JPH06301205A - Photosensitive resin composition and photosensitive element using the same - Google Patents

Abstract

PURPOSE:To enhance thermal stability, to enable development with water or an aq. alkali soln. and to form a soldering mask excellent in resolution and heat resistance to soldering by incorporating a specified polymer, a reactant an epoxy compd. and a photo-initiator. CONSTITUTION:The objective photosensitive resin compsn. contains a vinyl polymer (a) having groups represented by the formula in the side chain, a reactant (b) of water-soluble hydantoin epoxy resin with unsatd. monocarboxylic acid, an epoxy compd. (c) having one or more epoxy grops in one molecule and a photo-initiator (d) which generates free radicals under active light. This compsn. is laminated on a substate film to obtain the objective photosensitive element. In the formula, each of R1 and R2 is H, alkyl or aryl and R3 is alkyl or hydroxyalkyl. Tris(2,3-epoxypropyl) isocyanurate or water-soluble hydantoin epoxy resin is preferably used as the epoxy compd. (c).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, more specifically, a photosensitive resin composition for forming a protective film which can be used for printed wiring board production, precision metal processing, etc., and a photosensitive resin composition using the same. Regarding elements.

[0002]

2. Description of the Related Art Conventionally, in the printed wiring board industry,
Photosensitive resin compositions having excellent properties are used for solder masks, resists for chemical plating, and the like. The main purpose of the solder mask is to limit the soldering area during soldering, prevent solder bridges, etc., prevent corrosion of bare copper conductors, and maintain electrical insulation between conductors for a long period of time. As the solder mask, a printing mask containing a thermosetting resin such as an epoxy resin or an aminoplast resin as a main component is usually used. However, in recent years, along with the miniaturization and high performance of electric devices, miniaturization of individual parts such as resistors and capacitors, leadlessness, and increased pin count of IC parts,
Narrow pin pitch, diversification of package form,
Furthermore, the printed wiring boards on which these parts are mounted are also becoming denser in conductor patterns (thin lines, narrower conductor gaps, smaller via holes, and more layers). Surface mounting technology for mounting chip parts that can achieve higher densities is becoming popular in place of conventional lead insertion parts and pin insertion mounting, and in order to respond to this, the solder resist used for printed wiring boards is also located. A high-precision one having excellent precision and resolution has been demanded, and it has become difficult to cope with the conventional printing method of forming a pattern by using screen printing.

Therefore, the advent of a photosensitive resin composition for forming a highly accurate and highly reliable solder mask excellent in dimensional accuracy and resolution by a photographic developing method (a method of forming an image by developing after image exposure) has been developed. Has been desired. Conventionally, as a photosensitive resin composition for forming a solder mask, a photosensitive resin composition containing an acrylic polymer and a photopolymerizable monomer as main components (Japanese Patent Laid-Open Nos. 53-56018 and 54-1018).
No. gazette) is known. However, these photosensitive resin compositions have a drawback that the heat resistance of the cured film is not sufficient because of the large amount of acrylic polymer used for imparting film property. On the other hand, as a photosensitive resin composition having good heat resistance, a composition containing a photosensitive epoxy resin having a chalcone group in its main chain and an epoxy resin curing agent as main components (Japanese Patent Laid-Open Nos. 54-82073, 5 and 5).
8-62636) has been proposed. But,
These photodimerization type photosensitive resin compositions have low sensitivity, so that it is difficult to form a thick film resist, and since it is necessary to use a flammable organic solvent such as cyclohexanone as a developing solution, it is also safe. Not preferable.

Further, a composition containing an epoxy group-containing novolac type epoxy acrylate and a photopolymerization initiator as main components (JP-A-61-272, etc.) has also been proposed. These components have excellent heat resistance and are useful, but it is necessary to use a 1,1,1-trichloroethane / lower alcohol mixed solution as a developing solution, which is a problem in developing solution management. In addition, the use of 1,1,1-trichloroethane is not preferable in terms of environmental protection because it may cause groundwater contamination. The photosensitive resin composition for forming a solder mask, which is excellent in safety and economy and can be developed with an alkaline aqueous solution, is a composition containing a carboxyl group-containing polymer, a monomer, a photopolymerization initiator and a thermosetting resin as main components. (JP-A-48-73
No. 148, No. 57-178237, No. 58-
No. 42040, No. 59-151152, etc.) are known. In these compositions, an epoxy resin, a melamine resin, a urea resin or the like is used as a thermosetting resin, and an example in which an epoxy resin insoluble in an organic solvent such as triglycidyl isocyanurate is dispersed is also disclosed. However, these compositions do not always have sufficient characteristics such as resolution, solvent resistance, and solder heat resistance when absorbing moisture. Further, in JP-A-61-243869, an oligomer obtained by reacting a reaction product of a novolac type epoxy resin and acrylic acid (acid equivalent / epoxy equivalent ratio 0.95 to 1.05) with an acid anhydride is disclosed. A liquid resist ink composition containing a photopolymerization initiator, an epoxy resin such as triglycidyl isocyanurate, an epoxy resin curing agent such as imidazole, a filler and a solvent has been proposed. This composition can be developed with an aqueous alkaline solution and has excellent properties as a solder mask. However, this composition has a short pot life because the epoxy group and the carboxyl group are mixed, and has a narrow drying margin (time and temperature conditions until the reaction proceeds due to heating during drying and development cannot be performed). It has the drawback of poor workability.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art, has high thermal stability, and has a wide working margin.
Photosensitive resin composition which can be developed with water or alkaline aqueous solution excellent in safety and economy, and can form a highly reliable solder mask excellent in resolution, solder heat resistance and the like, and a photosensitive element using the same The purpose is to provide.

[0006]

The present invention provides a compound represented by the general formula (I) in the side chain (a).

[Chemical 2] [Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group or an aryl group, and R ₃ represents an alkyl group or a hydroxyalkyl group], a vinyl polymer having a group (b). Reaction product of water-soluble hydantoin epoxy resin and unsaturated monocarboxylic acid, (c) 1 in 1 molecule
An epoxy compound having one or more epoxy groups and (d)
The present invention relates to a photosensitive resin composition containing a photoinitiator which generates free radicals by active light, and a photosensitive element obtained by laminating this composition on a support film.

Hereinafter, each component contained in the photosensitive resin composition of the present invention will be described in detail. The photosensitive resin composition of the present invention contains, as an essential component (a), a vinyl polymer having a group represented by the above general formula (I) in its side chain. The component (a) is composed of a unit of a polymerizable unsaturated monomer having a group (amine imide group) represented by the general formula (I) and a unit of another polymerizable monomer used as necessary. .
As the polymerizable unsaturated monomer having an amine imide group,
The following general formula (II) and general formula (III)

[0008]

[Chemical 3]

[Wherein R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (methyl group, ethyl group, propyl group, hexyl group, etc.), halogen (chlorine, bromine, etc.) or cyano group, and R ₁ , R ₂ and R ₃ represent the above, X represents an alkyl group, an aryl group or an aralkyl group, and n is 1 to 4
Represents an integer of] and the like. Specifically, as the monomer represented by the general formula (II), 1,1,1-trimethylamine methacrylimide,
1,1-dimethyl-1-ethylamine methacrylimide, 1,1-dimethyl-1- (2-hydroxypropyl) amine methacrylimide, 1,1-dimethyl-1-
(2′-phenyl-2′-hydroxyethyl) amine methacrylimide, 1,1-dimethyl-1- (2′-hydroxy-3′-phenoxypropyl) amine methacrylimide, 1,1,1-trimethylamine acrylimide, etc. Is mentioned. Examples of the monomer represented by the general formula (III) include monomers represented by the following formulas (IV) and (V).

[0010]

[Chemical 4]

[0011] In addition, JOURNALOF POLYMER SCIENCE
PART A-1) Volume 6, pages 363-373, 1968 / same volume, 2197-2207, 1968 / same volume 9, 34
Pp. 53-3470, 1971, The Journal of Organic Chemistry
nic Chemistry) Vol. 33, No. 4, April, 1374-1
P. 378, 1968, Macromolecules
olecules) Volume 1, Issue 3, May-June, 254-260
Page, 1968 / Vol. 3, No. 6, November-December, 71
Pp. 5-722, 1970, Journal of Applied Polymer Science (JOURNALOF APPLIED POL
YMER SCIENCE) Vol. 15 2609-2621, 19
71, Chemical Reviews, Vol. 73, No. 3, pp. 255-281, 1973, Industry Engineering Chemistry, Production Research Development (Ind. Eng. Che
m., Prod. Res. Develp.) Vol. 13, No. 3, 197-2
01, 1974 / Vol. 19, No. 3, 338-349
Pp. 1980, Applied Polymer Symposium No. 26, 387-39.
The polymerizable unsaturated monomer having an amine imide group described in P. 7, 399 to 410, 1975, Fine Chemical 12.15, 14-24 (1985) and the like can be mentioned. The polymerizable unsaturated monomer is not limited to these.
Moreover, you may use these individually or in combination of 2 or more types. The amount of the polymerizable unsaturated monomer having an amine imide group contained in the vinyl polymer (a) in the present invention is usually 5% or more based on the moles of the polymer,
It is preferably 10% or more.

As another polymerizable monomer used as necessary, (meth) acrylic acid alkyl ester [(meth) acrylic acid means acrylic acid and methacrylic acid. The same applies hereinafter] (for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid 2
-Ethylhexyl, etc.), (meth) acrylic acid hydroxyalkyl ester (for example, (meth) acrylic acid hydroxyethyl, (meth) acrylic acid hydroxypropyl,
(Meth) acrylic acid hydroxyhexyl, etc.), aromatic vinyl monomer (for example, styrene, α-methylstyrene,
α-chlorostyrene etc.), halogen-containing monomer (eg vinyl chloride, vinylidene chloride etc.), alkyl or cycloalkyl vinyl ether (eg methyl vinyl ether, cyclohexyl vinyl ether etc.), vinyl ester (eg vinyl acetate etc.), nitrile Group-containing monomers (for example, (meth) acrylonitrile, etc.), amide group-containing monomers (for example, (meth) acrylamide, crotonamide, N-methylolacrylamide, fumaric acid diamide, etc.), carboxyl group-containing monomers ( For example, (meth) acrylic acid, maleic acid, maleic anhydride, etc.) can be mentioned. You may use these individually or in combination of 2 or more types.

The component (a) in the present invention comprises a unit of a polymerizable unsaturated monomer having a group (amine imide group) represented by the general formula (I) and optionally other polymerizable monomer. Although it can be obtained by polymerization, an amine imide group can be introduced after copolymerization. The method of introducing an amine imide group into the side chain after copolymerization is described in the above-mentioned documents and the like. For example, instead of a monomer having an amine imide group, a (meth) acrylic acid alkyl ester (for example, (meth ) Methyl acrylate, (meth)
Ethyl acrylate, 2-ethylhexyl (meth) acrylic acid, etc., (meth) acrylic acid hydroxyalkyl ester (for example, (meth) acrylic acid hydroxyethyl,
(Meth) acrylic acid hydroxypropyl, (meth) acrylic acid hydroxyhexyl, etc.) are used for copolymerization, and then a compound having at least one dimethylhydrazine and an epoxy group in the molecule and having no unsaturated group ( (For example, ethylene oxide, propylene oxide, phenyl glycidyl ether, glycidyl phthalimide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, adipic acid diglycidyl ester) Is added and the reaction is carried out by mixing with stirring.

The molecular weight of the vinyl polymer having a group represented by the general formula (I) in the side chain used as the component (a) in the present invention is usually 1,000 to 500,000, preferably 5,000 to. It is 100,000. When the molecular weight is less than 1,000, the film forming property tends to be poor,
When it is 500,000 or more, the developability tends to be poor.

The photosensitive resin composition of the present invention further contains a reaction product of a water-soluble hydantoin epoxy resin and an unsaturated monocarboxylic acid as the component (b). The water-soluble hydantoin epoxy resin used here is 5,
5-Dimethylhydantoin bisepoxide, 5,5-diethylhydantoin bisepoxide, 5-benzylhydantoin bisepoxide, 5-isopropylhydantoin bisepoxide, 5-pentamethylhydantoin bisepoxide, 5,5-tetramethylenehydantoin bisepoxide and the hydantoin Examples thereof include condensation reaction products of a bisepoxide derivative and a hydantoin derivative such as 5,5-dimethylhydantoin and 5,5-diethylhydantoin. Further, as the unsaturated monocarboxylic acid,
(Meth) acrylic acid, β-furylacrylic acid, β-styrylacrylic acid, α-cyanocinnamic acid, cinnamic acid and the like can be mentioned. For the production of the reaction product of these water-soluble hydantoin epoxy resin and unsaturated monocarboxylic acid, the acid equivalent / epoxy equivalent ratio is in the range of 0.8 to 1.5, preferably 0.9 to
It is carried out by a conventional method within the range of 1.1. For example, the hydantoin epoxy resin is dissolved in an inert organic solvent such as methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate or cyclohexanone, and a tertiary amine such as triethylamine, tri-n-butylamine or diethylcyclohexylamine as a catalyst, benzyltrimethyl chloride. It can be obtained by stirring and reacting a quaternary ammonium salt such as ammonium with hydroquinone, p-methoxyphenol or the like as a polymerization inhibitor at 70 to 120 ° C. with the unsaturated monocarboxylic acid.

The photosensitive resin composition of the present invention comprises the component (c)
As an epoxy compound having one or more epoxy groups in one molecule. Examples of such compounds include phenyl glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, allyl glycidyl ether, glycidyl methacrylate, octylene oxide, diglycidyl ether of bisphenol A, bisphenol A type epoxy resin,
Bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, N-glycidyl type epoxy resin, alicyclic epoxy resin manufactured by Chisso Co. (Chissonox 206, Chisso nox 221, Chisso nox 201 etc.), Daicel chemistry Alicyclic epoxy resin manufactured by Kogyo Co., Ltd. (Sexaroid 2021, etc.),
Examples thereof include tris (2,3-epoxypropyl) isocyanurate and water-soluble hydantoin epoxy resin. Of these, tris (2,3-epoxypropyl) isocyanurate and water-soluble hydantoin epoxy resin are preferable. This water-soluble hydantoin epoxy resin is the same as that described above as the component (b).
You may use these epoxy compounds individually or in combination of 2 or more types.

The photosensitive resin composition of the present invention comprises the component (d)
As, it contains a photoinitiator that generates free radicals by actinic light. Examples of such compounds include 4-hydroxyethoxyphenyl- (2-hydroxy-2-propyl) ketone, 2-ethylanthraquinone, 2-t-
Butyl anthraquinone, octamethyl anthraquinone,
Substituted or unsubstituted polynuclear quinones such as 1,2-benzanthraquinone and 2,3-diphenylanthraquinone, α-ketaldonyl alcohols and ethers such as benzoin and pivalone, α-phenyl-benzoin, α, α- Α-hydrocarbon substituted aromatic acyloins such as diethoxyacetophenone, benzophenone, aromatic ketones such as 4,4′-bisdialkylaminobenzophenone, 2-methylthioxanthone, 2,4-diethylthioxanthone,
Thioxanthones such as 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2-ethylthioxanthone, 2-methyl-1- [4- (methylthio) phenyl]
-2-morpholino-propanone-1 and the like. Of these, those soluble in water such as 4-hydroxyethoxyphenyl- (2-hydroxy-2-propyl) ketone are preferable. You may use these individually or in combination of 2 or more types.

The photosensitive resin composition of the present invention comprises the component (a)
1 part of the reaction product of the water-soluble hydantoin epoxy resin as the component (b) and the unsaturated monocarboxylic acid is added to 100 parts by weight of the vinyl polymer having a group represented by the general formula (I) in the side chain. To 200 parts by weight, 1 part of the epoxy compound having one or more epoxy groups in one molecule which is the component (c).
˜100 parts by weight, 1 to 1 part of the photopolymerization initiator which is the component (d)
It is preferable to use 100 parts by weight in order to form a solder mask excellent in resolution, solder heat resistance, solvent resistance, plating resistance, and electrical insulation.

The photosensitive resin composition of the present invention may further contain other auxiliary components. Examples of such a secondary component include fine-particle inorganic or organic fillers, thermal polymerization inhibitors, dyes, pigments, defoamers, flame retardants, plasticizers, adhesion improvers, and epoxy resin curing accelerators. And latent curing agents, etc., and these are selected under the same consideration as that for a normal photosensitive resin composition.

The photosensitive resin composition of the present invention may further contain a photopolymerizable unsaturated compound, if necessary. There are various types of photopolymerizable unsaturated compounds that can be contained, and acrylic acid-based or methacrylic acid-based compounds are practical. Examples of acrylic acid compounds include acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, benzyl acrylate, carbitol acrylate, methoxyethyl acrylate, ethoxyethyl. Acrylate, butoxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, butylene glycol acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, pentaerythritol monoacrylate, trimethylol Propane monoacrylate, Le acrylate, 1,3-propylene glycol diacrylate,
1,4-butylene glycol diacrylate, 1,6-
Hexane glycol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, 2,2-bis- (4-acryloxydiethoxyphenyl) propane, 2,2-bis- (4-acryloxypropoxyphenyl) propane, Trimethylolpropane diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, triacrylic formal, tetramethylolmethane tetraacrylate, acrylic acid ester of tris (2-hydroxyethyl) isocyanuric acid, represented by the following formula And the like.

[0021]

[Chemical 5] (In the formula, n is a positive integer of 1 to 30),

[0022]

[Chemical 6] (Where n and m are positive integers selected such that n + m is 2 to 30),

[0023]

[Chemical 7]

Examples of the methacrylic acid compound include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, octyl methacrylate, ethylhexyl methacrylate, methoxyethyl methacrylate. , Ethoxyethyl methacrylate, butoxyethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxypentyl methacrylate, N,
N-dimethylaminomethacrylate, N, N-diethylaminomethacrylate, glycidylmethacrylate, tetrahydrofurfurylmethacrylate, methacryloxypropyltrimethoxysilane, allylmethacrylate,
Trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, neopentyl glycol dimethacrylate, 2,2-bis- (4-methacryloxydiethoxyphenyl) Propane, trimethylolpropane dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol trimethacrylate, tetramethylolmethane tetramethacrylate, methacrylic acid ester of tris (2-hydroxyethyl) isocyanuric acid, represented by the following formula: A compound etc. are mentioned.

[0025]

[Chemical 8] (In the formula, n represents an integer of 1 to 30),

[0026]

[Chemical 9] (In the formula, n and m represent positive integers selected so that n + m is 2 to 30),

[0027]

[Chemical 10]

Further, trimethylhexamethylene diisocyanate / 2-hydroxyethyl acrylate (1/2
(Molar ratio) Reactant, isocyanate ethyl methacrylate / water (2/1 molar ratio) Reactant, butyl crotonic acid, glycerin monocrotonate, vinyl butyrate, vinyl trimethyl acetate, vinyl caproate, vinyl chloroacetate, vinyl lactate , Vinyl benzoate, divinyl succinate, divinyl phthalate, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-allylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide, acrylamide, Nt- Butyl acrylamide, N-methylol acrylamide, N-isobutoxymethyl acrylamide, N-butoxymethyl acrylamide, diacetone acrylamide, hexyl vinyl ether, ethylhexyl vinyl ae , Vinyl tolyl ether, polyvinyl ether of polyhydric alcohol, styrene derivative having substituents such as alkyl group, alkoxy group, halogen, carboxyl group and allyl group at ortho and para positions, divinylbenzene, allyloxyethanol, dicarboxylic acid Diallyl ester of N-vinyloxazolidone, N-
Vinylimidazole, N-vinylpyrrolidone, N-vinylcarbazole and the like can be used. When these other photopolymerizable unsaturated compounds are used, the amount thereof is preferably in the range of 1 to 200 parts by weight with respect to 100 parts by weight of the component (a).

Next, the photosensitive element of the present invention will be described in detail. The photosensitive element of the present invention can be obtained by laminating a layer of the photosensitive resin composition on a support film. The photosensitive resin composition layer can be formed on the support film by a conventional method. For example, dip coating method, roll coating method, curtain coating method, screen printing method using a photosensitive resin composition,
Directly coat it on the substrate or printed wiring board to be processed and protected by spray coating, electrostatic spraying, etc. to a thickness of 1
A photosensitive layer having a thickness of 0 to 150 μm can be easily formed. When applying, the photosensitive resin composition can be dissolved in a solvent as required. Examples of the solvent include methyl ethyl ketone, methyl cellosolve acetate, ethyl cellosolve acetate, carbitol acetate, cyclohexanone, methyl cellosolve, propylene glycol monomethyl ether acetate, methylene chloride and propylene glycol monomethyl ether. Further, the photosensitive resin composition or a solution thereof is applied, for example, on a support film such as a polyethylene terephthalate film or a polyimide film by a knife coating method, a roll coating method, or the like, and dried, and if necessary, a polyolefin or the like is protected. The photosensitive element is made by laminating films.
This photosensitive element can be laminated under heat and pressure on a substrate or a printed wiring board using a heat roll to form a photosensitive layer. At this time, when the substrate has irregularities of 10 μm or more, it is preferable to stack under a vacuum of 200 mmHg or less in order to prevent air entrapment. As a device that can be used in this method, for example, a laminating device described in JP-B-55-13341 is used. When a support film opaque to actinic light is used, it is necessary to peel off the support film during exposure.

Exposure and development of the photosensitive layer thus formed are carried out by a conventional method. That is, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or the like is used as a light source, and imagewise exposure is performed on the layer of the photosensitive resin composition directly or through a negative film through a transparent film such as a polyethylene terephthalate film. After exposure, it is preferable to heat at 60 to 80 ° C. for 1 to 10 minutes. If the transparent film remains, it is peeled off and then developed. As a developing solution used for the developing treatment, general tap water or an alkaline aqueous solution is used in some cases. When using an alkaline aqueous solution,
Examples of the base include alkali metal phosphates such as sodium phosphate and potassium phosphate, alkali metal carbonates such as sodium carbonate, and the like. Particularly, an aqueous solution of sodium carbonate is preferable. The image-wise protective film obtained by the above method has properties suitable as a corrosion resistant film for ordinary etching, plating, etc.
By heat treatment at 00 ° C, adhesion, heat resistance,
Properties such as solvent resistance can be improved, and properties as a solder mask can be satisfied.

[0031]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. In addition, "part" in Examples and Comparative Examples means "part by weight" unless otherwise specified.

Example 1 (a) Synthesis of vinyl polymer (a) Methyl ethyl ketone 2 was placed in a heatable and coolable reaction vessel of 500 ml equipped with a thermometer, a stirrer, a condenser and a dropping device.
00 parts were added, the temperature was raised to 78 ° C., and 0.4 parts of 2,2′-azobis (isobutyronitrile) was added to each combination of the polymerizable monomers shown in Table 1 for 3 hours. Was dropped. The mixture was kept at 78 ° C. and stirred for about 6 hours to obtain intended vinyl polymer solutions (a-1 to a-6).

[0033]

[Table 1]

The symbols in the table mean the following substances. DHA-3: 1,1-dimethyl-1- (2-hydroxypropyl) amine methacrylimide 2-HEMA: 2-hydroxyethyl methacrylate MMA: methyl methacrylate MA: methacrylic acid

(B) Synthesis formula of reaction product (b) of water-soluble hydantoin epoxy resin and unsaturated monocarboxylic acid

[Chemical 11]

Hydint-in-epoxy resin 1 represented by
20 g, 72 g of acrylic acid, 1 g of benzyltrimethylammonium chloride and 0.5 g of p-methoxyphenol were charged and reacted at 100 ° C. to obtain a reaction product (b-1). Similarly, the expression

[0037]

[Chemical 12]

Hydint-in-epoxy resin 1 represented by
34 g, 72 g of acrylic acid, 1 g of benzyltrimethylammonium chloride and 0.5 g of p-methoxyphenol were charged and reacted at 100 ° C. to obtain a reaction product (b-2).

(C) Preparation of photosensitive resin composition Vinyl polymer solution (a-1) obtained in the above (a)
300 parts, reaction product (b-1) 30 obtained in (b) above
Part, 10 parts of triglycidyl isocyanurate, 7 parts of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 [component (d)] and 1 part of phthalocyanine green are mixed to prepare the present invention. A solution of the photosensitive resin composition of was prepared.

(D) Formation of cured film A solution of the obtained photosensitive resin composition was applied to a film having a thickness of 50 μm and a width of 1 μm.
A glass substrate printed wiring board having a copper pattern of 25 μm was coated on the entire surface with a bar coater so that the film thickness was 60 μm. Then, it is dried at 80 ° C. for 10 minutes to give a thickness of 40.
A photosensitive layer of μm (on the glass substrate) was formed. Next, through a negative mask, HMW-201 manufactured by Oak Manufacturing Co., Ltd.
Exposure was performed at 400 mJ / cm ² using a B type exposure machine. After exposure,
After drying at 80 ° C. for 5 minutes and standing at room temperature for 30 minutes, tap development was performed at 30 ° C. for 120 seconds using tap water. Then, heat treatment was carried out at 150 ° C. for 60 minutes to obtain a cured coating (solder mask) having excellent dimensional accuracy corresponding to a negative mask. This cured coating had excellent solder heat resistance, and was peeled off even after soldering for 20 seconds at 260 ° C. using rosin-based flux A-226 (manufactured by Tamura Kaken Co., Ltd.), and no blistering was observed. Also, the drying time during the formation of the photosensitive layer is 6
Even at 0 minutes, a cured film having excellent characteristics was obtained, and thermal stability was also excellent.

Example 2 Solution of vinyl polymer (a) obtained in (a) of Example 1
-2) 300 parts, 30 parts of the reaction product (b-1) obtained in (b) of Example 1, triglycidyl isocyanurate 1
0 parts, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 [component (d)] 7
And 1 part of phthalocyanine green were mixed to prepare a solution of the photosensitive resin composition of the present invention. Using this solution of the photosensitive resin composition, in the same manner as in (1) of Example 1, a cured film having high thermal stability, developable with water, and excellent resolution and solder heat resistance was obtained. Was given.

Example 3 Solution of vinyl polymer (a) obtained in (a) of Example 1
-3) 300 parts, 30 parts of the reaction product (b-1) obtained in (b) of Example 1, 10 parts of 5,5-dimethylhydantoin bisepoxide, 2-methyl-1- [4- (methylthio). Phenyl] -2-morpholinopropanone-1 [component (d)] (7 parts) and phthalocyanine green (1 part) were mixed to prepare a solution of the photosensitive resin composition of the present invention. Using this solution of the photosensitive resin composition, in the same manner as in (1) of Example 1, a cured film having high thermal stability, developable with water, and excellent resolution and solder heat resistance was obtained. Was given.

Example 4 Solution of vinyl polymer (a) obtained in (a) of Example 1
-4) 300 parts, 30 parts of the reaction product (b-2) obtained in (b) of Example 1, 10 parts of 5,5-dimethylhydantoin bisepoxide, 2-methyl-1- [4- (methylthio). Phenyl] -2-morpholinopropanone-1 [component (d)] (7 parts) and phthalocyanine green (1 part) were mixed to prepare a solution of the photosensitive resin composition of the present invention. Using this solution of the photosensitive resin composition, in the same manner as in (1) of Example 1, a cured film having high thermal stability, developable with water, and excellent resolution and solder heat resistance was obtained. Was given.

Example 5 Solution of vinyl polymer (a) obtained in (a) of Example 1
-5) 300 parts, 30 parts of the reaction product (b-2) obtained in (b) of Example 1, 10 parts of 5,5-dimethylhydantoin bisepoxide, 2-methyl-1- [4- (methylthio). Phenyl] -2-morpholinopropanone-1 [component (d)] (7 parts) and phthalocyanine green (1 part) were mixed to prepare a solution of the photosensitive resin composition of the present invention. Using this solution of the photosensitive resin composition, in the same manner as in (1) of Example 1, a cured film having high thermal stability, developable with water, and excellent resolution and solder heat resistance was obtained. Was given.

Example 6 Solution of vinyl polymer (a) obtained in (a) of Example 1
-6) 300 parts, 30 parts of the reaction product (b-2) obtained in (b) of Example 1, triglycidyl isocyanurate 1
0 parts, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 [component (d)] 7
And 1 part of phthalocyanine green were mixed to prepare a solution of the photosensitive resin composition of the present invention. Using this solution of the photosensitive resin composition, in the same manner as in (1) of Example 1, a cured film having high thermal stability, developable with water, and excellent resolution and solder heat resistance was obtained. Was given.

[0046]

EFFECTS OF THE INVENTION By using the photosensitive resin composition and the photosensitive element of the present invention, it is possible to develop with water or an alkaline aqueous solution, which is excellent in safety and economy, and is excellent in resolution, solder heat resistance and the like. A reliable solder mask can be formed.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location H01L 21/027 H05K 3/28 D 7511-4E

Claims (4)

[Claims] 1. A compound represented by the general formula (I): [Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group or an aryl group, and R ₃ represents an alkyl group or a hydroxyalkyl group], a vinyl polymer having a group (b). Reaction product of water-soluble hydantoin epoxy resin and unsaturated monocarboxylic acid, (c) 1 in 1 molecule
An epoxy compound having one or more epoxy groups and (d)
A photosensitive resin composition comprising a photoinitiator that generates free radicals by actinic light. 2. The photosensitive resin composition according to claim 1, wherein the epoxy compound as the component (c) is tris (2,3-epoxypropyl) isocyanurate. 3. The photosensitive resin composition according to claim 1, wherein the epoxy compound as the component (c) is a hydantoin epoxy resin. 4. The method according to claim 1, 2 or 3 on a support film.
A photosensitive element formed by laminating layers of the photosensitive resin composition described.