JPS61291618A - Active energy ray-curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition highly adhesive to glass, ceramics, etc., capable of forming patterns with both high chemical resistance and mechanical strength, by blending each specific linear polymer and esterified epoxy resin. CONSTITUTION:The objective composition can be obtained by blending, (A) a linear polymer with a glass transition temperature >=50 deg.C and weight-average molecular weight >=ca. 3.0X10<4> and (B) a resin prepared by esterification, by unsaturated carboxylic acid, of part of the epoxy groups present in an epoxy resin containing at least one kind of compound having in one molecule two or more epoxy groups. The component B is such that 0.30-0.70 (pref. 0.45-0.55) equivalent per equivalent of the epoxy group contained has been esterified. The amounts to be blended are 20-80pts. by wt. and 80-20pts. by wt. for the components A and B, respectively. Furthermore, 0.1-20wt% per 100pts. by wt. of the components A plus B, of a radical polymerization initiator capable of activation by the action of active energy rays should be incorporated.

Description

Detailed Description of the Invention [Field of Industrial 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, particularly for use on supports such as glass, ceramics, and plastic films. To create an active energy ray-curable resin composition that has excellent properties, chemical resistance, and mechanical strength, and is capable of pattern formation. This active energy ray-curable resin composition is a resin composition that can be shaped into a solid photoreceptor sheet (dry film).

[Conventional technology]

In recent years, active energy ray-curable resins have been used in paints, inks,
It is widely used as a sealing material, resist material, and pattern forming material. In addition, active energy ray-curable resins as pattern-forming materials were initially used to create printing plates, but more recently they have been used in electronic industry fields such as printed wiring and integrated circuits, as well as in the Showa 57-43876
As disclosed in the issue, it is also being used as a structural material for devices such as inkjet recording devices.

However, active energy ray-curable resins used for pattern formation, especially dry film types, have excellent adhesion to supports such as glass, ceramics, or plastic films. There was nothing. On the other hand, known photo-curing paints and adhesives used for glass, metals, ceramics, etc., have excellent adhesion to the cured product, but they require exposure to strong active energy rays or long-term exposure. Moreover, they generally do not have properties suitable for pattern formation.In other words, they are used to irradiate active energy rays in a pattern and remove the unexposed areas by development to obtain a pattern. However, it was not possible to obtain precise, high-resolution patterns.

As described above, in the prior art, there has been no material that can form precise patterns with excellent adhesion on various types of supports, and that also has high durability as a structural material.

(Problems to be Solved by the Invention) The purpose of the present invention is to provide a resin with excellent adhesion to a support, precision, and high resolution, which could not be achieved with such conventional active energy ray-curable resins. An object of the present invention is to provide an active energy ray-curable resin composition capable of forming a pattern.

Another object of the present invention is that it can be shaped into a dry film that is convenient for pattern formation, and that the pattern that is hardened by irradiation with active energy rays and heat treatment as required has chemical resistance and mechanical resistance. An object of the present invention is to provide an active energy ray-curable resin composition that has excellent mechanical strength and high durability as a structural material.

[Means for solving problems]

The active energy ray-curable resin composition of the present invention has (i) a glass transition temperature of 50°C or higher, and a weight average molecular weight of about 3. A linear polymer having OX 10×104 or more, and (i
i) A resin obtained by esterifying 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 with an unsaturated carboxylic acid, and containing as an essential component. It is something.

[Preferred mode for carrying out the invention]

The active energy ray-curable resin composition of the present invention provides an appropriate property for maintaining the composition in the form of a solid film when the composition is put to practical use as a dry film, and is capable of being cured and formed. In order to impart excellent mechanical strength to the pattern, (i) the glass transition temperature is 50°C or higher,
And the weight average molecular weight is about 3. Contains a linear polymer having an OX of 10 x 104 or more as an essential component.

When the glass transition temperature and weight average molecular weight of the linear polymer are less than the above values, for example, when producing a dry film, it is formed as a film-like solid resin layer on a support such as a plastic film. The composition gradually flows during storage and causes phenomena such as wrinkles or uneven layer thickness, making it impossible to obtain a good dry film.

Specifically, such a linear polymer is, for example, a homopolymer that has a relatively rigid bamboo-like shape and whose main component is a monomer (^) that can provide the glass transition temperature as described above.
If necessary, as a second component, for example, a hydrophilic injection is included,
The composition of the present invention can be endowed with even better indigenous properties (8)
hydroxyl group-containing acrylic monomer, (C) amine or alkylamino group-containing acrylic monomer, CD) carboxyl group-containing acrylic or vinyl monomer, (E)
Monomers such as N-vinyl and lolidone or its derivatives, CF)donyldolysine or its derivatives, and (G
) The following general formula 1 can impart high cohesive strength to the composition of the present invention and improve the mechanical strength of the composition (wherein R1 is hydrogen or an -alkyl group having 1 to 3 carbon atoms, and R2 is the A divalent hydrocarbon group which may have an ether bond inside and may be substituted with a halogen atom, R3 represents an alkyl or phenylalkyl group having 3 to 12 carbon atoms, or a phenyl group. Examples include thermoplastic copolymer polymers obtained by using monomers as a copolymer component within 40 mol%.

Specifically, the monomers used as component (A) include methyl methacrylate, ethyl methacrylate,
Examples include alkyl methacrylates in which the alkyl group has 1 to 4 carbon atoms, such as isobutyl methacrylate and t-butyl methacrylate, acrylonitrile, and styrene. These monomers are preferably contained in an amount of 60 mol% or more in order to impart the above-mentioned glass transition temperature to the linear copolymer polymer.

Specifically, the monomers (8) to (G) above used as the second component include 2-hydroxyethyl (meth)acrylate (hereinafter referred to as (meth)acrylate) as the hydroxyl group-containing acrylic monomer of CB). When stated, it is meant to include both acrylate and methacrylate), 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, or monoester of 1,4-cyclohexane dimetatool and acrylic acid or methacrylic acid.
TONE Mloo (cabrolauton acrylate,
Union Carbide), Light Ester HO-mp
p (manufactured by Kyoeisha Yushi Kagaku Kogyo ■), Light Ester M-
60OA (trade name of ii-hydroxy-3-phenoxypro and acrylate, manufactured by Kyoeisha Yushi Kagaku Kogyo ■) and 1, dihydric alcohols, e.g.
, 10-decanediol, neopentyl glycol, his(ii-hydroxyethyl) terephthalate, an addition reaction product of bisphenol A and ethylene oxide or propylene oxide, etc., and a monoester of (meth)acrylic acid can be used in an amount of 4%.

As the amine or alkylamino group-containing acrylamide of (C), (meth)acrylamide, ff, N
-dimethylamine ethyl (meth)acrylamide, ff
, N-dimethyl(meth)acrylamide, ff, N-dimethylaminopropyl(meth)ac 1-noramide, N,
Examples include N-di-t-butylaminoethyl (meth)acrylamide.

Examples of the carboxyl group-containing acrylic or vinyl monomer (D) include (meth)acrylic acid, fumaric acid, itaconic acid, and those known under the trade names of Toagosei Chemical products such as Aronix M-5400 and Aronix M-5500. .

As vinyl and lysine or derivatives thereof (F),
2-donyldolysine, 4-vinyldolysine, 2-vinyl-6-methylpyridine, 4-vinyl-1-methylpyridine, 2-vinyl-5-ethyldolysine, 4-(4-bibenylinoethyl)pyridine, etc. can be mentioned.

All of the monomers (8) to (F) above have hydrophilic properties, and when the composition of the present invention is adhered to a support such as glass, ceramics, or plastic, they provide strong and adhesive properties. It is intended to give.

Specifically, the monomer represented by the general formula (G) (G) contains one hydroxyl group in one molecule (α-alkyl)
Examples include (α-alkyl) acrylic esters having one or more urethane bonds in one molecule, which are obtained by reacting acrylic esters with a monoisocyanate compound. Incidentally, R2 in the monomer represented by general formula 1 can be any divalent hydrocarbon group which may have an ether bond therein and may be substituted with a halogen atom, but is preferably As R2, the number of carbon atoms is 2
Examples include an alkylene group which may be substituted with ~12 halogen atoms, an alicyclic hydrocarbon group such as 1,4-bismethylenecyclohexane, and a hydrocarbon group containing an aromatic ring such as bisphenyldimethylmethane. can.

Containing at least one hydroxyl group in one molecule used when producing the monomer represented by the above general formula I (
As meth)acrylic acid esters, 2-hydroxyethyl (meth)acrylate, 2-human 0xypropyl (
meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, 5-hydroxypentyl(meth)acrylate, 6-hydroxyethyl(meth)acrylate ) Acrylate or light ester HO-mpp (Kyoeisha Yushi Kagaku Kogyo ■
(manufactured by).

In addition to the above, (α-alkyl)acrylic acid esters containing one hydroxyl group in one molecule include (a) esters of aliphatic or aromatic dihydric alcohols and (meth)acrylic acid, and (b) monoesters. (Meth)acrylic esters of epoxy compounds can likewise be used.

The dihydric alcohol used in (a) above includes 1.
4-Cyclohexane dimetatool, 1,10. - 2-10 of ethylene oxide or propylene oxide to decanediol, neopentyl glycol, bis(ii-hydroxyethyl) terephthalate, bisphenol A
Examples include molar addition reactants. In addition, as the monoepoxy compound used in the above (b), Evolite M
-1230 (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo ■), phenyl glycidyl ether, cresyl glycidyl ether, butyl glycidyl ether, octylene oxide,
Examples include n-butylphenol glycidyl ether.

Further, as monoisocyanate compounds used in producing the monomer represented by general formula 1, alkyl monoisocyanates prepared by adding one incyanato group to an alkyl group having 3 to 12 carbon atoms, and phenyl Examples include isocyanate and cresyl monoisocyanate.

The monomer represented by general formula I is preferably contained in the linear copolymer polymer in an amount of up to 40 mol%; if the content exceeds 40 mol%, the softening point of the resulting composition decreases. This causes problems such as a decrease in surface hardness of the pattern obtained by curing the composition and deterioration of chemical resistance due to swelling.

The composition of the present invention can be provided in various forms depending on the purpose of use, such as a solution or a solid film, but it is easier to use it in the form of a dry film, and it is easier to control the film thickness. It is also easy and particularly advantageous. Of course, there is no problem in using it in the form of a solution.

Although the case where a thermoplastic linear polymer is mainly used has been described above, in the present invention, a linear polymer having thermal crosslinkability or photocrosslinkability can also be used.

The thermally crosslinkable linear polymer is, for example, a thermoplastic linear polymer having the following general formula II: CH2=C---(II) 0=C-NH-C)I2-0-R5 (However, , R4 represents hydrogen or an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms, and R5 represents hydrogen or an alkyl or acyl group optionally having a hydroxy group having 1 to 4 carbon atoms. It can be obtained by introducing such a thermally crosslinkable monomer as the second component of copolymerization. The monomer represented by the above general formula (2) not only has thermal crosslinkability but also has parent wood 1, and due to the thermal crosslinkability, the composition of the present invention has excellent properties as a structural material, such as heat resistance,
It exhibits excellent chemical resistance, mechanical strength, etc., and excellent adhesion to a support due to its hydrophilicity.

Specifically, the monomer represented by the above general formula (■) is N
-Methylol (meth)acrylamide (hereinafter referred to as (meth)
When it is written as acrylamide, it is meant to include both acrylamide and metaacryamide. ),
N-propoxymethyl (meth)acrylamide, N-n
-Butoxymethyl (meth)acrylamide, β-hydroxyethoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N~methoxymethyl (meth)acrylamide, N-acetoxymethyl (meth)acrylamide, α-hydroxymethyl- N-methylolacrylamide, α-hydrodiethyl-N-butoxymethylacrylamide, α-hydroxypropyl-N-propoxymethylacrylamide, α-ethyl-
Examples include acrylamide derivatives such as N-methylolacrylamide and α-propyl-N-methylolacrylamide.

As mentioned above, these monomers represented by the general formula (2) have not only hydrophilic properties but also condensation crosslinking properties when heated, and generally water molecules or alcohol are detached at a temperature of 100°C or higher to form a crosslinking bond and cure. This method allows the linear copolymer polymer itself to form a network structure, thereby imparting excellent chemical resistance and mechanical strength to the pattern obtained by curing.

When using thermosetting linear polymers, these monomers represented by the general formula
It is preferable that the linear polymer contains 0 mol %. When the content is within the above range, sufficient chemical resistance based on thermosetting is imparted. In contrast, the content is 30 mol%
If it exceeds this amount, problems such as the pattern obtained by curing becoming brittle will occur.

In addition to the monomer represented by the above general formula (III), by appropriately using a monomer that is ring-opened and crosslinked by heat, such as glycidyl (meth)acrylate, as a copolymerization component, the same as in the case of the above general formula H can be obtained. effect can be obtained.

The photocrosslinkable linear polymer can be obtained, for example, by introducing a photopolymerizable monomer into the linear polymer, as exemplified below. Such a method is, for example, copolymerizing a carboxyl monomer such as (meth)acrylic acid, or a monomer containing an amine group or a tertiary amine group, and then reacting with glycidyl (meth)acrylate, etc. ■ A method of reacting a polyisocyanate partial urecne compound having one isocyanate group and one or more acrylic ester groups in one molecule with a branched hydroxyl group, amino group or carboxyl group, ■ A method of reacting a branched chain hydroxyl group, amino group or carboxyl group; A method of reacting the hydroxyl group of the branch chain with acrylic acid chloride, ■ A method of reacting the hydroxyl group of the branch chain with an acid anhydride, and then reacting it with glycidyl (meth)acrylate. Methods include a method in which acrylamide groups are left in the side chains by condensation with a condensation crosslinkable monomer, and a method in which a hydroxyl group (glycidyl (meth)acrylate) of an O branch chain is reacted.

When the linear polymer in the present invention is thermally crosslinkable,
It is preferable to perform heating after forming a pattern by irradiation with active energy rays.On the other hand, in the case of photopolymerizable linear polymers, heating is also performed within an allowable range in terms of the heat resistance of the support. There is no problem with this, and it actually gives a more favorable result.

The linear polymers used in the present invention are broadly classified into those without curability, those with photocrosslinkability, and those with thermal crosslinkability, as described above, but in any case, the composition of the present invention can be cured. In the process (i.e., pattern formation by active energy ray irradiation and thermal curing as necessary), shape retention is imparted to the composition to enable precise patterning, and the pattern obtained by curing is It provides excellent adhesion, chemical resistance, and high mechanical strength.

A part of the epoxy groups present in the epoxy resin, which is another component used in the composition of the present invention and is made of one or more compounds containing two or more epoxy groups in one molecule, is esterified with an unsaturated carboxylic acid. The tree Jl & (i
i) (hereinafter abbreviated as halfesterized epoxy resin) allows the composition of the present invention to exhibit curability with active energy rays, and also allows the resin composition of the present invention to be used in various materials such as glass, plastics, ceramics, etc. The resin composition of the present invention can be applied in liquid form onto a support and then cured to form a cured film, or when used in the form of a dry film adhered to various supports. The cured film has better adhesion to the support, water resistance,
It is a component for imparting chemical resistance, dimensional stability, etc.

The half-esterified epoxy tree 11(ii) contained in the resin composition of the present invention is obtained by adding a predetermined amount of unsaturated carboxylic acid to an epoxy resin in the coexistence of an addition catalyst and a polymerization inhibitor.
80-120 in the presence or absence of a solvent
It can be obtained by a method such as reacting under temperature conditions of 0.degree. C. to esterify a portion of the epoxy groups present in the epoxy resin with a carboxylic acid (hafesterization).

Examples of epoxy resins containing one or more compounds containing two or more epoxy groups in one molecule that can be used to form the halfesterized epoxy resin (ii) include bisphenol A type, novolak type, and alicyclic type. Epoxy resins represented by, or bisphenol S, bisphenol F, tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, glycerin triglycidyl ether, pentaerythol triglycidyl ether, isocyanuric acid triglycidyl ether, and the following general formula Examples include polyfunctional epoxy resins such as epoxyurethane resins represented by m (wherein R represents an alkyl group or an oxyalkyl group), and mixtures of one or more thereof.

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 Epicort 828.834.871.1001,
+004 (product name, manufactured by Shell Chemical Co., Ltd.), DER33
1-J, 337-J, 661-J, 664-
Examples of di-novolac type epoxy resins include Epicoat 152, +54, +72, (trade name, Shell Chemical Co., Ltd.), Araldite EPN 1138 (trade name, Ciba Geigy Co., Ltd.), DER431, 438 and 439 (
(trade name, manufactured by Dow Chemical Company) etc. Examples of alicyclic epoxy resins include Araldite CY-175 and -176.
, -179, -182, -184, -192 (product name,
Ciba Geigy), Chissonox 090.091.
092, 30+, 313 (product name, manufactured by Chisso ■),
CYRACURE 6100.6110
．． 6200 and ERL 4090.4617.2256
．． 54N (product 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, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1.6- Hexanesiol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl ether to hydrogenated hisphenol,
2,2-dibromoneopentyl glycol diglycidyl ether, etc.: Polyhydric glycidyl ethers derived from aromatic polyhydric alcohols include diglycidyl ethers of 2 to 16 mol adducts of alkylene oxide of hisphenol A, bisphenol F Alkylene oxide 2~
Examples include diglycidyl ether as a 16-mol adduct and diglycidyl ether as a 2-16-mol adduct of alkylene oxide of bisphenol S.

Various unsaturated carboxylic acids can be used to halfesterize the epoxy resin, but in order to impart better curability with activation energy to the resin composition of the present invention, A basic 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 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.

Moreover, as the above-mentioned (meth)acrylic acid ester having one hydroxyl group, 2. -Hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (
Mention may be made of meth)acrylate, 3-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxybutyl (meth)acrylate, and the like.

Examples of addition reaction catalysts that can be used in the halfesterization reaction of epoxy resins include overpressure 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 ethyl sulfide. Compounds of the sulfoxy group such as sulfoxyl-'', compounds with tertiary amine necks such as N,N-dimethylaniline, dolysine, triethylamine, benzyldimethylamine, and their hydrochlorides or salts, such as tetramethylammonium Examples include quaternary ammonium salts such as chloride, trimethyldodecylhenzyl ammonium chlorite, triethylbenzylammonium chloride, sulfonic acid compounds such as para-toluenesulfonic acid, and mercaptan compounds such as ethyl mercaptan and propyl mercaptan. be able to.

Furthermore, examples of polymerization inhibitors that can be used in halfesterization include hydroquinone, alkyl or aryl M-substituted hydronon, tert-butylcatechol,
Mention may be made of dorogallol, naphthylamine, B-naphthol, cuprous chloride, 2,6-dibutyl-p-cresol, phenothiazine, pyridine, N-nitron diphenylamine, and ditrohenzene.

Further, examples of solvents that can be used when the halfesterization is carried out in the presence of a solvent include toluene, xylenedi, methyl isobutyl ketone, methyl ethyl ketone, ethyl acetate, butyl acetate, and isobutyl acetate.

The amount of epoxy resin and unsaturated carboxylic acid used during halfesterization is such that the ratio of the epoxy group of the epoxy resin to the carboxyl group of the unsaturated carboxylic acid is preferably +:
0.3 to I: 0.7, more preferably l: 0.4
5 to I: appropriately selected so as to be 0.55.

That is, if the esterification rate of the epoxy group by the unsaturated carboxylic acid in the halfesterified epoxy resin is higher than the above range, the resin composition of the present invention will not have good chemical resistance, dimensional stability, etc. derived from the epoxy resin. If it is lower than the above range, the resin composition of the present invention will not have sufficient curability with high resolution due to the action of active energy rays based on the (meth)acrylic acid ester group. I can't get it.

As described above, the active energy ray-curable resin composition of the present invention has curability due to the action of active energy rays based on the (meth)acrylic acid ester group of the halfesterized epoxy resin contained as an essential component, and the epoxy group. After curing the resin composition of the present invention by irradiating it with active energy rays,
C. or higher for about 10 minutes to 3 hours to further thermally cure the resulting cured film, which is more effectively provided with good chemical resistance, dimensional stability, etc. derived from the epoxy resin.

Examples of active energy rays used for curing the active energy ray-curable resin composition of the present invention include ultraviolet rays and electron beams, which have already been widely put into practical use. Examples of ultraviolet light sources include high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, etc. that contain a large amount of light with a wavelength of 250 nm to 450 nm, and the intensity of light in the vicinity of 3δ5 nm is 1m'll
/cm'-10h+W/cm' The electron beam irradiation device is preferably about 0.5
A device with a nodal dose of ˜20 M Rad is practically suitable.

The active energy ray-curable resin composition of the present invention is cured by the above-mentioned active energy rays.
When using active energy rays of 0 nm to 450 nm, it is preferable to add to the resin composition a radical polymerization initiator that can generate organic free radicals that can be activated by the action of the active energy rays. As the initiator, any known substance having the property of being activated by active energy rays, generating organic free radicals, and initiating radical polymerization can be used without particular limitation.

Specific examples of such radical polymerization initiators include benzyl, benzoin alkyl ethers: benzoin isobutyl ether, benzoin isopropyl ether, hengein-n-butyl ether, benzoin ethyl ether, benzoin methyl ether, etc.; .4'-bis(N-diethylamino)benzophenone, benzophenone methyl ether, etc., azitraquinone neck: 2-dithylanthraquinone, 2-t-butylanthraquinone, etc., xacytone M:
2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, etc., acetophenone m:2,2-
Dimethoxy-2-phenylacetophenone, α,α-dichloro-4-phenoxyacetophenone, p-tert
-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 2,2-jethoxyacetophenone, p-dimethylaminoacetophenone, etc.
Alternatively, hydroxycyclohexylphenyl ketone (Irgacure 184 manufactured by Ciba Geigy), 1-(4
-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one (Darocur 1116 manufactured by Merck (VERCK) ■), 2-hydroxy-2-methyl-
1-phenyl-propan-1-one (Darocur 117
3 (manufactured by Merck ■) and the like are preferably used. In addition to these radical polymerization initiators, an amine compound may be added as a photopolymerization accelerator.

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

Furthermore, in the active energy ray-curable resin composition of the present invention, the epoxy group contained in the halfesterized epoxy resin (ii) is also photopolymerized by the action of active energy rays. An aromatic omnilam salt compound having photosensitivity containing an element belonging to Group V (a group) as shown in the official gazette, or Japanese Patent Publication No. 52
Aromatic omnilum salt compounds having photosensitivity and containing elements belonging to Group Va as shown in Japanese Patent No. 14279 can be blended.

A photosensitive aromatic omnilam salt compound of an element belonging to group VTa or group Va typically has the following general formula (1): [(R')a (R7)b CR8)eX]; [MQ
eDo11-41...(■)゛(In the above formula, R6 is a monovalent organic aromatic group, R7 is a monovalent organic aliphatic group selected from an alkyl group, a dicycloalkyl group, and a substituted alkyl group) , R8 is a polyvalent organic group constituting a heterocyclic or condensed ring structure selected from aliphatic groups and aromatic groups, An element that reaches Group Va selected from bismuth, M represents a total pressure or a metalloid, and Q represents a halogen group, respectively,
a is O~3 when X is an element belonging to group Vla
an integer of 0 to 0 if X is an element belonging to Group Va
an integer of 4, b is an integer of 0 to 2, C is an integer of O or 1 when X is an element belonging to group Via, X is an integer of group Va
In the case of an element belonging to the group, fl(t
The valence of M 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 ahib and C is 3 (X of When X is an element in Group Va, there are compounds represented by 4 (the valence of has the property of releasing 1Fr Lewis acid, which cures the epoxy resin.

Specific examples of photosensitive aromatic omnilam salt compounds containing elements belonging to group VTa or group Va that can be blended into the resin composition of the present invention include, for example, elements belonging to group Mention may be made of the photosensitive aromatic omnilam salts and the photosensitive aromatic omnilam salts of elements belonging to group Va such as, for example.

The composition ratio of the materials constituting the active energy ray-curable resin composition of the present invention is 20 to 80% by weight of the linear polymer (i), preferably 20 to 50% by weight, and 80 to 20% by weight of the halfesterized epoxy resin. %, preferably 50-80
When a radical polymerization initiator activated by active energy rays is used, the polymerization initiator is a resin component [(i)(ii)]-1100% by weight consisting of a linear polymer and a halfesterized epoxy resin. 0.
It ranges from 1 to 20 parts by weight, preferably from 1 to 10 parts by weight. In addition, when using a photosensitive aromatic omnilam salt containing an element belonging to Group Via or Group Va, the content of the compound is the linear gold polymer and the halfesterized epoxy resin [(i)/(ii )] The amount is in the range of 0.2 to 15 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the resin component consisting of fat.

When using the active energy ray-curable resin composition of the present invention in solution form or when coating it on a plastic film, etc., which is a film base material when forming a dry film, the solvent used is alcohol. Examples include wood-loving solvents such as glycol ethers, glycol esters, and the like. Of course, these wood-philic solvents are the main agents, and if necessary, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and inbutyl acetate, aromatic hydrocarbons such as toluene and xylene, and their halogens are used. Substituted product, methylene chloride, 1
．． It is also possible to use an appropriate mixture of a chlorine-containing aliphatic solvent such as 1.1-trichloroethane. Incidentally, these solvents can also be used as a developer for the composition of the present invention.

In addition to the radical polymerization initiator or solvent described above, the active energy ray-curable resin composition of the present invention includes, for example, a condensation crosslinking catalyst, a thermal polymerization inhibitor, a coloring agent (dye and pigment), a particulate filler, and an adhesion promoter. Additives such as agents and plasticizers can be included as necessary.

Examples of the condensation crosslinking catalyst include sulfonic acids typified by para-toluenesulfonic acid, and carboxylic acids such as formic acid. Examples of thermal polymerization inhibitors include hydroquinone and its derivatives, paramethoxyphenol, and phenothiazine.As colorants, oil-soluble dyes and pigments may be added to the extent that they do not substantially prevent the transmission of active energy rays. As the filler, extender pigments, plastic particles, etc., which are commonly used in paints, are used to increase the hardness, coloration, adhesion, and mechanical strength of the coating film.

As adhesion promoters, silane coupling agents and low molecular surfactants as inorganic surface modifiers are effective in the composition of the present invention.

Furthermore, an epoxy resin curing agent may be added to the active energy ray-curable resin composition of the present invention, if necessary. Examples of the epoxy resin curing agent that can be added to the resin composition of the present invention include polyamine,
Examples include polyamides, acid anhydrides, boron trifluoride-amine complexes, dicyandiamide, imidazoles, and complexes of imidazole and metal salts.

The active energy ray-curable resin composition of the present invention can be used as a protective coating for glass, an adhesive, an insulating layer of a liquid crystal display element, or a transparent or opaque coloring on a glass plate, imparting waterproof properties, imparting hot water properties, and stain resistance. It can be used for surface modification such as imparting properties. Further, due to its excellent chemical resistance, it is useful as a masking material for glass etching or metallizing such as electroless steel plating, and as a solder mask for printed wiring boards. Further, it is useful for forming fine liquid flow paths, cooling paths, or nozzles using water resistance, especially nozzles in inkjet recording heads. Furthermore, it is possible to obtain a photosensitive liquid or dry film for screen printing plates that is uniquely durable and can be used for both water-based and oil-based inks.

Examples of how to use the active energy ray-curable resin composition of the present invention for the various uses mentioned above are as follows.

1) The composition of the present invention is applied onto a support to a desired thickness in the range of 1 to 100 μm, the solvent is evaporated to dryness, and the bond is irradiated with active energy rays at 80° C. or higher for 10 minutes or more. The support is heated for about 3 hours. In addition, when a thermosetting linear polymer is used, the temperature of this heat treatment is set at a temperature of at least 100° C. for about 5 minutes to 60 minutes.

2) The composition of the present invention is applied onto a support to a desired thickness ranging from 1 to 100 scales, and the solvent is evaporated to dryness.

After that, the transmittance of active energy rays is at least 1%.
The following mask pattern is placed on the composition, and active energy rays are irradiated from above the mask. Next, the non-irradiated areas are removed by developing with a developer that dissolves the composition. Next, the support is heated at a temperature of at least 80°C or higher for about 10 minutes to 3 hours.

In addition, when thermosetting linear polymers are used, the temperature of this heat treatment is at least 100°C for 5 minutes or more.
It will take about 60 minutes.

The cured film obtained in the above manner has excellent not only resolution but also adhesion to the support, mechanical strength, water resistance, chemical resistance, and dimensional stability.

Furthermore, the active energy ray-curable resin composition of the present invention includes:
By forming it into a dry film, adhering it onto a support, and then subjecting it to exposure and heat treatment as described above,
A cured film or a pattern consisting of a cured film of the resin composition of the present invention can be obtained on a support, and in this case also, the adhesiveness to the support, mechanical strength, water resistance, chemical resistance, and dimensional stability are improved. A cured film with excellent properties can be obtained.

〔Effect of the invention〕

The active energy ray-curable resin composition of the present invention has excellent sensitivity and resolution as a pattern forming material,
High-resolution patterns can be formed at high and high resolution.

Moreover, the active energy ray-curable resin composition of the present invention effectively utilizes the characteristics of the linear polymer and halfesterized epoxy resin as essential components. In addition to the excellent adhesion to the support and mechanical strength provided by the linear polymer, it mainly has excellent chemical resistance and dimensional stability provided by the halfesterized epoxy resin. The pattern formed by the composition has excellent visibility when viewed as a coating material, and is suitable as a protective coating or a structural member that requires long-term durability.

Furthermore, when a linear polymer having curability is used, it is possible to obtain an active energy ray-curable resin composition that has even better adhesion, mechanical strength, or chemical resistance.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Methyl methacrylate, t-butyl methacrylate and dimethylaminoethyl methacrylate (=70/2
0/10 molar ratio) in toluene, and the weight average molecular weight ? , 8 X104 , a linear polymer compound with a glass transition temperature of 89°C (this will be referred to as LP-1) v! Obtained.

Also, the epoxy equivalent is 183 to 193 and bisphenol A
A mixture of type Ebicuron 855 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) 2009, triethylbenzylammonium chloride 49 as a catalyst, and hydroquinone 0.59 as a thermal polymerization inhibitor was heated to 80°C to remove the epoxy groups 1 present. The reaction was carried out by dropping 0.5 equivalent of acrylic acid based on the equivalent amount. After dropping Acrylic M, stirring was continued for 4 hours to complete the reaction. In this way, an epoxy halfester (referred to as HE-1) in which the epoxy group was partially esterified with acrylic acid was obtained.

An active energy ray-curable resin composition having the following composition was prepared using the linear polymer compound LP-1 and epoxy Hafestel HE-1 obtained as described above.

LP-1100 parts by weight HE-112On Irgacure 651 IQ, II
Crystal violet 0.5//L-butylhydroquinone 0.5〃1-1 mixture of MI8/toluene 300〃This composition was subjected to ultrasonic cleaning treatment in a cleaning liquid Guiflon (manufactured by Daikin Engineering Co., Ltd.) and dried. on a Pyrex board,
It was coated with a bar coater so that the thickness after drying was about 50 μm.

Using a mask for resolution testing, in which a polyethylene terephthalate film (Lumirror T type) with a thickness of 16 μm was laminated on the surface of this composition, the center wavelength was around 365 m, and the light energy was 12 mW at the irradiated surface.
/cm' exposure light source for semiconductors using an ultra-high pressure mercury lamp [Mask alignment equipment MA-10J (
(manufactured by Mikasa) for 60 seconds. After exposure 1.1
．． 1- Trichloroethane/ethanol (= 80/2
Development was carried out for 45 seconds in an ultrasonic cleaner using the developer of 0). The resolution of the resin composition after development accurately reproduced a pattern of lines/intervals with a width of 50 scales.

The substrate was then heat dried, post-exposed to IOJ/cm2 and heated at 150° C. for 30 minutes. When this board was subjected to a cross-cut tape peeling test using an industrial Serote tape, it showed an adhesion of +00/+00.
The area where the cross-cut was clearly removed was completely adhered.

Furthermore, this board was immersed in a NaOH aqueous solution of PI (=9.0) and a boiling test was conducted for 4 hours. After the boiling test, a cross-cut tape peeling MtC test and a peeling test on the 50- pattern portion were conducted again. However, no deterioration in adhesion such as peeling or lifting was observed in either case.Also, no deterioration such as whitening of the coating film was observed at all.

Example 2 Methyl methacrylate, butyl carbamylethyl methacrylate and butoxymethyl acrylamide (=80
/10/10 molar ratio) in toluene to produce a linear polymer compound (this v!LP) having a weight average molecular weight j, 4
−2) was obtained.

Also, the epoxy equivalent is 450 to 500 and bisphenol A
Example 1 was carried out in exactly the same manner as in Example 1, except that a type of epoxy resin Kron 1050 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) was used.
．． Add epoxy halfester (
this! (referred to as HE-2) was obtained.

The process was carried out in exactly the same manner as in Example 1, except that an alicyclic epoxy resin Celoxide 2021 (manufactured by Daicel Chemical Co., Ltd.) with an epoxy equivalent of 128 to 145 was used, and 0.5 equivalent of acrylic acid was used to make the epoxy group. Epoxy halfester (referred to as HE-3) was obtained in the following manner.

Linear polymer compound LP-2 with thermal crosslinkability obtained as above and epoxy Hafestel HE-2,H
Using E-3 and HE-1 obtained in Example 1, a live energy ray-curable resin composition having the following composition was prepared.

LP-2100 parts by weight HE-15Q tt HE-250tt HE-320u Irgacure 65+ +0 1/para-toluenesulfonic acid 311 Crystal Violet 0.5 t-butylhydroquinone 0.5 MIB/toluene 1.1 mixture A pattern was formed in the same manner as in Example 1 using the above active energy ray curable resin composition.

The resulting pattern image was clear and had a resolution of 50μ.

Next, post-exposure and heating were carried out in the same manner as in Example 1, and a cross-cut tape peeling test was conducted.
00 was exhibited, and the area where the cross-cut was clearly removed was completely adhered.

Further, this substrate was immersed in a NaOH aqueous solution with pH=9.0, and a boiling test was conducted for 8 hours. After the boiling test, a cross-cut tape peeling test and a peeling test on the 50u+ pattern were carried out again, but no deterioration in adhesion such as peeling or lifting was observed in either case. Furthermore, no deterioration such as whitening of the coating film was observed.

Example 3 Methyl methacrylate, acrylic acid, and 2-hydroxyethyl methacrylate (=-70/10/20 molar ratio)
A copolymer was obtained by solution polymerization in toluene. Next, glycidyl methacrylate was added in an amount equivalent to the carboxyl group in this copolymer, and the reaction was carried out at 80°C using triethylbenzylammonium chloride as a catalyst. Weight average molecular weight 1, IXIO', glass transition temperature 96
A linear polymer compound (LP-
3) was obtained.

In addition, 1 equivalent of epoxy group (1 equivalent of epoxy group) was carried out in exactly the same manner as in Example 1, except that a cresol novolac type epoxy resin Evicron N-665 (manufactured by Dainippon Ink Chemical Industries, Ltd.) with an epoxy equivalent of 200 to 230 was used. Acrylic acid was added in an amount of 0.5 equivalent to obtain an epoxy halfester (referred to as HE-4).

The linear polymer compound LP-3 having photocrosslinking properties obtained as described above and the epoxy Herfestel HE-4 and Example 1.2 were obtained. An active energy ray-curable resin composition having the following composition was prepared using HE-1 and HE-3.

LP-3100 parts by weight HE-150 HE-320II HE-45Q tt Irgacure 651 1Q u2-ethyl-4-methylimidazole 7.0 Crystal Violet 0.5 t-Butylhydroquinone 0.5 t MIB/Toluene A 1=1 mixture of 300 〃This composition was coated with a bar coater on a silicon wafer on which an oxide film of 5 in 2 had been formed so that the thickness after drying would be 50. Next, a pattern for a resolution test was formed in the same manner as in Example 1. The formed pattern accurately reproduced a line/space pattern with a width of 50u+.

The silicon wafer was then thermally dried and post-exposed at 10 J/cm' using the same ultraviolet light source used for pattern exposure. When this silicon wafer was subjected to a cross-cut tape peeling test, no peeling of the coating film was observed.

Further, this substrate was immersed in a NaOH aqueous solution having a pH of 9.0, and a boiling test was conducted for 8 hours. After the boiling test, a cross-cut tape peeling test and a peeling test on the 50-pattern part were performed again, but no deterioration in adhesion such as peeling or floating was observed in either case. Furthermore, no deterioration such as whitening of the coating film was observed.

Example 4 The same procedure as in Example 1 was carried out except that a cresol novolac type epoxy resin Evicron N-680 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) with an epoxy equivalent of 205 to 250 was used. Acrylic acid is 0.
This was added in an amount of 5 equivalents to obtain epoxy halfester (referred to as HE-5).

Linear polymer compounds LP-2, epoxy halfester HE-1, and HE that exhibit thermal crosslinking properties obtained in Examples 1 to 3
An active energy ray-curable resin composition having the following composition was prepared using the above-mentioned HE-3 and HE-5.

LP-2100 parts by weight HE-15Qu HE-32On HE-55Qn Irgacure 651 10 Copper phthalocyanine 0,511 t-butylhydroquinone 0.5 1:1 mixture of MI8/toluene 300 ulocm x 10cm Pyrex glass plate with thiol groups Two solutions of 1% ethanol containing the silane coupling agent γ-mercaptopropyltrimethoxysilane were applied onto a glass plate using a sprayer. Coating was done by rotating the glass plate at 2500 rpm for 25 seconds.
Heat treated for 0 minutes. Mill dispersion t16 of the resin composition
A resin composition layer having a film thickness of 50+u+ was formed by applying the resin composition to a polyethylene terephthalate film of u with a wire bar and drying at 100° C. for 20 minutes. Next, this film was laminated on the Pyrex glass plate at 120° C. and a circumferential speed of 1 m/n+in using a laminator HRL-24 (trade name, manufactured by DuPont Co., Ltd.). Thereafter, in the same manner as in Example 1, it was possible to form a clear pattern colored blue with lines and intervals of 50-.

Next! Post-exposure of OJ/cm2 and 150℃11
After 5 minutes of heat treatment and complete curing, a cross-cut tape peel test was performed and the result was 10o/100.
It showed good adhesion, and the clear removal of the cross-cut was completely covered.

Further, this substrate was immersed in an aqueous Na leaf solution with a pH of 9.0, and a boiling test was conducted for 8 hours. After the boiling test, a cross-cut tape peel test WJA and a peel test on a 50 μm pattern were performed again, but no peeling occurred in either case.
No deterioration of indigenous characteristics such as floating was observed. Furthermore, no deterioration such as whitening of the coating film was observed.

Example 5 The procedure was carried out in exactly the same manner as in Example 1 except that a phenol novolac type epoxy resin Eviclon N-730 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) with an epoxy equivalent of 170 to 190 was used. Acrylic acid is 0.
Epoxy halfester (referred to as HE-6) was obtained by adding 5 equivalents.

Linear polymer compound LP-3 with photocrosslinking properties obtained in Examples 1 to 3, Epoxy Hafestel HE-1,1
-IE-3 and the above-mentioned 1-IE-6 were used to prepare an active energy ray-curable resin composition having the following composition.

LP-3100 parts by weight HE-150ti HE-320tt HE-650tt Irgacure 651 10 u Triphenylsulfonium tetrafluoroborate 7.0/1 Nostal Violet 0.5 t-Butylhydroquinone 0.5 in MIS/ 1:1 mixture of toluene 300 A pattern was formed in the same manner as in Example 1 using the above active energy ray curable resin composition.

The resulting pattern image was clear and had a resolution of 50-.

Next, post-exposure and heating were carried out in the same manner as in Example 1, and a cross-cut tape peeling test was conducted.
00 was shown, and the area where the cross-cut was clearly scratched was completely adhered.

Further, this substrate was immersed in a NaOH aqueous solution having a pH of 9.0, and a boiling test was conducted for 8 hours. After the boiling test, a cross-cut tape peeling test and a peeling test on a 50μ pattern were carried out again, but no deterioration in adhesion such as peeling or lifting was observed in either case. Furthermore, no deterioration such as whitening of the coating film was observed.

Example 6 Methyl methacrylate, tetrahydrofurfuryl acrylate, and n-butyl acrylate (= 50/30/2
0 molar ratio) in toluene to obtain a weight average molecular weight of 8. A linear polymer compound (referred to as LP-4) having OX 10' and a glass transition temperature of 55° C. was obtained.

Epoxy Herfestel HE- obtained in Examples 1 to 3
Using 3, HE-4 and the above-mentioned linear polymer compound LP-4, an active energy ray-curable resin composition having the following composition was prepared.

LP-4100 parts by weight HE-32011 HE-4100n 2-ethyl-4-methylimidazole 8/Irgaquia 651 10 1/crystal violet 0.5 t-butylhydro-based 0.5 MIB/toluene 1 .1 mixture 300 u A pattern was formed in the same manner as in Example 1 using the above active energy ray curable resin composition.

The resulting pattern image was clear and had a resolution of 50 scales.

Next, post-exposure and heating were carried out in the same manner as in Example 1, and a cross-cut tape peeling M test was conducted.
00 adhesion was 11, and the area where the cross-cut was clearly scratched was completely adhered.

Further, this substrate was immersed in a Na leaf wet liquid with pH=9.0, and a 4-hour boiling test was conducted. After the boiling test, a cross-cut tape peeling test and a peeling test on a 50μ pattern were carried out again, but no deterioration in adhesion such as peeling or lifting was observed in either case. Furthermore, no deterioration such as whitening of the coating film was observed.

Example 7 Using the linear polymer compound LP-4 obtained in Example 6, the epoxy halfester HE-3 obtained in Example 2, and HE-5 obtained in Example 4, the following composition was prepared. An active energy ray-curable resin composition was prepared.

LP-4100 parts by weight HE-320u HE-5100 // 2-ethyl-4-methylimidazole 8 Irgacure 651. IQ u crystal violet 0.5 t-butylhydroquinone 0.5 MIB/toluene 1.1 mixture 300 horns A pattern was formed in the same manner as in Example 1 using the above active energy ray curable resin composition. did.

The resulting pattern image was clear and had a resolution of 50μ.

Next, post-exposure and heating were carried out in the same manner as in Example 1, and a cross-cut tape peeling test was conducted.
It showed an adhesion of 0.00, and the adhesive was completely adhered to the surface, with no clear scratches removed.

Further, this substrate was immersed in an aqueous Na leaf solution having a pH of 9.0, and a 4-hour boiling test was conducted. After the boiling test, a cross-cut tape peeling test and a peeling test on a 50μ pattern were carried out again, but no deterioration in adhesion such as peeling or lifting was observed in either case. Furthermore, no deterioration such as whitening of the coating film was observed.

Example 8 Using the linear polymer compound LP-4 obtained in Example 6, the epoxy halfester HE-3 obtained in Example 2, and HE-6 obtained in Example 5, the following composition was prepared. An active energy ray-curable resin composition was prepared.

LP-4100 parts by weight HE-3201/ HE-610011 2-ethyl-4-methylimidazole 8 Irgacure 651 IQ // Crystal Violet 0.5 t-butylhydroquinone 0.5 MIBK/Toluene 1=1
Mixture 300 A pattern was formed in the same manner as in Example 1 using the above active energy ray curable resin composition.

The resulting pattern image was clear and had a resolution of 50 scales.

Next, post-exposure and heating were carried out in the same manner as in Example 1, and a cross-cut tape peeling test was conducted.
It showed an adhesion of 0.00, and the area where the cross-cut was clearly scratched was completely adhered.

Further, this substrate was immersed in an NaOH aqueous solution with pH=9.0, and a 4-hour boiling test was conducted. After the boiling test, a cross-cut tape peeling test and a peeling test on the 50 scale pattern were performed again, but no peeling occurred in either case.
No deterioration in second adhesion such as floating was observed. Furthermore, no deterioration such as whitening of the coating film was observed.

Comparative Example 1 Using LP-1@ obtained in Example], an active energy ray-curable resin composition having the following composition was prepared.

LP-1100 parts by weight Trimethylolpropane triacrylate 6011 Evicron 855 60, t Irgacure 65110/1 2-ethyl-4-methylimidazole 8t) Crystal violet 0.51° t-Butylhydro-based 0.57/NIB/Toluene 1
．． 1 mixture 300 lt A pattern was formed in the same manner as in Example 1 using the above active energy ray curable resin composition.

The resulting pattern image is blurry and has a resolution of 200
-, and patterns with line widths smaller than this were dissolved and removed during development.

Next, post-exposure and heating were performed in the same manner as in Example 1, and a cross-cut tape peeling test was performed. +00/+0
0, the @ property was good.

In addition, this substrate was immersed in an aqueous Na ice solution with a pH of 9.0, and a 4-hour boiling test was conducted. After the boiling test, the cross-cut tape peeling test was performed again and the result was IQ/10.
It was less than 0, indicating low indigenousness.

Comparative Example 2 Using LP-1 obtained in Example], an active energy ray-curable resin composition having the following composition was prepared.

LP-1100 parts by weight UE-820011+20 II Irgacure 651 10 u Crystal Violet 0.5/lt-butylhydroquinone 0.5〃MI8/Toluene 1
: 1 mixture 300 n Car 1: Acrylic acid ester of Evicron 855 Product of Dainippon Ink & Chemicals Co., Ltd. A pattern was formed in the same manner as in Example 1 using the above active energy ray curable resin composition.

The resulting pattern image was clear and had a resolution of 50u.

Next, post-exposure and heating were performed in the same manner as in Example 1, and a cross-cut tape peeling test was performed, resulting in a score of 10/+00.
The cost was relatively low.

Further, this substrate was immersed in an aqueous Na leaf solution with a pH of 9.0, and a 4-hour boiling test was conducted. The pattern had already peeled off in the boiling test.

As is clear from the above Examples and Comparative Examples, the active energy ray-curable resin composition of the present invention is capable of forming a high-resolution pattern, and at the same time has high adhesion to the support. It can be seen that it has excellent mechanical strength and chemical resistance.

Claims (1)

[Scope of Claims] 1) (i) A linear polymer having a glass transition temperature of 50° C. or higher and a weight average molecular weight of approximately 3.0×10^4 or higher, and (ii) an epoxy group in the molecule. An active energy ray-curable resin composition comprising a resin obtained by esterifying a part of the epoxy groups present in an epoxy resin containing at least one compound having two or more of the following with an unsaturated carboxylic acid. 2) The component (ii) is a resin obtained by esterifying 0.30 to 0.70 equivalents of 1.0 equivalents of epoxy groups present in the epoxy resin.
The active energy ray-curable resin composition described in 1. 3) The component (ii) is a resin obtained by esterifying 0.45 to 0.55 equivalents of 1.0 equivalents of epoxy groups present in the epoxy resin.
The active energy ray-curable resin composition described in 1. 4) Any one of claims 1 to 3, characterized in that it contains 20 to 80 parts by weight of the linear polymer (i) and 80 to 20 parts by weight of the resin (ii). An active energy ray-curable resin composition according to claim 1. 5) 0.1 to 20% by weight of a radical polymerization initiator that can be activated by the action of active energy rays, based on 100 parts by weight of the linear polymer (i) and the resin (ii). The active energy ray-curable resin composition according to any one of claims 1 to 4, characterized in that the active energy ray-curable resin composition is formed by blending. 6) 0.2 to 15% by weight of an element belonging to Group VIa or Group Va of the periodic table based on 100 parts by weight of the linear polymer in (i) and the resin in (ii). The active energy ray-curable resin composition according to any one of claims 1 to 5, characterized in that it contains an aromatic onium salt compound having photosensitivity.