ltd.) Next, the composition of the present invention was obtained by mixing the above-mentioned materials at the lit ratio shown below using a conventional mixing technique.

Materials (A) (B) (C) (D)-] (D)-2 (E) (F) Methylene blue methyl cellosolve 250 Methyl ethyl ketone 100 The liquid composition of the present invention obtained as above was purified by Apply it to the treated glass plate with a thickness of about 80μ, 1
It was dried with hot air at 00°C for 15 minutes to obtain a dry film of about 40 bars on a glass plate. Next, this glass plate was exposed for 10 seconds under a normal high-pressure mercury lamp with an irradiation energy of 100 mW/cm2. Thereafter, heat treatment was performed at 150°C for 30 minutes.

The glass plate coated with the composition of the present invention obtained as described above was soaked in a 1% caustic soda aqueous solution for 10 hours.
Ux processed. When the thus obtained laminate was test-folded, the exposed (cured) film adhered firmly to the glass plate, and no whitening or blistering was observed over a long period of time.

Example 2 The liquid composition of Example 1 was applied onto a glass plate whose surface had been cleaned, and then air-dried to obtain a dry film having a thickness of 50 g after drying. In addition to this, the minimum or 2
A glass mask having a group of equally spaced lines with a spacing of 1J of 0 μm was exposed using an ultraviolet irradiation device (Mask Aligner MA-10, manufactured by Mikasa) that generates highly parallel light rays. Further, the same operation was repeated by changing the exposure conditions.After 30 minutes had passed after exposure, 1, 1.
Spray development was performed using 1-1 dichloroethane.

In this method, three exposure energies (80+nj/cr
tf, 100mj/crn”, 120m, i/c
Three discontinuous groups of samples (sample groups rm) were obtained with rn').

Three different samples were obtained with different exposure times (30 seconds, 60 seconds, 90 seconds) for each of Samples ① to ②.

As a comparative example, an active energy linear resin composition was prepared in the same manner as in Example 1 except that 100 parts by weight of the graft copolymer polymer (8) was used and the linear polymer (B) was not used. A comparative resin composition was obtained.

Then, using this comparative resin composition, the above method was repeated to prepare comparative sample groups ① to ②.

The samples thus obtained were evaluated for pattern resolution, residue in undeveloped areas, and pattern swelling using conventional evaluation methods.

The evaluation results are shown in the table below.

Table-1 ○: Pattern is formed with good resolution and undeveloped areas remain? M”a pattern bulge was not observed.

x: Residues and/or pattern blisters were observed in undeveloped areas.

The results shown in Table 1 show that the active energy ray-curable composition of the present invention is always stable regardless of exposure conditions or development conditions.

Example 3 The components shown below were used as components constituting the composition of the present invention.

Grafting to Hokuden 1H--A A macromonomer having a methacryloyl group at one end of the molecule 'jn was prepared using 50 parts by weight of 2-hydroxyethyl methacrylate and 5 parts of butoxymethylacrylamide in the same manner as in Example 1. I got it. The number average molecular weight of this macromonomer by GPC method was about 2,000.

20 parts by weight of this macromonomer and 80 parts by weight of methyl methacrylate were solution polymerized in a solvent of methyl cellosolve/methyl ethyl ketone (MEK) = 60/40 (weight ratio) to obtain a number average molecular weight of about 5,000 and a weight average molecular weight of I A thermosetting graft copolymer polymer having a weight of about 30,000 was obtained.

Methyl methacrylate, tricyclodecane methacrylate, and butoxymethyl acrylamide, 60:3
A linear acrylic copolymer obtained by polymerization at a molar ratio of 0:IO. The number average molecular weight is approximately 60,000, and the weight average molecular weight is approximately 260,000.

Half-esterified epoxy C) Epicoat 152 (phenol-borac type epoxy resin manufactured by Yuka Shell Epoxy ■, epoxy resin)
172-179) 50% acrylic ester ethylene Dl), 100% acrylic ester of phenol novolac type epoxy resin (degree of condensation 3-4) 2), neopentyl glycol diacrylate Photosensitive direction group onium salt (1) (UVI 10
14, General Electric Co., Ltd.) Ellen A.D.
UL KeJ Darocure+173 (manufactured by Merck & Co.) Next, the above materials were mixed in the weight ratio shown below to obtain a composition solution of the present invention.

Material Part by weight (^) 80 (B) 20 (C) +00 (D)-160 (D)-240 (E) a, 5 (F)
2.5 Methylene Blue 1 Methyl Cellosolve 200 Methyl Ethyl Ketone 100 The liquid composition of the present invention obtained as above was applied to a printed wiring board in which a conductor circuit of copper foil with a thickness of 60 mm was formed on a glass cloth epoxy base. On top, the thickness after drying is 50
It was coated on the entire surface using a roll coater so that it became μ. Drying at that time was performed in a hot air oven at 100°C for 3 minutes. Next, after the coating film has cooled, a solder mask pattern is overlaid on top of the coating film, and the UV intensity at around 365r+m is 7 mW/cm2, and collimation (ultra high pressure with highly parallel declination angle of 3°) is applied. Exposure was carried out using a mercury lamp for 35 seconds. After exposure, spray development was carried out using !, 1.1 trichloroethane at 20° C. for 50 seconds. Development proceeded stably and a clear pattern was obtained.

After development, dry, irradiate for 5 minutes with the same ultra-high pressure mercury lamp, and
V-bost cure was applied, and then heat treatment was performed at 150° C. for 15 minutes to perform heat curing.

As a result of testing the protective film obtained as described above, the protective film was found to have excellent acid resistance, alkali resistance, and chemical resistance.

〔Effect of the invention〕

As explained above, since the active energy ray-curable resin composition of the present invention contains the graft copolymer polymer (^) as a constituent component, it can be applied to various supports without adding additives or the like. to ensure sufficient adhesion and linear polymer (
Since it contains B> as a constituent component, it has excellent development characteristics during pattern formation. At the same time, it has chemical resistance, durability, etc. that make it suitable for use in a variety of applications.

Furthermore, since the composition of the present invention uses a graft copolymer polymer and a linear polymer in combination as its constituent polymer substances, only the graft copolymer polymer is used as the polymer substance. Compared to the case where active energy rays are used, less active energy ray irradiation is required to create a coating film that is resistant to solvents for developing solutions, resulting in high sensitivity, improved resolution, and pattern formation regardless of the type or condition of the substrate. This improves the properties of the buttering process and expands the range of working conditions. Because of this, its uses can be greatly expanded compared to conventional ones.

Claims (1)

[Scope of Claims] 1) (A) The following general formula (x) and ( y) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(x) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(y) [However, R^1 is hydrogen, or the number of carbon atoms is 1~ 3
represents an alkyl group or a hydroxyalkyl group, R
^2 represents hydrogen, or an alkyl group or acyl group having 1 to 4 carbon atoms which may have a hydroxy group, and R^3 represents an alkyl group having 2 to 6 carbon atoms, or a halogen-substituted alkyl group. Alkyl groups, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, 2≦m+n≦6, n≠0, m≠0) Alkyl ether groups, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, 2≦m+n≦4, including cases where n=0 or m=0). ] Graft copolymerization in which a branch chain having a structural unit derived from at least one of the monomers represented by the following is added, and the number average molecular weight is 5,000 or more and the weight average molecular weight is 50,000 or less. Polymer and (B) Methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, acrylonitrile, isobornyl methacrylate, isobornyl acrylate, tricyclodecane acrylate, tricyclodecane It has a structural unit derived from one or more monomers selected from the group consisting of methacrylate, tricyclodecaneoxyethyl methacrylate, styrene, dimethylaminoethyl methacrylate, and cyclohexyl methacrylate, and has the general formula (x) or (y) ) has a structural level derived from at least one type of monomer among the monomers represented by (), and has a number average molecular weight of 50,000 or more, a weight average molecular weight of 350,000 or less, and a glass transition temperature of 60°C or more. (C) A part of the epoxy groups present in an epoxy resin containing at least one compound having two or more epoxy groups in the molecule is esterified with an unsaturated carboxylic acid. a resin, (D) a monomer having an ethylenically unsaturated bond, and (E)
An active energy ray-curable resin composition comprising a polymerization initiator that generates a Lewis acid upon irradiation with active energy rays. 2) The weight ratio of the graft copolymer polymer (A) and the linear polymer (B) is (A):(B)=80:20 to 50.
The active energy ray-curable resin composition according to claim 1, wherein the active energy ray-curable resin composition is 3) The total weight (A) + (B) of the graft copolymer polymer (A) and the linear polymer (B), the resin (C), and the monomer (D) having an ethylenically unsaturated bond. ), the weight ratio of (C) + (D) is {(A) + (
B)}: {(C)+(D)}=100:50-100:
The active energy ray-curable resin composition according to claim 1 or 2, which has a molecular weight of 200%. 4) The weight ratio of the resin (C) and the monomer (D) having an ethylenically unsaturated bond is (C):(D)=25:75
The active energy ray-curable resin composition according to claim 3, wherein the ratio is 75:25. 5) Total weight (A) + (B) of the graft copolymer polymer (A), the linear polymer (B), the resin (C), and the monomer (D) having an ethylenically unsaturated bond. )+(C
)+(D) and the polymerization initiator (E) is {(A)
+(B)+(C)+(D)}:(E)=100:1~1
The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the ratio is 00:10. 6) The polymerization initiator (E) is one or more selected from the group consisting of aromatic halonium salt compounds and photosensitive aromatic onium salt compounds containing elements belonging to Group VIa or Group Va of the Periodic Table. The active energy ray-curable resin composition according to any one of claims 1 to 5. 7) Based on a total of 100 parts by weight of the graft copolymer polymer (A), the linear polymer (B), the resin (C), and the ethylenically unsaturated bond-containing monomer (D), 1
The active energy ray-curable resin composition according to any one of claims 1 to 6, which contains ~10 parts by weight of a radical polymerization initiator that can be activated by the action of active energy rays.