JPH06222559A - Photosensitive resin composition and photosensitive element using the same - Google Patents

Abstract

PURPOSE:To enable manufacture of a solder mask superior in safety and economy, developable with water or an aqueous solution of alkali, superior in resolution and resistance to soldering heat and the like, and high in reliability by incorporating a specified vinyl polymer, a specified photopolymerizable compound, a specified epoxy compound and a specified photoinitiator. CONSTITUTION:The photosensitive resin composition comprises the vinyl polymer having on the side chains groups each represented by the formula, the photopolymerizable compound having at least one terminal ethylene group, the epoxy compound having at least one epoxy group, preferably, such as tris(2,3-epoxypropyl)-isocyanurate or water-soluble hydantoin epoxy resins, and the photopolymerization initiator to be allowed to produce free radicals by irradiation with active rays. In the formula, each of R1 and R2 is H, an alkyl or aryl; and R3 is alkyl or hydroxy-alkyl or each of R2 and R3 may combine with each other to form a hetero ring together with the N atom.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to printed wiring board manufacturing,
The present invention relates to a photosensitive resin composition and a photosensitive element for forming a protective film that can be used for precision metal processing.

[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 electrical equipment, miniaturization of individual parts such as resistors and capacitors, leadlessness, multi-pinning of IC parts, narrowing of pin pitch, and variety of package forms. In addition, 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). As for the mounting method, instead of the conventional pin insertion mounting that inserts with leaded components, surface mounting technology that mounts chip components that can achieve higher density has become popular, and it is used for printed wiring boards to cope with this. As for solder resists, high precision with excellent positional accuracy and resolution has been demanded, and it is difficult to deal with the conventional printing method that forms a pattern using screen printing. It has come.

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 development 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 (JP-A-53-560).
18 and 54-1018, etc.) are known. However, these photosensitive resin compositions have a drawback in that the heat resistance of the cured coating is not sufficient due to the large amount of acrylic polymer used for imparting film properties.

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 No. Sho 5)
4-82073, 58-62636, etc.)
Is proposed. However, these photodimerization type photosensitive resin compositions have low sensitivity, so that it is difficult to form a thick film resist, and further, since it is necessary to use a flammable organic solvent such as cyclohexanone as a developing solution, it is safe. The top is also unfavorable.

A composition containing a novolac type epoxy acrylate containing an epoxy group and a photopolymerization initiator as main components (JP-A-61-272, etc.) has also been proposed. These components are also excellent in heat resistance and useful, but it is necessary to use a 1,1,1-trichloroethane / lower alcohol mixed solution as a developing solution, which is problematic in developing solution management. Further, 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 highly safe and economical and can be developed with an aqueous alkali solution, contains a carboxyl group-containing polymer, a monomer, a photopolymerization initiator and a thermosetting resin as main components. Composition (Japanese Patent Application Laid-Open No. Sho 4
8-73148, 57-178237,
No. 58-42040, No. 59-151152, etc.) are known. In these compositions, epoxy resin, melamine resin, urea resin, etc. are used as the thermosetting resin, and triglycidyl isocyanurate, etc.,
An example in which an insoluble epoxy resin is dispersed and used in an organic solvent is also disclosed. However, these compositions do not always have sufficient properties such as resolution, solvent resistance, and solder heat resistance when absorbing moisture.

JP-A-61-243869 discloses a product 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. A liquid resist ink composition containing an oligomer, 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 coexist, and further has a dry margin (time and temperature conditions until the reaction proceeds due to heating during drying and development cannot be performed). Since it is narrow, it has the drawback of poor workability.

[0011]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art, can be developed with water or an alkaline aqueous solution having high thermal stability, wide workability, and excellent safety and economy, and The present invention provides a photosensitive resin composition capable of forming a highly reliable solder mask having excellent resolution and solder heat resistance, and a photosensitive element using the same.

[0012]

The present invention provides (a) a vinyl polymer having a group represented by the general formula (1) in a side chain,

[Chemical 2] [R ₁ and R ₂ represent a hydrogen atom, an alkyl group or an aryl group, R ₃ represents an alkyl group or a hydroxyalkyl group (R ₂ and R ₃ may combine to form a heterocycle with a nitrogen atom) )] (B) A photopolymerizable compound having one or more terminal ethylene groups, (c) an epoxy compound having one or more epoxy groups in one molecule, and (d) a photoinitiator which produces free radicals by active light. And a photosensitive element comprising a support film and a layer of the photosensitive resin composition laminated on the support film.

Each component contained in the photosensitive resin composition of the present invention will be described in detail below. The photosensitive resin composition of the present invention has the side chain represented by the general formula (1) as the essential component (a).
It contains a vinyl polymer having a group represented by.

The essential component (a) is composed of a unit of a polymerizable unsaturated monomer containing an amine imide group represented by the general formula (1) and a unit of another polymerizable monomer which is optionally used. Examples of the polymerizable unsaturated monomer containing an amine imide group include a monomer represented by the general formula (2) and a monomer represented by the general formula (3).

[Chemical 3] [In the formula, 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 atom, bromine atom, etc.) or cyano group;
₁ , R ₂ and R ₃ are the same groups as in the case of the general formula (1). X represents an alkyl group, an aryl group or an aral group,
n represents an integer of 1 to 4]

Specifically, as the monomer represented by the above general formula (2), 1,1,1-trimethylamine methacrylimide, 1,1-dimethyl-1-ethylamine methacrylimide and 1,1-dimethyl are used. -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 and the like can be mentioned.

Examples of the monomer represented by the above general formula (3) include the monomers of the following formulas (4) and (5).

[Chemical 4]

In addition, Journal of Polymer
Science Part A-1 Vol. 6, pp. 363-373
1968 / Vol. 2197-2207 1968 / Vol. 9 Vol. 3453-3470 1971 (JOUN
AL OF POLYMER SCIENCE PART A-1 Vol.6,363-373 (1968)
/2197/2207(1968)/Vol.9,3453-3470(1971)), The Journal of Organic Chemistry Vol. 33
No. 4 April pp. 1374-1378 1968 (Th
e Journal of Organic Chemistry Vol.33, No.4, April, 1
374-1378 (1968)), Macromolecules Vol. 1, No. 3, May-June, pages 254-260, 1968 / Vol. 3, No. 6, November-December, pages 715-722 1.
970 (Macromolecules Vol.1, No.3, May-June, 254-2
60 (1968) /Vol.3,No.6,November-December,715-722 (197
0)), Journal of Applied Polymer Science 15: 2609-2621 1971 (JO
URNAL OF APPLIED POLYMER SCIENCE Vol.15,2609-2621
(1971)), Chemical Reviews Vol. 73, No. 3
255-281, 1973 (Chemical Reviews Vol.
73, No. 3, 255-281 (1973)), Industry Engineering Chemistry, Production Research Development Vol. 13, No. 3, 197-201.
Page 1974 / Vol.19, No.3, 338-349
Page 1980 (Ind.Eng.Chem., Prod.Res.Develp.Vol.1
3, No.3,197-201 (1974) /Vol.19,No.3,338-349 (1980)),
Applied Polymer Symposium No. 26, 387
~ 397 pages 399 ~ 410 pages 1975 (Applied
Polymer Symposium No.26,387-397,399-410 (1975)),
Fine Chemicals 12.15, 14-24 (198
The polymerizable unsaturated monomer containing an amine imide group described in 5) and the like can be mentioned, but the polymerizable unsaturated monomer containing an amine imide group is not limited thereto. . Moreover, you may use these individually or in combination of 2 or more types. The amount of the polymerizable unsaturated monomer containing an amineimide group contained in the vinyl polymer (a) in the present invention is usually 5% or more, preferably 10% or more based on the moles of the polymer. .

Other polymerizable monomers used as necessary include (meth) acrylic acid alkyl ester [eg,
Methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.],
Hydroxyalkyl (meth) acrylate [hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyhexyl (meth) acrylate, etc.], aromatic vinyl monomer (styrene, α-methylstyrene, α- Chlorostyrene, etc.), halogen-containing monomers (vinyl chloride, vinylidene chloride, etc.), alkyl or cycloalkyl vinyl ethers (methyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, etc.), nitrile group-containing monomers (acrylonitrile, etc.) ), An amide group-containing monomer [(meth) acrylamide, crotonamide, N-methylolacrylamide, fumaric acid diamide, etc.], and a carboxyl group-containing monomer [(meth) acrylic acid, maleic acid, maleic anhydride, etc.] Given Be done. You may use these individually or in combination of 2 or more types.

The essential component (a) in the present invention is obtained by copolymerizing a unit of a polymerizable unsaturated monomer containing an amine imide group represented by the general formula (1) and optionally other polymerizable monomer. Or an amine imide group may be introduced after copolymerization.

The method of introducing an amine imide group into the side chain after the copolymerization is described in the above-mentioned documents and the like. For example, instead of the amine imide group-containing monomer, a (meth) acrylic acid alkyl ester [eg (meth)] Methyl acrylate, ethyl (meth) acrylate, (meth) acrylic acid 2
-Ethylhexyl, etc.], hydroxyalkyl (meth) acrylate [hydroxyethyl (meth) acrylate,
(Meth) acrylic acid hydroxypropyl, (meth) acrylic acid hydroxyhexyl, etc.]
Thereafter, a compound having at least one dimethylhydrazine and an epoxy group in the molecule and having no unsaturated group (ethylene oxide, propylene oxide, phenylglycidyl ether, glycidyl phthalimide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6 -Hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether,
Adipic acid diglycidyl ester, etc.) is added, and the mixture is reacted by stirring and mixing.

The molecular weight of the vinyl polymer having a group represented by the formula (1) in the side chain of the essential component (a) in the present invention is usually 1,000 to 500,000, preferably 5,000.
It is 0 to 100,000. When the molecular weight is less than 1,000, the film formability tends to be poor, and when it exceeds 500,000, the developability tends to be poor.

The photosensitive resin composition of the present invention contains a photopolymerizable compound having at least one terminal ethylene group as an essential component (b). Examples of these 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 monoacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, pentaerythritol monoacrylate, trimethylolpropane monoacrylate, allyl acrylate, 1 , 3-propy Glycol diacrylate,
1,4-butylene glycol diacrylate, 1,6-
Hexylene glycol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2-bis (4-acryloxypropylxyphenyl) propane, Trimethylolpropane diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, triacrylformal, tetramethylolmethane tetraacrylate, acrylic acid ester of tris (2-hydroxyethyl) isocyanuric acid,

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

[Chemical 6] [Wherein, n and m are positive integers selected so that n + m is 2 to 30],

[Chemical 7] 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, hydroxy Propyl methacrylate, hydroxybutyl methacrylate, hydroxypentyl methacrylate, N, N-dimethylaminomethacrylate, N, N-diethylaminomethacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, methacryloxypropyltrimethoxysila , Allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 2,2-bis (4-methacryloxy) Diethoxyphenyl) propane, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, tetramethylolmethane tetramethacrylate, methacrylic acid ester of tris (2-hydroxyethyl) isocyanuric acid,

[Chemical 8] [In the formula, n is a positive integer of 1 to 30],

[Chemical 9] [Wherein, n and m are positive integers selected so that n + m is 2 to 30],

[Chemical 10] Trimethylhexamethylene diisocyanate / 2-hydroxyethyl acrylate (1/2 mole ratio) reaction product, isocyanate ethyl methacrylate / water (2/1 mole ratio) reaction product, butyl crotonic acid, glycerin monoclonate, vinyl butyrate , Vinyl trimethyl acetate, vinyl caproate, vinyl chloroacetate, vinyl lactate, vinyl benzoate, divinyl succinate, divinyl phthalate, methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N
-Aryl methacrylamide, N-hydroxyethyl-
N-methylmethacrylamide, acrylamide, Nt
-Butylacrylamide, N-methylolacrylamide, N-isobutoxymethylacrylamide, N-butoxymethylacrylamide, diacetone acrylamide, hexyl vinyl ether, ethylhexyl vinyl ether, vinyl triether, polyvinyl ethers of polyhydric alcohols, and styrene derivatives such as ortho and para. Styrene having a substituent such as an alkyl group, an alkoxy group, a halogen, a carboxyl group, or an acryl group at the position,
Divinylbenzene, allyloxyethanol, diallyl ester of dicarboxylic acid, N-vinyloxazolidone,
N-vinylimidazole, N-vinylpyrrolidone, N-
Examples thereof include vinylcarbazole. These photopolymerizable compounds having one or more terminal ethylene groups may be used alone or in combination of two or more.

The photosensitive resin composition of the present invention contains, as an essential component (c), an epoxy compound having one or more epoxy groups in one molecule. Examples of this compound 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, bisphenol S type epoxy resin, phenol novolak type epoxy resin,
Cresol novolac type epoxy resin, N-glycidyl type epoxy resin, alicyclic epoxy resin manufactured by Chisso Co. (Cissonox 206, Chisso nox 221, Chisso nox 201 etc.), alicyclic epoxy resin manufactured by Daicel Chemical Industries (Sexaroid 2021 etc.) ), 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. Specific examples of the water-soluble hydantoin epoxy resin include 5,5-
Dimethylhydantoin bisepoxide, 5,5-diethylhydantoin bisepoxide, 5-benzylhydantoin bisepoxide, 5-isopropylhydantoin epoxide, 5,5-pentamethylenehydantoin bisepoxide, 5,5-tetramethylenehydantoin epoxide, the hydantolenbis Epoxide derivative and 5,5
Examples thereof include an epoxy resin which is a condensation reaction product with a hydantoin derivative such as dimethylhydantoin and 5,5-diethylhydantoin. You may use these epoxy compounds individually or in combination of 2 or more types.

The photosensitive resin composition of the present invention contains, as an essential component (d), a sensitizer and / or a sensitizer system capable of generating free radicals by actinic light. As a sensitizer,
For example, 2-ethylanthraquinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-
Substituted or unsubstituted polynuclear quinones such as benzanthraquinone and 2,3-diphenylanthraquinone, benzoin,
Α-Ketaldonyl alcohols and ethers such as pivalon, α-phenyl-benzoin, α-hydrocarbon-substituted aromatic acyloines such as α, α-diethoxyacetophenone, benzophenone, 4,4′-bisdialkylaminobenzophenone Aromatic ketones such as 2-methylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone,
Thioxanthones such as 2-ethylthioxanthone, 2-
Methyl-1- [4- (methylthio) phenyl] -2-monofolinopropanone-1 and the like are used, and these may be used alone or in combination of two or more kinds.

The photosensitive resin composition of the present invention has 1 terminal ethylene group per 100 parts by weight of a vinyl polymer (a) having at least one group represented by the general formula (1) in its side chain. 1 to 200 of the photopolymerizable compound (b) having one or more
1 to 100 parts by weight of an epoxy compound (c) having one or more epoxy groups in one molecule, a sensitizer and / or a sensitizer system (d) that generates a free radical by actinic light.
Is preferably used in the range of 1 to 100 parts by weight in order to form a solder mask excellent in resolution, solder heat resistance, solvent resistance, plating resistance, electric insulation and the like.

In the photosensitive resin composition of the present invention, fine particles of inorganic or organic fillers, thermal polymerization inhibitors, dyes, pigments, defoamers, flame retardants, plasticizers, adhesion improvers are added as secondary components. , Epoxy resin curing accelerators and latent curing agents. The selection of these subcomponents is carried out in the same manner as in the usual photosensitive resin composition.

The photosensitive resin composition of the present invention can be prepared by a conventional method such as a dip coating method, a roll coating method, a curtain coating method, a screen printing method, a spray method or an electrostatic spray method.
The photosensitive layer having a thickness of 10 to 150 μm can be easily formed by directly coating the substrate or the printed wiring board to be processed and protected. When applying, the photosensitive resin composition may be dissolved in a solvent as needed. Examples of the solvent include methyl ethyl ketone, methyl cellosolve acetate, and ethyl cellosolve acetate. Examples thereof include carbitol acetate, cyclohexanone, methyl cellosolve, propylene glycol monomethyl ether acetate, methylene chloride and propylene glycol monomethyl ether 1,1,1-trichloroethylene.

Further, the composition or a solution thereof is applied onto a 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. A photosensitive element can be produced by laminating films, and the photosensitive element can be laminated by heating and pressing the photosensitive element on a substrate or a printed wiring board using a heat roll to form a photosensitive layer. At this time, the substrate is 10
In the case of having irregularities of μm or more, it is preferable to stack under a vacuum of 200 mmHg or less in order to prevent air entrapment. As this device, for example, Japanese Patent Publication No. 55-1334
The laminating apparatus described in Japanese Patent No. 1 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, an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, or the like is used as a light source, and imagewise exposure is performed directly on the layer of the photosensitive resin composition or through a negative film through a transparent film such as a polyethylene terephthalate film. After exposure, it is preferable to heat at 60 ° C to 80 ° C for 1 to 10 minutes. If the transparent film remains, it is peeled off and then developed.

As the developing solution used for the developing treatment, general tap water or an alkaline aqueous solution is used in some cases. When an aqueous alkali solution is used, 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, and an aqueous solution of sodium carbonate is particularly preferable.

The image-like protective film obtained by the above method has suitable characteristics as a corrosion-resistant film for ordinary etching, plating, etc., but is subjected to heat treatment at 80 to 200 ° C. after development. As a result, the characteristics such as adhesion, heat resistance and solvent resistance can be improved, and the characteristics as a solder mask can be satisfied.

[0032]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In addition, "part" in an example means a "weight part" unless there is particular notice.

Example 1 (a) Synthesis of vinyl polymer (a)

[Table 1] DHA-3: 1,1-dimethyl-1- (2-hydroxypropyl) amine methacrylimide 2-HEMA: 2-hydroxyethyl methacrylate MMA: methyl methacrylate

200 parts of methyl ethyl ketone was placed in a 500 ml heatable and coolable reaction vessel equipped with a thermometer, a stirrer, a condenser tube and a dropping device, and the temperature was raised to 78 ° C.
A mixture prepared by adding 0.4 parts of 2,2′-azobis (isobutyronitrile) to each combination of the polymerizable monomers of was added dropwise over 3 hours. While maintaining the temperature at 78 ° C., stirring was continued for about 6 hours, and the solution of the desired vinyl polymer (a-1 to a-
6) was obtained.

(B) Preparation of Photosensitive Resin Composition The materials shown in Table 2 were blended to prepare a solution of the photosensitive resin composition of the present invention.

[Table 2]

(C) Formation of cured film A solution of the photosensitive resin composition obtained in (B) above was formed to a thickness of 5
A film thickness of 60 μm with a bar coater on the entire surface of a glass-based printed wiring board having a copper pattern of 0 μm and a width of 125 μm
Was applied. Then, it was dried at 80 ° C. for 10 minutes at room temperature to form a photosensitive layer having a thickness of 40 μm (on a glass substrate).

Next, using a HMW-201B type exposure machine manufactured by ORC Manufacturing Co., Ltd. through a negative mask, 400 mJ
Exposed at / cm ² . After exposure, heat at 80 ° C for 5 minutes, leave at room temperature for 30 minutes, and then tap water at 30 ° C for 12 minutes.
Spray developed for 0 seconds. 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. Further, even when the drying time at the time of forming the photosensitive layer was 60 minutes, a cured film having similarly excellent properties was obtained, and thermal stability was also excellent.

Example 2 The materials shown in Table 3 were blended to prepare a solution of the photosensitive resin composition of the present invention.

[Table 3] In the same manner as in Example 1 (C), a cured film having high thermal stability, being developable with water, and having excellent resolution and solder heat resistance was obtained.

Example 3 The materials shown in Table 4 were blended to prepare a solution of the photosensitive resin composition of the present invention.

[Table 4] In the same manner as in Example 1 (C), a cured film having high thermal stability, being developable with water, and having excellent resolution and solder heat resistance was obtained.

Example 4 The materials shown in Table 5 were blended to prepare a solution of the photosensitive resin composition of the present invention.

[Table 5] In the same manner as in Example 1 (C), a cured film having high thermal stability, being developable with water, and having excellent resolution and solder heat resistance was obtained.

Example 5 The materials shown in Table 6 were blended to prepare a solution of the photosensitive resin composition of the present invention.

[Table 6] In the same manner as in Example 1 (c), a cured film having high thermal stability, capable of being developed with a 1 wt% sodium carbonate aqueous solution in 90 seconds, and having excellent resolution and solder heat resistance was obtained. .

Example 6 The materials shown in Table 7 were blended to prepare a solution of the photosensitive resin composition of the present invention.

[Table 7] In the same manner as in Example 1 (C), a cured film having high thermal stability, being developable with water, and having excellent resolution and solder heat resistance was obtained.

[0043]

EFFECT 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 H05K 3/18 D 7511-4E 3/28 D 7511-4E

Claims (4)

[Claims] 1. A vinyl polymer having a group represented by the general formula (1) in the side chain (a): [Wherein R ₁ and R ₂ represent a hydrogen atom, an alkyl group or an aryl group, and R ₃ represents an alkyl group or a hydroxyalkyl group (R ₂ and R ₃ combine to form a heterocycle with a nitrogen atom). (B) a photopolymerizable compound having one or more terminal ethylene groups (c) an epoxy compound having one or more epoxy groups in one molecule, and (d) light for generating free radicals by active light. A photosensitive resin composition containing an initiator. 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 water-soluble 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.