JPH11242331A - Photosetting resin composition and photosensitive element using this composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the photosetting film good in imaging performance and superior in mechanical characteristics and heat resistance and flame retardation and electric characteristics by incorporating a reaction product of an epoxy resin selected from a specified bisphenol F type epoxy resin and a monocarboxylic acid having unsaturated groups, a specified photosetting resin, a flame retarder, a photoinitiator, a diluent, and a hardener as essential components. SOLUTION: This photosetting resin composition is composed essentially of the photosetting resin obtained by allowing the reaction product of the epoxy resin selected from the bisphenol F type epoxy resin represented by the formula or a rubber-modified epoxy resin with the monocarboxylic acid having unsaturated groups to react with a polybasic acid anhydride having saturated or unsaturated groups, the flame retarder, photoinitiator, the diluent, and the hardener. In the formula, X is an H atom or the like; and (n) is an integer of >=1. This photosetting resin composition is favorably used for manufacture of printed circuit boards, high density multilayer substrate, semiconductor packages, and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable resin composition used in the field of electric and electronic materials such as printed wiring boards and semiconductors, and more particularly to a flexible printed wiring board, a high-density multilayer board, and a tape carrier. Etc.
Solder resist excellent in image forming property, heat resistance, mechanical properties, flame retardancy, chemical resistance, etc., interlayer insulating film (build-up material)
Alternatively, the present invention relates to a photocurable resin composition used as a plating resist or the like.

[0002]

2. Description of the Related Art Heretofore, a permanent mask resist in the production of a printed wiring board has been produced by a method of screen-printing a heat or ultraviolet curable resist ink. In recent years, with the high integration of electronic devices, it has become necessary to increase the definition of wiring patterns and insulating patterns in printed wiring boards. Since sagging or the like occurs, it is difficult to form a high-definition resist image. Then, the resist image forming method by photolithography has been developed, and various inks such as a solder resist and a marking resist have shifted from a conventional thermosetting type to an ultraviolet setting type capable of forming an image.

[0003] In the method using an ultraviolet curable ink,
A liquid type photosensitive resist is applied on a substrate by screen printing, curtain coating or spray application, or a dry film type photosensitive resist is thermocompressed on the substrate, and then irradiated with actinic rays such as ultraviolet rays through a negative mask. Then, a resist image is formed by developing. As described above, there are a liquid type and a dry film type of a photosensitive resist, and in the case of a dry film type photosensitive resist, air is easily entrained when air is thermally pressed to a base material, so that adhesion is reduced or the resist is deteriorated. There is a concern that the image may be disturbed and the resist performance may be degraded. On the other hand, there are a solvent development type and an alkali development type in the permanent mask resist, but the alkali development type is predominant from the viewpoint of work environment and global environmental protection. As such a thing, what is indicated by Unexamined-Japanese-Patent No. 61-243869 and Unexamined-Japanese-Patent No. 1-141904 is known.

Up to now, the mainstream of protecting a circuit of a flexible printed wiring board has been a method in which a mold made of a film of polyimide, polyethylene terephthalate or the like is formed according to a pattern, punched out, and then bonded by thermocompression bonding using an adhesive. However, this method can form a cover coat material having excellent bending characteristics, withstand voltage characteristics, etc., but it is inefficient and has low dimensional accuracy because a cover lay film that has been manually drilled is bonded during processing. There is. In the thermocompression bonding process, a large and expensive hot press is used,
Since it is necessary to perform the treatment for a long time at a high temperature and a high pressure, there is a disadvantage that the production cost is increased.

Further, there is a method of applying a flexible ultraviolet-curable or thermosetting resist ink to a required portion by screen printing to form a solder resist. There is a great demand for high accuracy and high resolution of the solder resist, and there is a problem that pattern accuracy cannot be obtained by a screen printing method using an ultraviolet curable or thermosetting resist ink.

In the field of flexible printed wiring boards, an alkali-developable photosensitive liquid solder resist has been used to meet the demand for higher density. Although the pattern accuracy can be obtained, the coating film is hard and does not have sufficient flexibility and folding resistance, and if the flexibility and folding resistance are good, the coating film tack is large and the workability is high. There is a problem, and heat resistance and chemical resistance are insufficient. Further, there is a problem that the range of use is limited due to insufficient flame retardancy.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a cured film having good image forming properties and excellent mechanical properties, heat resistance, flame retardancy and electrical properties. It is an object of the present invention to provide a photocurable resin composition suitably used for manufacturing substrates, semiconductor packages, and the like.

[0008] The present invention also provides an excellent image-forming property, flame-retardant property obtained by laminating a layer of the photocurable resin composition on a support.
It is an object of the present invention to provide a photosensitive element from which a cured film having mechanical properties, heat resistance and electrical insulation can be obtained.

[0009]

The present invention provides a compound represented by the general formula (I):
A reaction product of an epoxy resin (a) selected from bisphenol F type epoxy resin or rubber-modified epoxy resin represented by and an unsaturated group-containing monocarboxylic acid (b),
Photocurable resin (A), flame retardant (B), photoinitiator (C), diluent (D) and curing agent (C) obtained by reacting a saturated or unsaturated group-containing polybasic acid anhydride (c). It is intended to provide a photocurable resin composition containing E) as an essential component.

[0010]

Embedded image (X is a hydrogen atom or

[0011]

Embedded image n is an integer of 1 or more. The present invention also provides a photosensitive element obtained by laminating a layer of the photocurable resin composition on a support.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The photocurable resin (A) used in the present invention is incompatible with the epoxy resin (a) selected from the bisphenol F type epoxy resin represented by the general formula (I) or the rubber-modified epoxy resin. It is obtained by reacting a reaction product (A ') with a saturated group-containing monocarboxylic acid (b) with a saturated or unsaturated group-containing polybasic acid anhydride (c). Specifically, in the first reaction, a hydroxyl group is formed by an addition reaction between the epoxy group of the epoxy resin (a) and the carboxyl group of the unsaturated group-containing monocarboxylic acid (b), and the generated hydroxyl group in the next reaction It is presumed that a half ester reaction occurs between the acid anhydride group of the polybasic acid anhydride (including the hydroxyl group originally contained in the epoxy resin (a)) and the saturated or unsaturated group-containing polybasic acid anhydride (c).

In the general formula (I), X is

[0014]

Embedded image Can be obtained by, for example, reacting a hydroxyl group of a bisphenol F type epoxy resin represented by the general formula (II) with epichlorohydrin. In order to promote the reaction between the hydroxyl group and epichlorohydrin, it is preferable to carry out the reaction in a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethylsulfoxide at a reaction temperature of 50 to 120 ° C. in the presence of an alkali metal hydroxide. Reaction temperature is 50 ° C
If the reaction temperature is lower than 120 ° C., side reactions often occur, which is not preferable.

[0015]

Embedded image (N is 1 or more, preferably an integer of 2 to 20.) Examples of the rubber-modified epoxy resin include the above-described bisphenol F epoxy resin, bisphenol A epoxy resin, and salicylaldehyde epoxy resin (for example,
Epoxy resin represented by the following general formula (III)), phenol novolak type epoxy resin or cresol novolak type epoxy resin, part or all of the epoxy groups are carboxylic acid-modified butadiene-acrylonitrile rubber at both ends, amino-terminal modified It is obtained by modification with silicone rubber or the like.

[0016]

Embedded image (X is a hydrogen atom or

[0017]

Embedded image m is an integer of 1 or more. Also, if necessary, the epoxy resin (a) may include, for example,
A cresol novolak type epoxy resin, a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a salicylaldehyde type epoxy resin, or the like can be partially used in combination.

Examples of the unsaturated group-containing monocarboxylic acid (b) in the present invention include acrylic acid, a dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β
-Styrylacrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid, etc., and a half-ester compound which is a reaction product of a hydroxyl group-containing acrylate with a saturated or unsaturated dibasic anhydride, an unsaturated group A half-ester compound which is a reaction product of a contained monoglycidyl ether and a saturated or unsaturated dibasic acid anhydride is exemplified. These half-ester compounds can be obtained by reacting a hydroxyl group-containing acrylate or an unsaturated group-containing monoglycidyl ether with a saturated or unsaturated dibasic acid anhydride in an equimolar ratio. These unsaturated group-containing monocarboxylic acids (b) can be used alone or in combination of two or more.

The hydroxy group-containing acrylate and unsaturated group-containing monoglycidyl ether used in the synthesis of the above half ester compound which is an example of the unsaturated group-containing monocarboxylic acid (b) include, for example, hydroxyethyl acrylate,
Hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate,
Examples include polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, pentaerythritol pentamethacrylate, glycidyl acrylate, and glycidyl methacrylate. Examples of the saturated or unsaturated dibasic anhydride used in the synthesis of the half ester compound include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, and ethyltetrahydrophthalic anhydride. Acids, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

In the reaction between the epoxy resin (a) and the unsaturated group-containing monocarboxylic acid (b) in the present invention, the unsaturated group-containing monocarboxylic acid (b) is added to one equivalent of the epoxy group of the epoxy resin (a). ) Is preferably 0.8 to 1.05 equivalents, more preferably 0.9 to 1.0 equivalents.

The epoxy resin (a) and the unsaturated group-containing monocarboxylic acid (b) are dissolved in an organic solvent and reacted. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, toluene, xylene, and the like. Aromatic hydrocarbons such as tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc. Glycol ethers, ethyl acetate, butyl acetate, butyl cellosolve acetate, esters such as carbitol acetate, aliphatic hydrocarbons such as octane, decane, petroleum ether, petroleum naphtha, hydrogenated petroleum Sa, include petroleum solvents such as solvent naphtha. Further, it is preferable to use a catalyst to promote the reaction. As the catalyst used,
For example, triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine and the like can be mentioned. The amount of the catalyst used is based on 100 parts by weight of the total of the epoxy resin (a) and the unsaturated group-containing monocarboxylic acid (b).
0.1 to 10 parts by weight. It is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and the like, and the amount used thereof is a total of 100% by weight of the epoxy resin (a) and the unsaturated group-containing monocarboxylic acid (b). Parts by weight, preferably 0.01 to 1 part by weight. The reaction temperature is preferably from 60 to 150 ° C, more preferably from 80 to 120 ° C.

If necessary, the unsaturated group-containing monocarboxylic acid (b) may be replaced with a polybasic acid anhydride such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride or the like. Can be used in combination.

The photocurable resin (A) in the present invention can be obtained by reacting the above-mentioned reaction product (A ') with a polybasic acid anhydride (c) containing a saturated or unsaturated group.

Examples of the saturated or unsaturated group-containing polybasic anhydride (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, and ethyltetrahydrophthalic anhydride. , Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

In the reaction of the reaction product (A ') with the saturated or unsaturated group-containing polybasic anhydride (c), the reaction product (A') has one saturated or unsaturated hydroxyl group per equivalent. The acid value of the photocurable resin (A) can be adjusted by reacting 0.1 to 1.0 equivalent of the group-containing polybasic acid anhydride (c). The acid value of the photocurable resin (A) is 30 to 150 mg.
KOH / g, preferably 50 to 120 mgK
More preferably, it is OH / g. Acid value is 30mgK
If it is less than OH / g, the solubility of the photocurable resin composition in a dilute alkali solution will decrease, and if it exceeds 150 mgKOH / g, the electrical properties of the cured film will tend to decrease. The reaction temperature of the reaction product (A ') with the saturated or unsaturated group-containing polybasic anhydride (c) is preferably from 60 to 120C.

As the photocurable resin (A) used in the present invention, besides the resin obtained by the above-mentioned method, a commercially available product such as ZFR1178 and ZFR1179 (both manufactured by Nippon Kayaku) may be used. Can also.

Part of the photocurable resin (A) in the present invention is a cresol novolak type epoxy resin, a bisphenol F type epoxy resin, a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin or a salicylaldehyde type epoxy resin. It can be replaced with a styrene-maleic acid resin such as an acid-modified resin, a styrene-maleic anhydride copolymer modified with hydroxyethyl acrylate, or a styrene-maleic anhydride copolymer modified with hydroxyethyl methacrylate.

The amount of the photocurable resin (A) contained in the photocurable resin composition of the present invention is preferably 20 to 80 parts by weight, more preferably 20 to 80 parts by weight, per 100 parts by weight of the photocurable resin composition. It is used in an amount of 30 to 70 parts by weight.

Examples of the flame retardant (B) used in the present invention include brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds, aromatic condensed phosphoric acid esters, halogen-containing condensed phosphoric acid esters and the like. And the like.

Examples of the brominated epoxy compound include dibromophenol, tribromophenol, dibromocresol, bromophenoxyethanol, tribromoaniline,

[0031]

Embedded image (Y is a hydrogen atom or

[0032]

Embedded image p is 0 or 1 or more, preferably an integer of 1 to 20. )

[0033]

Embedded image (Z is

[0034]

Embedded image q is 0 or 1 or more, preferably an integer of 1 to 10. ) And the like.

As the acid-modified brominated epoxy compound, for example, a reaction product of a brominated epoxy resin (d) and an unsaturated group-containing monocarboxylic acid (e) is added to a saturated or unsaturated group-containing polybasic anhydride ( Photocurable resin (F) obtained by reacting f). Specifically, the reaction product (F ') of the brominated epoxy resin (d) and the unsaturated group-containing monocarboxylic acid (e) is reacted with a saturated or unsaturated group-containing polybasic anhydride (f). It is a photocurable resin (F) obtained by this.

The brominated epoxy resin (d) includes, for example, the compound represented by the general formula (IV) and the compound represented by the general formula (V).

Examples of the unsaturated group-containing monocarboxylic acid (e) include acrylic acid, a dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid and the like.

In the reaction between the brominated epoxy resin (d) and the unsaturated group-containing monocarboxylic acid (e), the unsaturated group-containing monocarboxylic acid ( e) is preferably reacted at a ratio of 0.8 to 1.05 equivalents, more preferably 0.1 to 1.05 equivalents.
9 to 1.0 equivalent.

The brominated epoxy resin (d) and the unsaturated group-containing monocarboxylic acid (e) are reacted by dissolving them in an organic solvent. Examples of the organic solvent include ethyl methyl ketone,
Ketones such as cyclohexanone, toluene, xylene,
Aromatic hydrocarbons such as tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether,
Dipropylene glycol diethyl ether, glycol ethers such as triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, butyl cellosolve acetate, esters such as carbitol acetate, octane, aliphatic hydrocarbons such as decane, petroleum ether,
Examples include petroleum-based solvents such as petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. Further, it is preferable to use a catalyst to promote the reaction. Examples of the catalyst used include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine and the like. The amount of the catalyst used is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total of the epoxy resin (d) and the unsaturated group-containing monocarboxylic acid (e). It is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and the like. The amount of the polymerization inhibitor used is the total of the brominated epoxy resin (d) and the unsaturated group-containing monocarboxylic acid (e). It is preferably 0.01 to 1 part by weight based on 100 parts by weight. The reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C.
It is.

The acid-modified brominated epoxy compound can be obtained by reacting the above reaction product (F ') with a saturated or unsaturated group-containing polybasic acid anhydride (f).

Examples of the polybasic anhydride (f) containing a saturated or unsaturated group include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, and ethyltetrahydrophthalic anhydride. , Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

In the reaction of the reaction product (F ') with the saturated or unsaturated group-containing polybasic acid anhydride (f), the reaction product (F') is saturated or unsaturated with respect to 1 equivalent of the hydroxyl group. The acid value of the acid-modified brominated epoxy compound can be adjusted by reacting 0.1 to 1.0 equivalent of the group-containing polybasic acid anhydride (c). The acid value of the acid-modified brominated epoxy compound is preferably from 10 to 150 mgKOH / g,
More preferably, it is 0 to 100 mgKOH / g.
When the acid value is less than 10 mg KOH / g, the solubility of the photocurable resin composition in a dilute alkali solution is reduced, and
If it exceeds H / g, the electrical properties of the cured film tend to decrease. The reaction temperature of the reaction product (F ') with the saturated or unsaturated group-containing polybasic anhydride (f) is preferably from 60 to 120C.

Examples of the antimony compound used as a flame retardant include antimony trioxide and antimony pentoxide. Antimony pentoxide is preferred from the viewpoint of the electrical properties of the cured film.

Examples of the phosphorus compound used as a flame retardant include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricylyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylyl phosphate, Tris (chloroethyl) phosphate,
Phosphate compounds such as tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate and tris (tribromoneopentyl) phosphate, or CR-733S, CR-741, CR747, PX
Aromatic condensed phosphoric acid esters such as -200 (all manufactured by Daihachi Chemical), CR-505, CR-509, CR-530,
CR504L, CR-570, CR380, CR387
(Above, manufactured by Daihachi Chemical Co., Ltd.).

The amount of the component (B) flame retardant contained in the photocurable resin composition of the present invention is determined by the photocurable resin composition 100
It is preferably used in an amount of 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight.

It is preferable to use a combination of a brominated epoxy compound and an antimony compound or a combination of an acid-modified brominated epoxy compound and an antimony compound as a flame retardant. The antimony compound is preferably blended in an amount of 10 to 500 parts by weight based on 100 parts by weight of the brominated epoxy compound or the acid-modified brominated epoxy compound.

Examples of the photoinitiator of the component (C) used in the present invention include benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, , 2-Diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1
Acetophenones such as -hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone , 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-
Amylanthraquinone, anthraquinones such as 2-aminoanthraquinone, 2,4-dimethylthioxanthone,
Thioxanthones such as 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4, Benzophenones such as 4'-bisdiethylaminobenzophenone, Michler's ketone, 4-benzoyl-4'-methyldiphenyl sulfide;
There are 4,6-trimethylbenzoyldiphenylphosphine oxide and the like, and these can be used alone or in combination of two or more.

Further, light such as tertiary amines such as ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, pentyl-4-dimethylaminobenzoate, triethylamine and triethanolamine. The polymerization initiators can be used alone or in combination of two or more.

[0049] The amount of the photoinitiator contained in the photocurable resin composition of the present invention is based on 100 parts by weight of the photocurable resin composition.
Preferably 0.5 to 20 parts by weight, more preferably 2-1.
5 parts by weight are used. If the amount is less than 0.5 part by weight, the exposed portion tends to be eluted during development, and if it exceeds 20 parts by weight, the heat resistance tends to decrease.

As the diluent for the component (D) used in the present invention, for example, an organic solvent and / or a photopolymerizable monomer can be used. Examples of the organic solvent include ethyl methyl ketone, ketones such as cyclohexanone, toluene,
Aromatic hydrocarbons such as xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Glycol ethers such as, ethyl acetate, butyl acetate, butyl cellosolve acetate, esters such as carbitol acetate, octane, aliphatic hydrocarbons such as decane,
Examples include petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. Examples of the photopolymerizable monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and ethylene glycol, methoxytetraethylene glycol, and polyethylene glycol. Glycol mono- or di (meth) acrylates, N, N-dimethyl (meth) acrylamide, N-methylol (meth)
(Meth) acrylamides such as acrylamide, N, N
-Aminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, hexanediol, trimethylolpropane, pentaerythritol,
Ditrimethylolpropane, dipentaerythritol,
Polyhydric alcohols such as tris-hydroxyethyl isocyanurate or phenols such as polyhydric (meth) acrylates of ethylene oxide or propylene oxide adduct thereof, phenoxyethyl (meth) acrylate, and polyethoxydi (meth) acrylate of bisphenol A (Meth) acrylates of ethylene oxide or propylene oxide adducts, glyceryl diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate and other glycidyl ethers (meth) acrylates, melamine (meth) acrylate, and caprolactone modified Tris (acryloxyethyl) isocyanurate and the like can be mentioned.

In the present invention, the diluent may be used alone or in combination of two or more kinds. The amount of the diluent contained in the photocurable resin composition may vary depending on the amount of the photocurable resin composition.
The amount is preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight in 0 parts by weight. If the amount is less than 5 parts by weight, the photosensitivity is low, and the exposed part tends to elute during development.
When the amount exceeds the weight part, the heat resistance tends to decrease.

As the curing agent of the component (E) used in the present invention, a compound which is itself cured by heat, ultraviolet rays, or the like, or a carboxy group or a hydroxyl group of the photocurable resin component in the composition of the present invention may be used. Compounds that cure with ultraviolet light or the like are preferred. By using a curing agent, heat resistance, adhesion, chemical resistance, and the like of the final cured film can be improved. Examples of the curing agent include epoxy compounds, melamine compounds, urea compounds, and oxazoline compounds as thermosetting compounds. Examples of the epoxy compound include bisphenol A epoxy resin, bisphenol F epoxy resin, and alkyl-substituted bisphenol F
Epoxy resin, hydrogenated bisphenol A epoxy resin, brominated bisphenol A epoxy resin, novolak epoxy resin, bisphenol S epoxy resin,
Examples include a heterocyclic epoxy resin such as triglycidyl isocyanurate and a bixylenol type epoxy resin.
Examples of the melamine compound include triaminotriazine, hexamethoxymelamine, hexabutoxylated melamine and the like. Examples of the urea compound include dimethylol urea.

The curing agent used in the present invention may be used alone or in combination of two or more. The amount of the curing agent contained in the photocurable resin composition is determined by the amount of the photocurable resin composition 1
It is preferably used in an amount of 2 to 50 parts by weight, more preferably 10 to 40 parts by weight, per 100 parts by weight. If less than 2 parts by weight,
The heat resistance of the final cured coating film tends to decrease, and if it exceeds 50 parts by weight, the developability tends to decrease.

An epoxy resin curing agent can be used in combination with the photocurable resin composition of the present invention for the purpose of further improving various properties such as heat resistance, adhesion and chemical resistance of the final cured film. Specific examples of such an epoxy resin curing agent include:
For example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-
Imidazole derivatives such as methyl-5-hydroxymethylimidazole: guanamines such as acetoguanamine and benzoguanamine: diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazide Polyamines such as: organic acid salts thereof and / or epoxy adducts: amine complexes of boron trifluoride: ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl Triazine derivatives such as -S-triazine: trimethylamine, triethanolamine,
N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, m-
Tertiary amines such as aminophenol: polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolak and alkylphenol novolak: organic phosphines such as tributylphosphine, triphenylphosphine and tris-2-cyanoethylphosphine: tri-n- Phosphonium salts such as butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride: quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride: polybasic anhydride: diphenyliodonium tetrafluoroporoate , Triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hex Hexafluorophosphate, and the like.

The epoxy resin curing agent may be used alone or in combination of two or more. The amount of the curing agent contained in the photocurable resin composition is preferably 100 parts by weight of the photocurable resin composition. 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight.

The photocurable resin composition of the present invention further comprises
For the purpose of further improving various properties such as adhesion and coating film hardness,
If necessary, known inorganic fillers such as barium sulfate, barium titanate, silica, talc, calcined kaolin, magnesium carbonate, aluminum oxide, aluminum hydroxide, and mica may be used alone or in combination of two or more. it can. The amount is preferably 2 to 80 parts by weight, more preferably 5 to 50 parts by weight, per 100 parts by weight of the photocurable resin composition.

The photocurable resin composition of the present invention may contain, if necessary, known phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and the like. Colorants, polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, thickeners such as bentone, montmorillonite, silicone-based, fluorine-based, vinyl resin-based defoamers, silane coupling agents, etc. Various known and commonly used additives can be used.

The photocurable resin composition of the present invention can be obtained by uniformly kneading and mixing the components with a roll mill, a bead mill or the like.

The photocurable resin composition of the present invention is, for example,
An image is formed as follows and used for preparing a cured coating film. That is, a flexible printed wiring board is coated with a film thickness of 10 to 200 μm by a method such as a screen printing method, a spray method, a roll coating method, a curtain coating method, an electrostatic coating method, and then the coating film is heated to 60 to 110 ° C. After drying in
The negative film is brought into direct contact (or non-contact via a transparent film) and irradiated with active light (eg, ultraviolet light), and then the exposed portion is dissolved and removed (developed) with a dilute alkaline aqueous solution. Next, the exposed part is post-exposed (ultraviolet light exposure)
And / or sufficient post-heating to obtain a cured film. Post-exposure is preferably, for example, 1 to 5 J / cm ² , and post-heating is preferably performed at 100 to 200 ° C. for 30 minutes to 12 hours.

[0060]

The present invention will be described more specifically with reference to Synthesis Examples and Examples of the present invention. In addition, in a synthetic example, the part and% in an Example show a weight part and weight% unless there is particular notice.

Synthesis Example 1 990 parts of YDF2004 (a bisphenol F type epoxy resin manufactured by Toto Kasei), 72 parts of acrylic acid, and 400 parts of carbitol acetate were charged and heated to 90 ° C. with stirring to dissolve the reaction mixture. Next, the mixture was heated to 100 ° C. and reacted until the acid value became 1 mgKOH / g. Next, 150 parts of tetrahydrophthalic anhydride and 120 parts of carbitol acetate were charged, heated to 80 ° C., reacted for about 6 hours, and cooled to obtain a photocurable resin (I) (component A) having a solid concentration of 70%. Was.

Synthesis Example 2 YDB400 (manufactured by Toto Kasei, brominated bisphenol A)
Epoxy resin) 400 parts, epichlorohydrin 900
After dissolving 400 parts of dimethyl sulfoxide, 7
At 0 ° C., 50 parts of sodium hydroxide were added over 1 hour.
After the addition, the reaction was continued for another 3 hours, and then the excess unreacted epichlorohydrin and dimethyl sulfoxide were removed under reduced pressure. Thereafter, the resultant was dissolved in 700 parts of methyl isobutyl ketone, and 10 parts of 30% sodium hydroxide was added thereto.
The reaction was carried out at a temperature of 1 hour. After completion of the reaction, the resultant was washed with water and separated into oil and water, and then methyl isobutyl ketone was distilled and recovered from the oil layer to obtain an epoxy resin. The obtained epoxy resin accounts for about 90% of the hydroxyl groups in YDB400, calculated from the epoxy equivalent.
Was epoxidized with a glycidyl group.

Next, 450 parts of the obtained epoxy resin, 144 parts of acrylic acid, and 200 parts of carbitol acetate were charged and heated to 90 ° C. with stirring to dissolve the reaction mixture. Next, it is heated to 100 ° C., and the acid value is 1 mgKOH / g.
The reaction was continued until Next, 150 parts of tetrahydrophthalic anhydride and 120 parts of carbitol acetate were charged.
Heated to 80 ° C, reacted for about 6 hours, cooled, solid concentration 7
0% of the photocurable resin (II) (component B) was obtained.

Synthesis Example 3 YDB400 (manufactured by Toto Kasei, brominated bisphenol A)
(Type epoxy resin), 400 parts of acrylic acid, and 120 parts of carbitol acetate were charged, and heated and stirred at 90 ° C. to dissolve the reaction mixture. Next, the mixture was cooled to 60 ° C., charged with 2 parts of trimethylbenzylammonium chloride, heated at 100 ° C., and reacted until the acid value became 1 mgKOH / g. Next, tetrahydrophthalic anhydride 15
0 parts and 85 parts of carbitol acetate are charged at 80 ° C.
And reacted for about 6 hours and cooled to obtain a photocurable resin (III) (component B) having a solid content concentration of 75%.

Synthesis Example 4 YDB400 (manufactured by Toto Kasei, brominated bisphenol A)
(Type epoxy resin), 400 parts of acrylic acid, and 120 parts of carbitol acetate were charged, and heated and stirred at 90 ° C. to dissolve the reaction mixture. Next, the mixture was heated to 100 ° C. and reacted until the acid value became 1 mgKOH / g. Next, 98 parts of maleic anhydride and carbitol acetate 85
And heated to 80 ° C., reacted for about 6 hours and cooled,
A photocurable resin (IV) (component B) having a solid content of 73% was obtained.

Synthesis Example 5 280 parts of BREN-S (manufactured by Nippon Kayaku, brominated novolak type epoxy resin), 55 parts of acrylic acid, and 120 parts of carbitol acetate were charged, and the mixture was heated to 90 ° C. and stirred to dissolve the reaction mixture. did. Next, the mixture was heated to 100 ° C. and reacted until the acid value became 1 mgKOH / g. Next, 110 parts of tetrahydrophthalic anhydride and 60 parts of carbitol acetate were charged, heated to 80 ° C., reacted for about 6 hours and cooled, and a photocurable resin (V) having a solid concentration of 70% (B) (component B)
I got

Synthesis Example 6 220 parts of FAE 2500 (manufactured by Nippon Kayaku, rubber-modified salicylaldehyde type epoxy resin), 72 parts of acrylic acid, and 120 parts of carbitol acetate were charged, and heated to 90 ° C. with stirring to dissolve the reaction mixture. . Next, the mixture was cooled to 60 ° C., charged with 2 parts of trimethylbenzylammonium chloride, and heated to 100 ° C. to give an acid value of 1 mgKOH / g.
The reaction was continued until Next, 150 parts of tetrahydrophthalic anhydride and 70 parts of carbitol acetate were charged, and 8 parts were added.
Heated to 0 ° C, reacted for about 6 hours, cooled, solid content 70
% Of the photocurable resin (VI) (component (A)).

Synthesis Example 7 Epicoat 1001 (bisphenol A type epoxy resin, manufactured by Yuka Shell Epoxy) 420 parts, acrylic acid 72
Parts, 200 parts of carbitol acetate, 90 ° C
The mixture was heated and stirred to dissolve the reaction mixture. Next, the mixture was cooled to 60 ° C. and trimethylbenzyl ammonium chloride 2
And heated to 100 ° C., acid value is 1 mg KOH
/ G to obtain a photocurable resin (VII) having a solid concentration of 70% (part of the component A).

Synthesis Example 8 YDB400 (manufactured by Toto Kasei, brominated bisphenol A)
(Type epoxy resin), 400 parts of acrylic acid, 72 parts of acrylic acid, and 200 parts of carbitol acetate were charged, heated to 90 ° C. and stirred to dissolve the reaction mixture. Next, the mixture was cooled to 60 ° C., charged with 2 parts of trimethylbenzylammonium chloride, heated to 100 ° C., and reacted until the acid value became 1 mg KOH / g.
III) (Component B) was obtained.

Synthesis Example 9 Epicoat 1004 (manufactured by Yuka Shell Epoxy, bisphenol A type epoxy resin) 930 parts, acrylic acid 72
Parts, 400 parts of carbitol acetate, 90 ° C
The mixture was heated and stirred to dissolve the reaction mixture. Next, the mixture was cooled to 60 ° C., and 2 parts of triphenylphosphine was charged.
The mixture was heated to ° C. and reacted until the acid value became 1 mgKOH / g. Next, 150 parts of tetrahydrophthalic anhydride and 100 parts of carbitol acetate were charged, heated to 80 ° C., reacted for about 6 hours, and cooled to obtain a photocurable resin (IX) (solid resin) having a solid concentration of 70%. Was.

Examples 1 to 5 and Comparative Example 1 The compositions were formulated according to the composition shown in Tables 1 and 2, and
The mixture was kneaded with this roll mill to prepare a photocurable resin composition.
This is applied to a copper polyimide film substrate on which a copper wiring pattern is formed so as to have a thickness (after drying) of about 30 μm by using a 120-mesh tetron screen by a screen printing method. It was dried in a hot air circulation type dryer for minutes. Next, a negative mask having a predetermined pattern is brought into close contact with the coating film using an ultraviolet exposure apparatus,
Exposure is performed at 500 mJ / cm ² . Thereafter, spray development was performed with a 1% aqueous solution of sodium carbonate for 60 seconds at a pressure of 1.8 kgf / cm ² , and the exposed portion was dissolved and developed. The developability and photosensitivity were evaluated using the obtained image.
After heating for a time, a test plate was prepared. The test plates were tested for adhesion, solvent resistance, acid resistance, alkali resistance, solder heat resistance, bending resistance, folding resistance, and flame retardancy as described below. Table 1,
Table 2 summarizes the evaluation results. In addition, the test method and the evaluation method are as follows.

[Developability]: The following evaluation criteria were used.・ ・ ・: The composition was completely removed after development, and development was possible. ・ ・ ・: Slight residue was left after development. After drying, 21 steps of step tablets (manufactured by Stoffer Co., Ltd.) are brought into close contact with the coating film, and the integrated exposure amount is 50
The film was irradiated with ultraviolet rays of 0 mJ / cm ² and developed with a 1% aqueous solution of sodium carbonate for 60 seconds. Thereafter, the number of steps of the coating film left undeveloped was confirmed. ○: 8 steps or more △: 5 to 7 steps ×: 4 steps or less [Adhesion]: One test piece according to JIS K5400
A 100 mm-thick grain was prepared and subjected to a peeling test with a cellophane tape. The state of peeling was evaluated by the following criteria.・ ・ ・: No peeling at least 90/100 △: no peeling at least 50/100 to less than 90/100 ×: no peeling at 0/100 to less than 50/100 [solvent resistance]: The test piece was immersed in isopropyl alcohol at room temperature for 30 minutes, and after confirming that there was no abnormality in appearance, a peeling test was performed using a cellophane tape. ○ ・ ・ ・ ・ No abnormality in the appearance of the coating film and no peeling ×× ・ ・ An abnormality in the appearance of the coating film or peeling [Acid resistance]: The test piece was placed in a 10% hydrochloric acid aqueous solution at room temperature. After immersion for 30 minutes and confirming that there was no abnormality in the appearance, a peeling test was performed using a cellophane tape. ○ ・ ・ ・ No abnormality in coating film appearance and no peeling × ・ ・ ・ ・ No abnormality in coating film appearance or peeling [Alkali resistance]: Test specimen was treated with 5% aqueous sodium hydroxide solution After immersion at room temperature for 30 minutes and confirming that there was no abnormality in the appearance, a peeling test was carried out using a cellophane tape. ○ ・ ・ ・ ・ No abnormalities in the appearance of the coating film and no peeling × ・ ・ ・ ・ No abnormalities in the appearance of the coating film or peeling [Solder heat resistance]: Apply rosin-based flux to the test piece It was immersed in a solder bath at 260 ° C. for 10 seconds. This was defined as one cycle, and after six cycles were repeated, the appearance of the coating film was visually observed. ○ ・ ・ ・ ・ There is no abnormality (peeling, swelling) in the appearance of the coating film and there is no peeling of the solder. [Bending resistance]: Performed according to JIS K5400. Using a test piece, the diameter of the mandrel was 2 mm, and the presence or absence of cracks was observed. When a crack occurred, it was evaluated as x, and when no crack occurred, it was evaluated as ○.

[Folding resistance]: Goby folding (180 °) was performed, and the presence or absence of cracks was observed. When a crack occurred, it was evaluated as x, and when no crack occurred, it was evaluated as ○.

[Flame retardancy]: A test piece was prepared and subjected to a combustion test according to the UL94 standard. ○ ・ ・ ・ ・ The flame extinguished within 10 seconds without residual flame until the clamp ×× ・ The flame persisted until the clamp or did not extinguish after more than 10 seconds

[0075]

[Table 1] * 1 ZFR1179: rubber-modified epoxy resin containing 60% solid content (acid manufactured by Nippon Kayaku) * 2 PX-200: aromatic condensed phosphoric acid ester (manufactured by Daihachi Chemical) * 3 Epicoat 828: bisphenol A type epoxy resin ( * 4 Epicoat 1001: bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy) * 5 Colorad DPHA: dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku) * 6 M-325: caprolactone-modified Tris (acry) Roxyethyl) isocyanurate (Toa Gosei) * 7 Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (Ciba-Geigy) * 8 Kayacure DETX-S: 2,4-diethyl Thioxanthone (Nippon Kayaku) * Cannot be developed Not rated due to

[0076]

According to the photocurable resin composition and the photosensitive element of the present invention, a cured film having good image forming properties and excellent mechanical properties, heat resistance, flame retardancy and electrical properties can be obtained. It is suitably used for manufacturing printed wiring boards, high-density multilayer boards, semiconductor packages and the like.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takahiko Kutsuna Inside the Kashima Plant of Hitachi Chemical Co., Ltd.

Claims (5)

[Claims] 1. A reaction product of an epoxy resin (a) selected from a bisphenol F type epoxy resin represented by the general formula (I) or a rubber-modified epoxy resin and an unsaturated group-containing monocarboxylic acid (b) is added to a saturated product. Alternatively, a photocurable resin (A), a flame retardant (B), a photoinitiator (C), a diluent (D) and a curing agent (E) obtained by reacting an unsaturated group-containing polybasic acid anhydride (c). A) a photocurable resin composition comprising as an essential component. Embedded image (X is a hydrogen atom or n is an integer of 1 or more. ) 2. The photocurable resin composition according to claim 1, wherein the flame retardant comprises a combination of a brominated epoxy compound and an antimony compound, or a combination of an acid-modified brominated epoxy compound and an antimony compound. 3. The photocurable resin composition according to claim 1, wherein the flame retardant is a phosphate compound, an aromatic condensed phosphate ester or a halogen-containing condensed phosphate ester. 4. An acid-modified brominated epoxy compound, which is a flame retardant, is obtained by adding a saturated or unsaturated group-containing polybasic acid to a reaction product of a brominated epoxy resin (d) and an unsaturated group-containing monocarboxylic acid (e). The photocurable resin composition according to claim 2, which is a photocurable resin (F) obtained by reacting an anhydride (f). 5. A photosensitive element obtained by laminating a layer of the photocurable resin composition according to claim 1, on a support.