JP2549422B2 - Active energy ray curable resin composition - Google Patents

Description

TECHNICAL FIELD 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 in particular, a copper clad laminate for printed wiring boards, metal, The present invention relates to an active energy ray-curable resin composition that can be laminated in a desired pattern shape on glass, ceramics, plastics and the like.

[Conventional technology]

In recent years, active energy ray-curable resin compositions have been
It is widely used as an ink, a sealing material, a resist material, a material for a protective film, a material for pattern formation, and the like. For example, as an active energy ray-curable resin composition used as a protective coating film for a printed wiring board or a resist material for forming a wiring pattern thereof, specifically, a dry material containing a polymer substance having a film forming ability is used. Film resists (trade name: RISTON: manufactured by Dupont Japan Limited), photographic thick film liquid resists (trade name: Provimer: manufactured by Ciba Geigy Co., Ltd.) and the like are known.

The composition as described above includes a polymer substance (hereinafter, simply referred to as a polymer substance) for imparting properties such as shaping into a film or shaping to a dry film to the composition, and an active energy. A main component is a line-curable substance. The adhesion of the composition to a support, the developability for pattern formation, the durability as a coating film, the applicability, the drying property, and the like are greatly affected by the type, molecular structure, and the like of the polymer substance. Therefore, when such a composition is used, selection of the type of the polymeric substance and molecular design have been carried out for the purpose of attaining the above-mentioned properties to desired levels.

[Problems to be Solved by the Invention]

However, even if the kind of the polymer substance is selected and the molecular design is performed as described above, the conventional active energy ray-curable resin composition still has sufficient properties in adhesion to various supports. Was not reached.

In order to solve this problem, it has been proposed to add an additive aid or a coupling agent capable of forming a complex with a metal such as a heterocyclic compound to such a resin (Japanese Patent Publication No. 5934, etc. Sho 58-24035). However, this method has a problem that, after a long period of time, the above-mentioned additive aids cause oxidation and corrosion of the composition.

On the other hand, a polymer substance having a graft copolymer having a polar group in a branched chain is disclosed in Japanese Patent Application Laid-Open It is disclosed in Japanese Patent Publication No. 61-283645. The active energy ray-curable resin composition containing the polymer substance disclosed therein was able to improve the adhesion of the coating film and further improve the durability without relying on an addition aid or the like. . However, in these techniques, there still remains a problem that molecular design of the polymer substance (graft copolymer) is difficult. That is, generally, it is not possible to synthesize the graft copolymer so that the weight average molecular weight of the entire graft copolymer becomes a desired value of molecular weight over a wide range (about 50,000 to 350,000) while keeping the molecular weight and content of the branch chains constant. With technical difficulties.

That is, in order to improve the development characteristics during pattern formation, that is, the dissolution rate of the unpolymerized portion, the swellability of the polymerized portion, and the resulting sensitivity, pattern sharpness, and resolution, the polymer The average molecular weight should not be too low. To obtain an average molecular weight that meets the above-mentioned objectives by grafting a large number of branch chains of a graft copolymer with a relatively large molecular weight to a chain with sufficient length for effective adhesion. Is difficult in terms of steric hindrance in the current synthesis technology.

In other words, if the average molecular weight of the polymeric substance is too low, the development characteristics of the material when patterning with it, i.e. the dissolution rate of the unpolymerized part, the swelling property of the polymerized part, and their resulting sensitivity, The sharpness and resolution of the pattern are subject to certain restrictions.

The present invention has been made in view of the above problems, and an object thereof is a steel-clad laminate for printed wiring boards, metal, glass, ultraviolet rays that can be laminated in a desired pattern shape on ceramics plastic, electronic. An object of the present invention is to provide an excellent resin composition that is cured by (irradiation of) active energy rays such as rays.

Another object of the present invention is to add an auxiliary agent or the like,
An object of the present invention is to provide an adhesive active energy ray-curable resin composition that is excellent for substrates.

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

Another object of the present invention is to provide an excellent active energy ray-curable resin composition that can be easily controlled (the characteristics thereof) so as to obtain desired characteristics according to various uses. [Means for Solving the Problems] The above object of the present invention is mainly based on (A) a structural unit derived from one or more monomers (hereinafter referred to as monomers) selected from the group consisting of alkyl methacrylate, acrylonitrile and styrene. The following general formulas (x) and (y) [Wherein R ¹ represents hydrogen, or an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ² represents hydrogen or an alkyl group optionally having a hydroxy group having 1 to 4 carbon atoms. Represents a group or an acyl group, R ³ is an alkyl group having 2 to 6 carbon atoms, or a halogen-substituted alkyl group, CH _{2 n} OCH _{2 m} (where 2 ≦ m + n ≦ 6, n ≠ 0, m ≠ 0 ) An alkyl ether group represented by (However, 2 ≦ m + n ≦ 4, including the case where n = 0 or m = 0) is a phenylalkyl group. ] A branch chain having a structural unit derived from at least one monomer (hereinafter referred to as a monomer) among the monomers represented by the following formula is added, and the number average molecular weight is 5,000 or more and the weight average molecular weight is 50,000 or less. And (B) methylmethacrylate, ethylmethacrylate, isobutylmethacrylate, t-butylmethacrylate, benzylmethacrylate, acrylonitrile, isobornylmethacrylate, isobornylacrylate, tricyclodecane. At least one monomer selected from the monomer group (z) consisting of acrylate, tricyclodecane methacrylate, tricyclodecane oxyethyl methacrylate, styrene, dimethylaminoethyl methacrylate, cyclohexyl methacrylate; A structural unit derived from a) as a monomer,
And having a structural unit derived from at least one monomer (hereinafter referred to as a monomer) among the monomers represented by the general formula (x) or (y), and having a number average molecular weight of 50,000 or more and a weight average molecular weight. Present in an epoxy resin containing at least one of a linear polymer having a glass transition temperature of 350,000 or less and a glass transition temperature of 60 ° C. or more and (C) a compound having two or more epoxy groups in the molecule. Achieved by an active energy ray-curable resin composition comprising a resin obtained by esterifying a part of the groups with an unsaturated carboxylic acid, and (D) a polymerization initiator that generates a Lewis acid upon irradiation with active energy rays. To be done.

Hereinafter, each component (A) constituting the composition of the present invention
(D) will be described in detail.

As the monomer used for the backbone chain of the graft copolymer (A), alkyl methacrylate, as described above,
At least one selected from the group consisting of acrylonitrile and styrene is used as a main component. As the monomer used for the branched chain, in addition to the monomer represented by the general formula (x) or (y), it is necessary to use the following polar monomer in combination, if necessary.

(I) Amino group- or alkylamino group-containing acrylic monomer (II) Carboxy group-containing acrylic or vinyl monomer (III) N-vinylpyrrolidone or its derivative (IV) Vinyl pyridine or its derivative It can be used as a component of copolymerization within the range of 25 mol% or less.

Examples of the method for polymerizing the graft copolymer (A) include “Polymer alloy basics and applications” (edited by The Society of Polymer Science,
Various conventionally known methods such as those described on pages 10 to 35 of Tokyo Kagaku Dojin Co., Ltd., 1981) can be used. These methods include chain transfer method,
There are a method using radiation, an oxidative polymerization method, an ion graft polymerization method, a macromonomer method and the like. Using these methods, the above-exemplified monomers and monomers are used to perform polymerization by appropriately selecting the polymerization conditions so that a graft copolymer having a number average molecular weight of 5,000 or more and a weight average molecular weight of 50,000 or less can be obtained. By doing so, the graft copolymer (A) that constitutes the composition of the present invention can be obtained.

When any one of the above methods is used, the length of the branch chains of the copolymer polymer (A) can be made uniform, so that the above method is particularly preferable from the viewpoint of material selection (design).

The linear polymer (B) contains the above-mentioned monomer as a main component and uses at least one of the monomers represented by the general formula (x) or (y).
Obtained by polymerizing using a conventionally known method while appropriately selecting the polymerization conditions so that the polymer has a number average molecular weight of 50,000 or more and a weight average molecular weight of 350,000 or less and a glass transition temperature of 60 ° C. or more. be able to. The monomer, that is, at least one monomer selected from the group of monomers represented by the general formula (x) or (y) is 5
It is preferably added in the range of mol% to 30 mol%. It is because if the linear polymer contains more than 30 mol% of these monomers, the concentration of polar groups in the cured coating increases,
It is not preferable because the effect of improving the adhesiveness does not increase any more and the water resistance decreases. On the other hand, if it is less than 5 mol%, not only the adhesion is improved but also the effect as a binder of the coating film becomes insufficient.

Among the above-mentioned monomers, methyl methacrylate, isobornyl methacrylate, isobornyl acrylate, tricyclodecane methacrylate and tricyclodecane acrylate are given for the purpose of imparting a high glass transition temperature to the formed cured film and enhancing water resistance. Etc. give particularly favorable results.

A part of the epoxy groups present in the epoxy resin composed of one or more compounds containing two or more epoxy groups in one molecule, which is contained in the active energy ray-curable resin composition of the present invention, is partially unsaturated carboxylic acid. The resin (C) (hereinafter abbreviated as a half-esterified epoxy resin) obtained by esterification by means of the resin composition of the present invention in the presence of a polymerization initiator (D) described later has high sensitivity to active energy rays. To exhibit sufficient curability, and in addition to this, the resin composition of the present invention is applied in liquid form on various supports made of glass, plastics, ceramics, etc. and then cured to form a cured film. When formed 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, water resistance, and chemical resistance. Is a component for imparting dimensional stability.

In the half-esterified epoxy resin (C) obtained by an ordinary method, for example, an epoxy resin containing one or more compounds having two or more epoxy groups in the molecule is added with a predetermined amount of unsaturated carboxylic acid. , In the presence of an addition catalyst and a polymerization inhibitor, in the presence or absence of a solvent, by reacting at a temperature condition of 80 ~ 120 ℃, a part of the epoxy group present in the epoxy resin is esterified with a carboxylic acid It can be obtained by a commonly used method such as (half-esterification).

Examples of the epoxy resin that can be used for forming the half-esterified epoxy resin (C) and include one or more kinds of compounds containing two or more epoxy groups in one molecule include bisphenol A type, novolak type, and alicyclic type. , Bisphenol S, bisphenol F, tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether,
Glycerin triglycidyl ether, pentaerythritol triglycidyl ether, isocyanuric acid triglycidyl ether and the following general formula (I) (However, R ⁴ is an alkyl or oxyalkyl group, R ⁵
Is Or a polyfunctional epoxy resin such as an epoxy urethane resin represented by (representing an alkyl group) and a mixture of one or more of these.

The following may be mentioned as specific examples of these polyfunctional epoxy resins.

That is, as the bisphenol A type epoxy resin, for example, Epicoat 828, 834, 871, 1001, 1004 (trade name, manufactured by Shell Chemical Co.), DER 331-J, 337-J, 661-J, 6
64-J, 667-J (Dow Chemical Company) and Epicron 800
(Trade name, manufactured by Dainippon Ink and Chemicals, Inc.), etc .; examples of novolac type epoxy resins include Epicoat 15
2, 154, 172, (trade name, manufactured by Shell Chemical Co., Ltd.), Araldite EPN 1138 (trade name, manufactured by Ciba Geigy), DER 43
1,438 and 439 (trade name, manufactured by Dow Chemical Co., Ltd.); Examples of alicyclic epoxy resin include Araldite CY-17
5, -176, -179, -182, -184, -192 (trade name, manufactured by Ciba Geigy), Chisso Knox 090, 091, 092, 301,
313 (trade name, manufactured by Chisso Corporation), Syracure (CYR
ACURE) 6100, 6110, 6200 and ERL 4090, 4617, 2256, 5
411 (trade name, manufactured by Union Carbide Co., Ltd.); As polyhydric glycidyl ethers of aliphatic polyhydric alcohol,
For example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane Triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 2,2-dibromoneopentylglycol diglycidyl ether, etc .; Polyhydric glycidyl ethers derived from aromatic polyhydric alcohols include alkylene oxides of bisphenol A Diglycidyl ether of 16 mol adduct, diglycidyl ether of 2 to 16 mol adduct of alkylene oxide of bisphenol F , A diglycidyl ether of a 2 to 16 mol addition product of alkylene oxide of bisphenol S, and the like.

As the unsaturated carboxylic acid that can be used for the half-esterification of the epoxy group of the above-mentioned epoxy resin, various ones can be used, but the resin composition of the present invention can be cured by a better activation energy. In order to impart the property, a monobasic unsaturated carboxylic acid having an acrylic or methacrylic vinyl group at least at one end of the molecule and a carboxyl group at the other end is used as a suitable one. be able to.

Representative examples of such unsaturated carboxylic acid include acrylic acid and methacrylic acid, but a monoester compound obtained by reacting a dicarboxylic acid with a (meth) acrylic acid ester having one hydroxyl group. Can also be used.

Examples of the above dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, isosebacic acid, tetrahydrophthalic acid and these. And the like.

Further, as the methacrylic acid ester having one hydroxyl group, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3 -Hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate and the like can be mentioned.

Examples of addition reaction catalysts that can be used in the half-esterification reaction of epoxy resins include metal halides such as zinc chloride and lithium chloride, for example, sulfide compounds such as dimethyl sulfide and methylphenyl sulfide, such as dimethyl sulfoxide and methyl ethyl. Compounds of the sulfoxide class, such as sulfoxide, eg
Compounds of tertiary amines such as N, N-dimethylaniline, pyridine, triethylamine, benzyldimethylamine and their hydrochlorides or hydrobromides such as tetramethylammonium chloride, trimethyldodecylbenzylammonium chloride and triethylbenzylammonium chloride Examples thereof include quaternary ammonium salts, compounds of sulfonic acids such as paratoluene sulfonic acid, and compounds of mercaptans such as ethyl mercaptan and propyl mercaptan.

Furthermore, examples of the polymerization inhibitor that can be used for half-esterification include hydroquinone, alkyl- or aryl-substituted hydroquinone, tert-butylcatechol, pyrogallol, naphthylamine, β-naphthol,
Examples thereof include cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, N-nitrosodiphenylamine and nitrobenzene.

Further, as the solvent that can be used when the half-esterification is carried out in the presence of a solvent, toluene, xylene, methyl isobutyl ketone, methyl ethyl ketone,
Mention may be made of ethyl acetate, butyl acetate and isobutyl acetate.

The amount of the epoxy resin and the carboxylic acid used in the half-esterification, the ratio of the epoxy group of the epoxy resin and the carboxyl group of the carboxylic acid is preferably 1: 0.3 to 1: 0.7, more preferably 1: 0.45 to 1 It is appropriately selected to be: 0.55.

That is, when the esterification rate of the epoxy group by the unsaturated carboxylic acid in the half-esterified epoxy resin is higher than the above range, the resin composition of the present invention has good chemical resistance and dimensional stability derived from the epoxy resin. When it is not lower than the above range, the resin composition of the present invention has a high resolution and sufficient curability due to the action of active energy rays, which is based on the methacrylic acid ester group. I can't.

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) and the curability due to the action of the active energy ray based on the acrylate ester group, and the heat based on the epoxy group. A cured film having curability, which is obtained by irradiating the resin composition of the present invention with active energy rays to cure the resin composition, and then heating the resin composition at 80 ° C. or higher for about 10 minutes to 3 hours for further thermosetting. In addition, good chemical resistance and dimensional stability derived from the half-ester epoxy resin are effectively imparted.

The polymerization initiator (D) which is contained in the resin composition of the present invention and generates a Lewis acid upon irradiation with active energy rays is a half-esterified epoxy resin (C) cured by the action of the Lewis acid, It is a component for allowing the resin composition of the invention to exhibit sufficient curability with high sensitivity to active energy rays, and is preferably, for example, JP-B-52-142.
Aromatic onium salt compounds containing an element belonging to Group VIa as disclosed in Japanese Patent Publication No. 78,
Aromatic onium salt compound having photosensitivity containing an element belonging to Group Va shown in Japanese Patent No. 52-14279, or aromatic halonium salt having photosensitivity shown in Japanese Patent Publication No. 52-14277. Etc. can be used. Each of these aromatic onium salt compounds or aromatic halonium salts has the property of releasing a Lewis acid upon irradiation with an active energy ray to cure the half-esterified epoxy resin (C).

The photosensitive aromatic onium salt compound having an element belonging to Group VIa or Group Va described above is typically represented by the following general formula II; [(R ³ ) _a (R ⁴ ) _b (R ⁵ ) _c X] _d ⁺ [MQ _e ] ^-(ef) ...
(II) (In the above formula, R ³ is a monovalent organic aromatic group, R ⁴ is an alkyl group, a monovalent organic aliphatic group selected from a cycloalkyl group and a substituted alkyl group, R ⁵ is an aliphatic group and A polyvalent organic group forming a heterocyclic ring or a condensed ring structure selected from an aromatic group, X is a group selected from sulfur, selenium and tellurium.
Group VIa or an element belonging to Group Va selected from nitrogen, phosphorus, arsenic, antimony and bismuth, M is a metal or a metalloid and Q is a halogen group, and a is an element belonging to Group VIa. Is an integer from 0 to 3, X
Is an integer of 0 to 4 when b is an element belonging to Group Va, b
Is an integer of 0 to 2, c is an integer of 0 or 1 when X is an element belonging to Group VIa, 0 is an integer of 2 when X is an element belonging to Group Va, and f is M Is an integer of 2-7, e is an integer greater than f and 8 or less, and the sum of a, b, and c is 3, when X is an element belonging to Group VIa,
4 and d = e− when X is an element belonging to Group Va
and a compound represented by f).

Further, as a light-sensitive aromatic halonium salt, the following general III; [(R ⁶ ) _g (R ⁷ ) _h X] _i ⁺ [MQ _j ] ^-(kl) (III) (wherein R ⁶ is a monovalent aromatic organic group, R ⁷ is a divalent aromatic organic group, X is a halogen group, M is a metal or metalloid and Q is a halogen metal, respectively, g is an integer of 0 or 2 and h Is an integer of 0 or 1, the sum of g and h is equal to the valence of 2 or X, i is equal to k−1, j
Is an integer from 2 to 7 and is equal to the cost of M, and k is an integer greater than 1 up to 8).

Specific examples of the photosensitizing aromatic onium salt compound containing an element belonging to Group VIa or Group Va, for example, A photosensitive onium salt of an element belonging to Group VIa such as, and Examples thereof include photosensitized aromatic onium salts of elements belonging to Group Va.

Further, specific examples of the light-sensitive aromatic halonium salt include, for example, Etc.

In addition to the polymerization initiator (D) that releases the Lewis acid as described above, polyamines, polyamides, acid anhydrides, boron trifluoride-amine complex, imidazoles that are generally widely known as curing agents for epoxy resins are used. If desired, a curing agent such as a complex of imidazole and a metal salt may be used.

The active energy ray-curable resin composition of the present invention, which is cured by active energy rays, has photopolymerizability as the graft copolymerization polymer (A) and / or linear polymer (B). And when using an active energy ray having a wavelength of 250 nm to 450 nm as the active energy ray, it can be activated by the action of the active energy ray,
It is preferable to add a radical polymerization initiator that generates organic free radicals and initiates radical polymerization to the resin composition.

Specific examples of such radical polymerization initiators include benzyl ether; benzoin isobutyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin ethyl ether, benzoin methyl ether, and other benzoin alkyl ethers; benzophenone, 4,4 Benzophenones such as ′ -bis (N, N-diethylamino) benzophenone and benzophenone methyl ether; anthraquinones such as 2-ethylanthraquinone and 2-tert-butylanthraquinone; 2,4-dimethylthioxanthone and 2,4-diisopropylthioxanthone Xanthones; 2,2-dimethoxy-2-phenylacetophenone, α, α-dichloro-4-phenoxyacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloro Acetophenone, 2,
Acetophenones such as 2-diethoxyacetophenone and p-dimethylaminoacetophenone; or hydroxycyclohexyl phenyl ketone (IRGACURE 18
4 Ciba-Geigy Co., Ltd.); 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-
On (manufactured by Darocur 1116 MERCK); 2
-Hydroxy-2-methyl-1-phenyl-propane-
1-one (produced by Darocur 1173 Merck Co., Ltd.) and the like are preferably used. In addition to these radical polymerization initiators, an amino compound may be added as a photopolymerization accelerator.

Examples of the amino compound used for the photopolymerization accelerator include ethanolamine, ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate, p
-Dimethylaminobenzoic acid n-amyl ester, p-dimethylaminobenzoic acid isoamyl ester and the like.

Next, the above-mentioned graft copolymer polymer (A), linear polymer (B), half-esterified epoxy resin (C), polymerization initiator (D) which are components of the active energy ray-curable composition of the present invention. The composition ratio (weight ratio) of () is appropriately determined according to the purpose.

The weight ratio of the graft copolymer (A) to the linear polymer (B) is preferably (A) :( B) = 80: 20 to 50:50. Good adhesion to a substrate based on a molecule and good patterning property based on a linear polymer can be obtained.

The weight ratio of the half-esterified epoxy resin (C) to the total amount (A) + (B) of the polymer substance is
The range of {(A) + (B) :( C)} = 100: 50 to 100: 200 is desirable. The polymerization initiator (D) is {(A) + (B) + with respect to the total amount (A) + (B) + (C) of the resin.
(C)}: (D) = It is desirable to use in the range of 100: 1 to 100: 10.

Further, when the above radical polymerization initiator (E) and / or the amino compound (F) as a photopolymerization accelerator is used, their addition amount {(E) + (F)} [(E) = 0,
(Including the case of (F) = 0) is the total amount of the resin (A)
+ (B) + (C) for {(A) + (B) +
(C)}: {(E) + (F)} = 100: 1 to 100: 10 is preferably used in the range.

Further, the active energy ray-curable resin composition of the present invention, if necessary, a condensation crosslinking catalyst, a thermal polymerization inhibitor, a colorant filler such as a dye or a pigment, a thermal stabilizer such as hydroquinone or paramethoxyphenol. Further, an adhesion promoter, a plasticizer, an extender pigment such as silica or talc, and a leveling agent for imparting coating suitability may be added.

Examples of the condensation crosslinking catalyst include sulfonic acids typified by paratoluenesulfonic acid and carboxylic acids such as formic acid. Examples of the thermal polymerization inhibitor include hydroquinone and its derivatives, paramethoxyphenol, phenothiazine and the like. As the colorant, oil-soluble dyes and pigments can be added in a range that does not substantially prevent the transmission of active energy rays. Filler increases the hardness of the coating, coloring,
In order to increase adhesion and mechanical strength, extenders, plastic fine particles and the like commonly used in paints are used. Examples of the adhesion promoter include a silane coupling agent as an inorganic surface modifier, and a low particle surfactant.

As the solvent used when the active energy ray-curable resin composition of the present invention is used in the form of a solution, or when it is applied onto a plastic film or the like which is a film substrate when forming a dry film, alcohols and glycols are used. Examples include hydrophilic solvents such as ethers and glycol esters. 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 halogen-substituted products thereof , Methylene chloride, 1,
A mixture appropriately containing a chlorine-containing aliphatic solvent such as 1,1-trichloroethane may also be used. These solvents can 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 described above can be coated on a support according to a usual method. For example, (1) coating a cured film on a substrate When forming, a liquid active energy ray-curable resin composition is applied to form a liquid film on a support. It is subsequently dried by evaporation. The dried coating film is cured by irradiation with active energy.

(2) When forming a protective cured layer in a desired pattern shape on a support, a liquid active energy ray-curable resin composition is applied on the support to form a liquid coating film. It is subsequently dried by evaporation. Then, the dried layer is scanned with a laser beam in a desired pattern, and the unexposed portion is removed with an appropriate solvent such as 1,1,1-trichloroethane to form a protective layer cured in a desired pattern shape on the support. Form.

(3) When forming a protective cured layer in a desired pattern shape on a support, a liquid active energy ray-curable resin composition is applied to form a liquid coating film, and then evaporated and dried. A photomask having a pattern having a desired shape through which the active energy ray does not pass is superimposed on the dry film layer, and the photomask is exposed with the active energy ray. Then, the unexposed portions are removed with a suitable solvent such as 1,1,1-trichloroethane, and a protective cured layer is formed on the support in a desired pattern shape.

(4) In the case of forming a photosensitive dry film and laminating the dry film on a support, a liquid active energy ray-curable resin is applied onto a polyethylene terephthalate film to form a liquid film, followed by evaporation drying. Then, a photosensitive dry film is obtained on the polyethylene terephthalate film. The dry film is laminated on a support by a usual laminating method to obtain a laminated body. Then, the photosensitive dry film laminated on the support is cured by irradiating it with an active energy ray in the same manner as in the above-mentioned method (1).

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

When the active energy ray-curable resin composition contains the monomer represented by the formula (X), the cured film obtained by the above method (1) to (4) is further heated to 80 ° C to 200 ° C.
It is desirable to heat-treat at a temperature of 3 ° C. for condensation curing.

Curing of the active energy ray-curable resin composition of the present invention,
Alternatively, examples of active energy rays used for pattern exposure of the composition include ultraviolet rays and electron beams that have already been widely used. As an ultraviolet light source,
Examples include high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps that contain a large amount of light with a wavelength of 250 nm to 450 nm. At a practically acceptable distance between the lamp and the irradiated object, the light intensity near 365 nm is 1 mW / cm ² ~ It is preferably about 100 mW / cm ² . The electron beam irradiation device is not particularly limited, but 0.
Devices with doses in the range of 5-20M Rad are practically suitable.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to the following examples.

Example 1 1-1 As the components (A) to (D) constituting the active energy ray-curable composition of the present invention, those shown below were prepared.

Graft copolymerization polymer (A) Using 80 parts by weight of 2-hydroxyethyl methacrylate and 20 parts by weight of butyl acrylate, using thioglycolic acid as a chain transfer agent and azobisisobutylnitrile as a polymerization initiator, radical chain transfer polymerization is carried out. An oligomer having a carboxy group at the end of the molecular chain was obtained.

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

The number average molecular weight of this macromonomer by the GPC method is
It was about 3,000. 30 parts by weight of this macromonomer 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. .

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

Half-esterified epoxy resin (C) 50% acrylic acid esterified product of orthocresol novolac type epoxy resin (condensation degree 6 to 7) Polymerization initiator (D) The polymerization initiators 1) and 2) of 2 are shown below. (D) -1 The above-mentioned photosensitive aromatic onium (l) salt compound (UVE-10
14, manufactured by GE) (D) -2 Irgacure 651 (manufactured by Ciba Geigy) Next, the above materials (A) to (D) -2 are mixed by a weight ratio ordinary method as shown below, An active energy ray-curable composition of the present invention was obtained.

Material Parts by weight (A) 80 (B) 20 (C) 100 (D) -16 (D) -26 Methylene blue 1 Methyl cellosolve 200 Methyl ethyl ketithone 100 1-3, Preparation of cured resin film The liquid composition of the present invention obtained as described above was applied to a glass plate having been subjected to a cleaning treatment to a thickness of about 80 μm,
It was dried with hot air at 15 ° C for 15 minutes. Next, this glass plate (coating thickness after drying: about 40 μm) was exposed under a high-pressure mercury lamp for 10 seconds at a maximum irradiation energy of 100 mW / cm ² by an active energy ray.

Then, this substrate was heated at 150 ° C. for 30 minutes to be heat-treated.

The glass plate coated with the composition of the present invention obtained as described above was subjected to a reflux treatment for 10 hours with a 1% aqueous solution of caustic soda. The exposed (cured) resin coating film after this treatment maintained good adhesion to the glass substrate and did not cause whitening or blistering even during long-term storage.

Example 2 The composition of Example 1 was applied onto a glass plate having a cleaned surface in the same manner as in Example 1 so that the film thickness after drying was 50 μm. On top of this, overlay a glass mask with a group of evenly spaced stripes with a minimum line width of 20 μm and a spacing of 20 μm.
It was exposed by an ultraviolet irradiation device (mask aligner MA-10, manufactured by Mikasa Co., Ltd.) that generates light rays with high parallelism. Further, the same operation was repeated by changing the exposure condition. 30 after exposure
After a lapse of minutes, development with 1,1,1-trichloroethane was performed.

With this method, three exposure energies (80mj / cm ² , 100m
Samples of three different groups (sample groups I-III) were obtained at j / cm ² and 120 mj / cm ² .

In each of Samples I-III, three different samples with different exposure times (30 seconds, 60 seconds, 90 seconds) were obtained.

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

Then, the above-mentioned method was repeated using this comparative resin composition to prepare comparative sample groups I to III.

The sample thus obtained was evaluated for the pattern resolution, the residue of the undeveloped portion and the pattern swelling by the usual evaluation method.

 The evaluation results are shown in the table below.

The results shown in Table 1 show that the composition of the present invention is always stable regardless of the conditions of exposure and development.

Example 3 3-1 As the components constituting the composition of the present invention, the components shown in (A) to (D) below were prepared.

Graft copolymer (A) A macromonomer having a methacryloyl group at one end of the molecular chain using 50 parts by weight of 2-hydroxyethyl methacrylate and 50 parts by weight of butoxymethylacrylamide in the same manner as in Example 1. I got The number average molecular weight of this macromonomer by the GPC method was about 2,000.

30 parts by weight of this macromonomer and methyl methacrylate
70 parts by weight and solution polymerization in a solvent of methyl cellosolve: methyl ethyl ketone (MEK) = 60:40 (weight ratio), a thermosetting graft having a number average molecular weight of about 6,000 and a weight average molecular weight of about 45,000. A copolymer polymer was obtained.

Linear polymer (B) Methyl methacrylate, tricyclodecane methacrylate, and N-methyl roll acrylamide were mixed at 60: 3.
Linear acrylic copolymer obtained by polymerization at a molar ratio of 0:10. The number average molecular weight is about 60,000 and the weight average molecular weight is about 260,000.

Half-esterified epoxy resin (C) Phenol novolac type epoxy resin (condensation degree of 5
6) 50% acrylic acid esterified product Polymerization initiator (D) The following two polymerization initiators (D) -1 and (D) -2 were prepared.

(D) -1. The above-mentioned light-transmitting aromatic onium salt compound (m) (D) -2. Darocur 1173 (manufactured by Merck & Co.) 3-2. Next, the above materials (A) to (D)- The composition solutions of the present invention were obtained by mixing 2 in the following weight ratio using a conventional method.

Material Parts by weight (A) 50 (B) 50 (C) 100 (D) -16 (D) -26 Methylene blue 1 Methyl cellosolve 200 Methyl ethyl ketone 100 3-3. Formation of cured resin protective film on printed board 3-2, the composition of the present invention in a liquid state obtained on a printed wiring board on which a conductor circuit of a copper foil having a thickness of 60 μm is formed on a glass cloth epoxy substrate is dried. Of 50 μm was applied on the entire surface by a roll coater by a usual method. Drying at that time was performed in a hot air oven at 100 ° C. for 3 minutes.

Then, after cooling, a solder mask pattern was overlaid on the composition, and the ultraviolet intensity near 365 nm was 7 m.
Exposure was carried out for 35 seconds using an ultra-high pressure mercury lamp that emits highly parallel UV light having a collimation deviation angle of 3 ° and W / cm ² . After exposure, use 1,1,1-trichloroethane at 20 ° C for 5
Spray development was performed for 0 seconds. The development proceeded stably, and a clear pattern was obtained. After the development, it was dried, irradiated with the same ultra-high pressure mercury lamp for 5 minutes, and then heat-treated at 150 ° C. for 15 minutes to complete the pattern formation of the cured protective film on the printed board.

The protective film on the printed wiring board obtained as described above is
It had excellent resistance to acids, alkalis and other chemicals.

〔The invention's effect〕

As described above, since the active energy ray-curable resin composition of the present invention contains the graft copolymerization polymer (A) as a constituent component, it can be applied to various supports without adding an auxiliary agent or the like. Since it has sufficient adhesiveness and has the linear polymer (B) as a constituent component, it has excellent developing characteristics during pattern formation. At the same time, it has sufficient chemical resistance and durability for use in various applications.

Furthermore, since the composition of the present invention is used in combination with a graft copolymer and a linear polymer as its constituent polymer, only the graft copolymer is used as the polymer. Compared to the case of using, it is possible to form a coating film with solvent resistance to the developing solution with less active energy ray irradiation. As a result, high sensitivity, improvement of resolution, pattern formation independent of substrate type or condition This improves the properties of the patterning process, such as the ability to perform, and expands the range of working conditions. For this reason, its application can be greatly expanded as compared with the conventional one.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area // (C08L 63/00 51:06 33:04)

Claims (5)

(57) [Claims] 1. A main chain comprising a structural unit derived from at least one monomer selected from the group consisting of (A) alkyl methacrylate, acrylonitrile and styrene, and the following general formula (x) or (y) [Wherein R ¹ represents hydrogen, or an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ² represents hydrogen or an alkyl group optionally having a hydroxy group having 1 to 4 carbon atoms. Represents a group or an acyl group, R ³ is an alkyl group having 2 to 6 carbon atoms, or a halogen-substituted alkyl group, CH _{2 n} OCH _{2 m} (where 2 ≦ m + n ≦ 6, n ≠ 0, m ≠ 0 ) An alkyl ether group represented by (However, 2 ≦ m + n ≦ 4, including the case where n = 0 or m = 0) is a phenylalkyl group. ] A branched chain having a structural unit derived from at least one of the monomers represented by
And a graft copolymer having a number average molecular weight of 5,000 or more and a weight average molecular weight of 50,000 or less, and (B) methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl meta. Selected from the group consisting of acrylate, acrylonitrile, isobornyl methacrylate, isobornyl acrylate, tricyclodecane acrylate, tricyclodecane methacrylate, tricyclodecaneoxyethyl methacrylate, styrene, dimethylaminoethyl methacrylate, cyclohexyl methacrylate Having a structural unit derived from at least one monomer, having a structural unit derived from at least one of the monomers represented by the general formula (x) or (y), and At least a linear polymer having an 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, and (C) a compound having two or more epoxy groups in the molecule. A resin obtained by esterifying a part of epoxy groups present in an epoxy resin containing one kind with an unsaturated carboxylic acid; and (D) a polymerization initiator generating a Lewis acid by irradiation with active energy rays. An active energy ray-curable resin composition comprising: 2. The weight ratio of the graft copolymer (A) to the linear polymer (B) is (A) :( B) = 80: 20-5.
The active energy ray-curable resin composition according to claim 1, wherein the ratio is 0:50. 3. The weight ratio of the total weight (A) + (B) of the graft copolymer (A) and the linear polymer (B) to the epoxy resin (C) is {(A) + ( B)}:
(C) = 100: 50-100: 200, The active energy ray-curable resin composition according to claim 1 or 2. 4. The total weight (A) of the graft copolymer (A), the linear polymer (B) and the resin (C).
The weight ratio of + (B) + (C) to the polymerization initiator (D) is {(A) + (B) + (C)} :( D) = 100: 1 to 100: 10.
The active energy ray-curable resin composition according to any one of claims 1 to 3. 5. The photoinitiator (D) is selected from the group consisting of an aromatic halonium salt compound and a photosensitizing aromatic onium salt compound containing an element belonging to Group VIa or Va of the periodic table. The active energy ray-curable resin composition according to any one of claims 1 to 4, which is one or more of the above.