JP3391780B1 - Photosensitive resin composition - Google Patents

Abstract

A photosensitive resin composition which comprises A a resin prepared by providing a phenolic novolac and/or cresolic novolac modified bis-phenol type epoxy resin, subjecting the epoxy group of the epoxy resin to an addition reaction with an unsaturated monobasic acid, to give a reaction product I, and further subjecting the hydroxyl group of the reaction product to an addition reaction with a saturated and/or unsaturated polybasic acid anhydride, B an epoxy resin, C a photopolymerization initiator and D a polymerizable unsaturated compound and/or a solvent. The photosensitive resin composition is particularly excellent in the developability with an aqueous dilute alkaline solution and is capable of forming a cured coating film which is excellent particularly in flexibility, heat resistance, soldering heat resistance, adhesion, water resistance, bending resistance, chemical resistance and the like.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive resin composition. More specifically, in the field of electronic materials such as printed wiring board solder resist, high-density multilayer board interlayer insulating film, semiconductor package solder resist, and flexible printed wiring board resist ink, it has excellent developability with a dilute alkaline aqueous solution and is hardened. Subsequent coating films are especially flexible, heat resistant, solder heat resistant, adhesive, water resistant, flex resistant,
The present invention relates to a photosensitive resin composition having excellent chemical resistance and the like.

[0002]

2. Description of the Related Art Conventionally, a permanent mask resist in the production of printed wiring boards has been manufactured by a method of screen-printing a heat- or ultraviolet-curable resist ink, but from the viewpoint of productivity, it is currently an alkali-developing liquid solder photo resist. It is shifting to resist. For example, Japanese Patent Publication 1-54
No. 390, a liquid resist ink composition which is excellent in photocurability, thermosetting property, heat resistance, solvent resistance, and acid resistance and which can be developed with an alkaline aqueous solution, contains a novolac epoxy compound and an unsaturated monocarboxylic acid. A liquid resist containing a photocurable resin obtained by reacting a saturated or unsaturated polybasic acid anhydride with the reaction product, a photopolymerization initiator, a diluent, and an epoxy compound having two or more epoxy groups. Ink compositions have been proposed and are currently in the mainstream.

However, in recent years, miniaturization of electronic devices
With the reduction in weight and performance, the miniaturization of semiconductor packages,
High pin count has been put into practical use and mass production is progressing. For example,
In semiconductor packages such as BGA (ball grid array) and CSP (chip size package), PCT resistance is particularly required from the viewpoint of high reliability. However, under such severe conditions, the conventional liquid photosensitive resists are presently available for only several hours to several tens of hours. Further, in the mounting method of the semiconductor package, the whole is heated by infrared rays and the solder is reflowed and fixed, so that the conventional solder resist and the coating film as in Japanese Patent Publication No. 1-54390 crack the coating film due to thermal shock. There is a decrease in so-called reflow resistance, such as the occurrence of cracks or peeling from the substrate, and improvement thereof is demanded. In order to solve these problems, it is necessary to increase the elongation of the coating film without significantly lowering the Tg. Therefore, it is necessary to study the skeleton of the epoxy acrylate and a part of the unsaturated monobasic acid introduced during the epoxy acrylate synthesis. A method of adjusting the crosslink density by substituting a saturated monobasic acid or the like and a method of introducing a rubber component have been studied, but they were not sufficient. Among these, bisphenol type epoxy acrylates have been studied in the study of the skeleton of epoxy acrylates, but the developability is insufficient especially with an aqueous sodium carbonate solution, and improvement of the developability has been desired.

[0004]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is that the developability in a dilute aqueous alkali solution is particularly excellent, and the coating film after curing is particularly flexible, heat resistant, solder heat resistant, and adhesive. Another object of the present invention is to provide a photosensitive resin composition having excellent water resistance, flex resistance, chemical resistance and the like.

[0005]

According to the invention of claim 1,
(A) Phenol novolac and / or cresol novolac-modified bisphenol type epoxy resin with an unsaturated monobasic acid added to the epoxy group (I)
A resin obtained by further adding a saturated and / or unsaturated polybasic acid anhydride to the hydroxyl group of (B) epoxy resin,
A photosensitive resin composition comprising (C) a photopolymerization initiator and (D) a polymerizable unsaturated compound and / or a solvent. In the invention of claim 2, the phenol novolac and / or cresol novolac-modified bisphenol epoxy resin in the component (A) has a hydroxyl group of the phenol novolac of 0.05 to 0.5 with respect to 1 equivalent of the epoxy group of the bisphenol epoxy resin. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is reacted at an equivalent ratio. The invention of claim 3 is characterized in that the phenol novolac and / or cresol novolac-modified bisphenol type epoxy resin in the component (A) is obtained by reacting with a phosphorus-based catalyst. The photosensitive resin composition described. The invention according to claim 4 is characterized in that the bisphenol type epoxy resin in the component (A) is an isocyanate-modified epoxy resin which is a reaction product of a bisphenol type epoxy resin and a diisocyanate compound. The photosensitive resin composition according to the item 1. Claim 5
In the invention of (A), 0.1 to 0.8 equivalent of a saturated and / or unsaturated polybasic acid anhydride is reacted with 1 equivalent of a hydroxyl group in the reaction product (I) in the component (A). It is a photosensitive resin as described in any one of Claim 1 thru | or 4 characterized by the above-mentioned. The invention of claim 6 is the photosensitive resin composition according to any one of claims 1 to 5, wherein the epoxy resin (B) is blended in an amount of 1 to 50% by weight based on the composition. The invention of claim 7 is the photosensitive resin composition according to any one of claims 1 to 6, wherein the photopolymerization initiator (C) is blended in an amount of 0.5 to 20% by weight based on the composition. is there. The invention according to claim 8 is the photosensitive resin according to any one of claims 1 to 7, wherein (D) the polymerizable unsaturated compound and / or the solvent is blended in an amount of 5 to 80% by weight based on the composition. It is a composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The (A) component phenol novolac and / or cresol novolac-modified bisphenol epoxy resin is an epoxy resin obtained by reacting a bisphenol epoxy resin with phenol novolac. As the bisphenol type epoxy resin used, known ones can be used, for example, bisphenol A,
Ether-type bisphenol-type epoxy resins obtained by reacting bisphenols such as bisphenol F, bisphenol S, and tetrabromobisphenol A with epihalohydrin, and aliphatic-type bisphenol-type epoxy resins such as bisphenol A dipropoxydiglycidyl ether, etc., Refers to all epoxy resins containing a bisphenol skeleton. Alternatively, a hydrogenated bisphenol type epoxy resin may be used.

The isocyanate-modified epoxy resin used in the present invention is a known epoxy resin having an oxazolidone ring structure in the skeleton obtained by reacting a bisphenol type epoxy resin with a diisocyanate compound, and the above-mentioned bisphenol type epoxy resin. What reacted with the diisocyanate compound can be used. As the diisocyanate compound used in the reaction, known compounds can be used, for example, menthane diisocyanate, butane-1,1-diisocyanate, ethane-1,2-diisocyanate, propane-1,3-diisocyanate, butane-
1,2-diisocyanate, 2-methylbutane-1,4-diisocyanate, pentane-1,5-diisocyanate,
ω, ω'-1,3-dimethylbenzene diisocyanate,
ω, ω'-1,4-dimethylnaphthalene diisocyanate,
Cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-phenylene diisocyanate, 1-methylbenzene-2,4-
Diisocyanate, diphenyl ether-4,4'-diisocyanate, naphthalene-1,4-diisocyanate,
Biphenyl 4,4'-diisocyanate, 3,3'-dimethylbisphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate, diphenylsulfone -4,4'-diisocyanate etc. can be mentioned. These substances may be used alone or in combination of two or more.

The isocyanate-modified epoxy resin is synthesized by using the above-mentioned bisphenol type epoxy resin and diisocyanate compound in the presence of an oxazolidone forming catalyst. Details of the isocyanate-modified epoxy resin having an oxazolidone ring are described in, for example, JP-B-53-45757 and JP-A-5-43657. Further, as a commercial product of an isocyanate-modified epoxy resin having an oxazolidone ring, trade name XAC415
1, XAC4152 (manufactured by Asahi Kasei Epoxy Co., Ltd.) or the like may be used.

Phenol novolac used in the present invention,
As the cresol novolac, a known novolac-based or cresol-based phenol resin can be used. Specifically, BRG-553, BRG-553B manufactured by Showa Highpolymer Co., Ltd.,
BRG-556, BRG-557, BRG-558, B
RG-5833Y and other phenol novolacs and CRM-
A cresol novolak such as 552 or CRM-553 is used.

The reaction of the bisphenol type epoxy resin with phenol and / or cresol novolac can be carried out according to a known method. For example, the addition reaction is carried out at a temperature of about 100 to 170 ° C. in the presence of an amine-based or phosphorus-based catalyst, without solvent or in the presence of a solvent. Examples of amine-based catalysts include amines such as tertiary amines and quaternary ammonium salts, and examples of phosphorus-based catalysts include triphenylphosphine. The reaction rate is
The hydroxyl group of phenol novolac is 0.05 to 0.5 with respect to 1 equivalent of the epoxy group of the bisphenol type epoxy resin.
The reaction is carried out at an equivalent ratio, preferably 0.1 to 0.4 equivalent. When the phenol novolac is less than 0.05 equivalent, no improvement in developability is observed, the viscosity exceeding 0.5 equivalent becomes too high, and the toughness of the cured product also decreases.

The unsaturated monobasic acid in the component (A) of the present invention is a monobasic acid having one carboxyl group and one or more polymerizable unsaturated bonds, and specific examples thereof include acrylic acid or methacrylic acid. Acids can be preferably used. Acrylic acid is preferable in order to obtain a particularly high actinic energy photocurability. Others, crotonic acid, cinnamic acid, sorbitan acid, acrylic acid dimer, monomethyl maleate, monopropyl maleate, monobutyl maleate,
Examples thereof include a carboxyl group-containing polyfunctional acrylate or methacrylate that is a reaction product of a polyfunctional acrylate or methacrylate having one hydroxyl group and one or more acryloyl groups, and a dibasic acid among the polybasic acid anhydrides described below. Two or more kinds of these unsaturated monobasic acids may be used in combination.

When an unsaturated monobasic acid is reacted with a novolak and / or cresol novolac-modified epoxy resin, 0.8 to 1.2 mol of the unsaturated monobasic acid is added to 1 equivalent of the epoxy group of the novolac-modified epoxy resin. The reaction is preferably carried out at a ratio of 0.9 to 1.1 mol. When the amount of unsaturated monobasic acid is less than 0.8 mol, storage stability becomes poor, and there is a problem such as gelation during synthesis. When it is more than 1.2 mol, odor is generated or heat resistance is increased. It may cause deterioration of sex.

Known solvents can be used in the reaction, such as ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether, Glycol ethers such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether, esters such as ethyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum naphtha,
Examples include organic solvents such as petroleum-based solvents such as hydrogenated petroleum naphtha and solvent naphtha. In addition, reactions such as carbitol (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane (meth) acrylate, tris (hydroxyethyl) isocinurate tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. It is also possible to use polar monomers. Known reaction catalysts can be used, for example, triethylamine, benzyldimethylamine, methyltriethylammonium chloride, benzyltrimethylammonium bromide,
Examples thereof include benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, chromium octanoate, zirconium octanoate, and the like. The amount of the catalyst used is preferably 0.01 to 5% by weight with respect to the total of the novolac and / or cresol novolac-modified epoxy resin and the unsaturated monobasic acid.
The reaction temperature is preferably 60 to 150 ° C. Also,
The reaction time is preferably 5 to 60 hours. In this way, the reaction product (I) can be obtained.

The saturated or unsaturated polybasic acid anhydride to be reacted with the reaction product (I) in the present invention includes maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride,
Dibasic acid anhydrides such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetra Examples thereof include polybasic acid anhydrides such as carboxylic acid anhydride and biphenyltetracarboxylic acid anhydride, and tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride are particularly preferable. The reaction amount of the saturated or unsaturated polybasic acid anhydride is 0.1 to 0.8 equivalents of the saturated and / or unsaturated polybasic acid anhydride, preferably 1 equivalent of the hydroxyl group in the reaction product (I). Is 0.3 to 0.7 equivalent. If the amount of the saturated and / or unsaturated polybasic acid anhydride added is less than 0.1 equivalent, sufficient alkali developability cannot be obtained, and if it exceeds 0.8 equivalent, the electrical properties of the cured coating film deteriorate. Will end up.

The amount of the component (A) in the composition of the present invention is preferably 10 to 80% by weight, more preferably 15 to 60% by weight.
Weight percent is preferred.

The (B) epoxy resin has, for example, one or more epoxy groups in one molecule, and is bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolac. Type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene-phenol novolac type epoxy resin, phenol-cresol novolac co-condensation type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin or halogenated epoxy compounds thereof , Triphenylol methane type epoxy resin, alkyl-substituted triphenylol methane type epoxy resin, tetraphenylol ethane type epoxy resin, etc. Epoxy resins obtained by reacting a down, polyfunctional hydroxy naphthalenes is reacted with epichlorohydrin obtained epoxy resin, silicone-modified epoxy resin, .epsilon.-caprolactone-modified epoxy resin,
Glycidylamine type epoxy resin obtained by reaction of epichlorohydrin with primary or secondary amine, 1,
Heterocyclic epoxy resins such as triglycidyl isocyanate such as 3,5-triglycidyl isocyanurate and the like can be mentioned. You may use together 1 type (s) or 2 or more types of these epoxy resins. Further, it is also effective to use an isocyanate-modified epoxy resin for the purpose of improving Toughness while securing Tg, or to use a phosphorus-containing epoxy resin from the viewpoint of imparting flame retardancy.

The epoxy resin (B) is a thermosetting component, and its purpose is to improve various properties as a solder resist such as adhesion, heat resistance and plating resistance.

The epoxy resin (B) is used alone or as a mixture of two or more kinds, and the amount of the epoxy resin contained in the composition of the present invention is 1 to 50% by weight, preferably 3 to 45% by weight in the composition. % By weight.

Further, in order to further improve properties such as adhesion, chemical resistance and heat resistance, it is desirable to use together with (B) epoxy resin and epoxy curing agent. Examples of such epoxy curing agents include imidazole derivatives, phenol derivatives, dicyandiamide, dicyandiamide derivatives, hydrazide derivatives, amines, acid anhydrides and the like. The above curing agents may be used alone or in combination of two or more. The amount of the curing agent used is such that the active hydrogen amount of the curing agent is 0.5 to 1 equivalent of the epoxy group of the epoxy resin (B).
A ratio of 1.2 equivalents is preferable.

Specific examples of the photopolymerization initiator (C) include benzoins, acetophenones, anthraquinones, thioxanthones, benzophenones, and the like. Examples of the benzoins include benzoin, benzoin methyl ether, and benzoin isopropyl ether. Derivatives such as acetophenones, acetophenone for acetophenones, derivatives of 2,2-dimethoxy-2-phenylacetophenone, and anthraquinones for 2-methylanthraquinone, 2-chloroanthraquinone, 2-ethylanthraquinone, 2-t-
Derivatives such as butylanthraquinone, thioxanthones include thioxanthone, 2,4-dimethylthioxanthone,
Derivatives such as 2,4-diethylthioxanthone and benzophenones include benzophenone and 4-benzoyl-4 ′.
-Methyldiphenyl sulfide, 4,4'-dichlorobenzophenone, N, N-dimethylaminobenzophenone and other derivatives, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc., 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholinopropanone-1 and the like, which can be used alone or in combination of two or more kinds. Further, the (C) photopolymerization initiator is
You may use together a well-known photosensitizer. Specific examples thereof include triethanolamine, tripropanolamine, triethylamine, N, N-dimethylamino acid benzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, and pentyl-4-dimethylaminobenzoate. The above-mentioned photosensitizers may be used alone or in combination of two or more. The (C) photopolymerization initiator is preferably added in an amount of 0.5 to 20% by weight based on the composition.

The (D) polymerizable unsaturated compound and / or solvent is used for the purpose of improving the curability with respect to active energy rays and / or the coatability when the photosensitive resin composition is used as a resist ink. Is.
As the polymerizable unsaturated compound, active energy ray curable monomers are preferable, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
N-pyrrolidone, N-acryloylmorpholine, N, N-
Dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminoethyl acrylate, N, N-
Dimethylaminopropyl acrylate, methoxy polyethylene glycol acrylate, ethoxy polyethylene glycol acrylate, melamine acrylate, phenoxyethyl acrylate, phenoxypropyl acrylate, ethylene glycol diacrylate, dipropylene glycol diacrylate, polydipropylene glycol diacrylate, trimethylolpropane triacrylate, penta Erythritol triacrylate,
Examples thereof include pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, glycerin diacrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate and various methacrylates corresponding thereto. These (D) polymerizable unsaturated compounds may be used alone or in combination of two or more.

On the other hand, as the solvent, methyl ethyl ketone,
Methyl isobutyl ketone, ketones such as cyclohexanone, aromatic hydrocarbons such as toluene and xylene, ethyl cellosolve, butyl cellosolve, carbitol, carbitol such as butyl carbitol, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, ethyl Examples thereof include carbitol acetate. These solvents may be used alone or in combination of two or more.

The amount of the polymerizable unsaturated compound (D) and / or the solvent used is 5 to 80% by weight, preferably 10 to 60% by weight, based on the composition. Above all, when the amount of the polymerizable unsaturated compound used is less than 5% by weight, the photosensitivity is too low,
On the other hand, when it exceeds 80% by weight, the viscosity becomes too low when the photosensitive resin composition is used as a resist ink, and the resistance as a cured coating film becomes insufficient.

In addition, when the photosensitive resin composition of the present invention is used as a liquid resist ink, inorganic fillers such as silica, calcium carbonate, barium sulfate, clay, talc, etc., and phthalocyanine green may be added, if necessary. ，
Color pigments such as phthalocyanine blue, titanium oxide and carbon black, various additives such as defoaming agents and leveling agents, hydroquinone, resorcinol, catechol, pyroganol, hydroquinone monomethyl ether, t-
A polymerization inhibitor such as butylcatechol or phenothiazine may be used.

[0025]

EXAMPLES The contents of the present invention will be described in detail below with reference to examples and comparative examples, and "part" in each example indicates a weight basis. The invention is not limited to these examples only.

Synthesis Example 1 (Synthesis Example of Photosensitive Resin-1) Bisphenol A was placed in a flask equipped with a stirrer and a reflux tube.
Type epoxy resin [Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent 186] 186 parts (1.0 equivalent), cresol novolac [CRM-552, manufactured by Showa Highpolymer Co., Ltd., weight average molecular weight 550, hydroxyl group Equivalent 12
2.2] Charge 36.7 parts (0.3 equivalent) and 100 ° C
The mixture was heated and stirred to uniformly dissolve the above mixture. Next, 1.1 parts of triphenylphosphine was charged into the system,
The reaction was carried out at 0 ° C. for 1 hour to obtain a cresol novolac-modified bisphenol A type epoxy resin (epoxy equivalent 318) having a weight average molecular weight of 2500. Next, set the temperature to 100 ° C.
Then, 141 parts of ethyl carbitol acetate was charged, 50.4 parts (0.7 mol) of acrylic acid and 0.08 part of methylhydroquinone were charged, the mixture was heated to 110 ° C., the reaction was continued for 6 hours, and the acid value was 0. A reaction product (I) of 0.5 mg KOH / g was obtained. To this, tetrahydrophthalic anhydride 5
Charge 6.2 parts (0.37 mol) and add 6 more parts at 90 ° C.
Reaction for a time, weight average molecular weight 3600, solid content acid value 6
3 mgKOH / g, 70% solid content concentration of photosensitive resin-1
Got

Synthesis Example 2 (Synthesis Example of Photosensitive Resin-2) In a flask equipped with a stirrer and a reflux tube, an isocyanate-modified epoxy resin [XAC415 having the following general formula was obtained.
2, Asahi Kasei Epoxy Co., Ltd., epoxy equivalent 338,
Softening point 76 ° C] 338 parts (1.0 equivalent), phenol novolac [BRG-553, Showa Highpolymer Co., Ltd., weight average molecular weight 1950, hydroxyl equivalent 103.7] 20.7
(0.2 equivalents), charged to 100 ° C., stirred,
The above mixture was dissolved uniformly. Next, 1.1 parts of triethylamine was charged into the system and reacted at 150 ° C. for 1 hour,
Phenol novolac modified bisphenol A type epoxy resin with a weight average molecular weight of 4300 (epoxy equivalent 448)
Got

[0028]

[Chemical 1]

Next, the temperature was lowered to 100 ° C., 218 parts of ethyl carbitol acetate was charged, and acrylic acid 5 was added.
7.6 parts (0.8 mol), methyl hydroquinone 0.0
Charge 8 parts, heat to 110 ° C and continue the reaction for 6 hours.
A reaction product (I) having an acid value of 0.5 mgKOH / g was obtained. To this, 91.2 parts (0.6 mol) of tetrahydrophthalic anhydride was charged, and the mixture was reacted at 90 ° C. for a further 6 hours to obtain a photosensitive resin having a weight average molecular weight of 6200, a solid content acid value of 66 mgKOH / g and a solid content concentration of 70%. Resin-2 was obtained.

Comparative Synthesis Example 1 (Synthesis Example of Photosensitive Resin-3) Cresol novolac type epoxy resin [Epotote YD]
CN-704, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 21
0, softening point 90 ° C.] 210 parts, acrylic acid 72 parts (1 mol), methylhydroquinone 0.28 parts, carbitol acetate 149.5 parts were charged and heated to 95 ° C. to uniformly dissolve the above mixture. After confirming the above, 1.4 parts of triphenylphosphine was charged and heated to 100 ° C.
The reaction was carried out for 0 hours to obtain a reaction product having an acid value of 0.5 mgKOH / g. This was charged with 66.9 parts (0.44 mol) of tetrahydrophthalic anhydride, heated to 90 ° C. and reacted for about 6 hours to give a solid content acid value of 70 mgKOH / g and a solid content concentration of 6
0% of the photosensitive resin (A-3) was obtained.

Comparative Synthesis Example 2 (Synthesis Example of Photosensitive Resin-4) Bisphenol A type epoxy resin [Epicoat 100
1. Yuka Shell Epoxy Co., Ltd., epoxy equivalent 47
3] 473 parts, acrylic acid 72 parts (1 mol), methylhydroquinone 0.54 parts, carbitol acetate 23
After charging 4 parts and heating to 95 ° C. and confirming that the above mixture was uniformly dissolved, 1.4 parts triphenylphosphine was charged and heated to 100 ° C. and reacted for about 30 hours to give an acid value of 0.5 mg KOH. / G of reaction product was obtained. To this, 127.7 parts (0.84 mol) of tetrahydrophthalic anhydride was charged, heated at 90 ° C. and reacted for about 6 hours to obtain a photosensitive resin having a solid content acid value of 70 mgKOH / g and a solid content concentration of 60%.
Got 4.

Examples 1 and 2 and Comparative Examples 1 and 2 Using the photosensitive resins obtained from the above-mentioned synthetic examples and comparative synthetic examples, the photosensitive resins were kneaded in a three-roll mill according to the compounding ratio shown in Table 1. A composition was prepared. Next, the photosensitive resin composition is applied to a pre-degreased printed circuit board by a screen printing method so as to have a dry film thickness of 30 to 40 μm, pre-dried at 80 ° C. for 20 minutes, then cooled to room temperature and dried. A coating film was obtained. A negative film having a resist pattern is brought into close contact with this coating film, exposed to 350 mJ / cm ³ using an ultraviolet exposure device, the negative film is removed, and then a 1% sodium carbonate aqueous solution is used to spray pressure 2.0 kgf / cm. ^It was developed at ² for 60 seconds to dissolve and remove the unexposed portion. Then, using a hot air dryer, 150
Heat curing was carried out at 30 ° C. for 30 minutes to obtain a test piece. The resulting coating film was evaluated for various physical properties according to the test methods described below. Table 2 shows the evaluation results of these tests. It was confirmed that Examples 1 and 2 have physical properties having both the heat resistance, which is an advantage of the cresol novolac system, and the flexibility, which is an advantage of the bisphenol type.

[0033]

[Table 1]

* 1: 1,3,5-triglycidyl isocyanurate [manufactured by Nissan Kagaku KK] * 2: Irgacure 907, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholinopropanone-1 [Ciba Geigy] * 3: Kayacure DETX-S, 2,4-diethylthioxanthone [Nippon Kayaku Co., Ltd.] * 4: Light acrylate TMP- A, trimethylolpropane triacrylate [manufactured by Kyoeisha Chemical Co., Ltd.] * 5: Aerosil 300, [manufactured by Nippon Aerosil Co., Ltd.]

(Developability) Predrying time is 20 minutes, 40
Minutes, 60 minutes, 80 minutes, 100 minutes dry coating film 1%
Using sodium carbonate aqueous solution, spray pressure 2.0 kgf
/ Cm ^{2 It} was developed for 60 seconds, the presence or absence of the coating film after development was observed and evaluated according to the following criteria. ◯: Ink was completely removed during development and development was possible. X: Some parts cannot be developed during development.

(Adhesion) According to the test method of JIS D 0202, cross-cuts were put on the coating film in a grid pattern, and then the state of peeling after a peeling test with cellophane tape was visually judged. The evaluation was performed based on the following criteria. ◯: No peeling at all. Δ: The cross cut part was slightly peeled off. X: The coating film is peeled off.

(Solder Heat Resistance) According to the test method of JIS C 6481, the test piece was immersed in a solder bath at 260 ° C. for 10 seconds, three times, and taken out. Then, the change in appearance was observed. The evaluation was performed based on the following criteria. ○: No change in appearance. Δ: Discoloration of the cured film was observed. X: There is floating, peeling, or latent solder in the cured film.

(Electroless Gold Plating Resistance) As a pretreatment of a test piece, it is immersed in an acidic degreasing solution at 30 ° C. → immersion rinsing → soft etching treatment → immersion rinsing → catalyst application (immersion in nickel plating catalyst solution at 30 ° C. for 7 minutes). ) → The immersion washing process was performed. Next, in the electroless nickel plating step, the test piece is dipped in a nickel plating solution (85 ° C., PH = 4.6) for 20 minutes → acid dipped for 1 minute (10 vol% sulfuric acid aqueous solution at room temperature) →
Immersion water washing is performed, and finally, as an electroless gold plating step, the test piece is immersed in a gold plating solution (95 ° C., PH = 6, 3% by volume of potassium gold cyanide for 3 minutes) → immersion water washing → 6
Immersion in hot water at 0 ° C Washing with water → After thoroughly washing with water → Drain the water well →
Electroless gold plating was performed in the drying step, and the test piece was observed for changes in appearance and peeling test using cellophane tape. The evaluation was performed based on the following criteria. Good: No change in appearance and no peeling of the resist. Δ: There is no change in appearance, but slight peeling of the resist is seen. X: The resist floated or the plating diving was observed, and the peeling of the resist was large in the peeling test.

(PCT test) The test piece was put at 121 ° C. and 2 at
m, the appearance of the coating film after standing for 100 hours in a saturated steam atmosphere was judged. The evaluation was performed based on the following criteria. ○: The coating film does not swell or peel off. X: Swelling or peeling.

(Flexibility test) According to JIS K5400, by using an Erichsen tester specified in JIS B7729 A method, the photosensitive resin composition is coated on a bond steel plate, dried, exposed, developed, and heated, A hard sphere was extruded from the back surface of the obtained test piece, and the extrusion distance until the coating film was cracked and peeled when the test piece was deformed was measured. The evaluation was performed based on the following criteria. ⊚: When the hard ball was extruded at a distance of 6 mm or more, cracking and peeling of the coating film did not occur. ◯: When the hard ball was extruded at a distance of 4 mm or more, the coating film was not cracked or peeled. X: The distance at which the hard sphere was extruded was less than 4 mm, and the coating film was cracked and peeled off.

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

According to the present invention, the developability in a dilute alkaline aqueous solution is particularly excellent, and the coating film after curing is particularly flexible,
Provided is a photosensitive resin composition having excellent heat resistance, solder heat resistance, adhesion, water resistance, bending resistance, chemical resistance, and the like. The photosensitive resin composition of the present invention is suitable for electronic material fields such as a printed wiring board solder resist, a high-density multilayer board interlayer insulating film, a semiconductor package solder resist, and a flexible printed wiring board resist ink.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A 2-123359 (JP, A) JP-A 2-116850 (JP, A) JP-A 63-262893 (JP, A) JP-A 1- 126362 (JP, A) JP 63-132233 (JP, A) JP 61-243869 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7 / 42

Claims (8)

(57) [Claims] 1. A hydroxyl group of a reaction product (I) obtained by adding an unsaturated monobasic acid to an epoxy group of (A) a phenol novolac and / or a cresol novolac-modified bisphenol epoxy resin is further saturated and / or unsaturated. Photosensitive resin composition containing a resin obtained by addition reaction with a saturated polybasic acid anhydride, (B) an epoxy resin, (C) a photopolymerization initiator, and (D) a polymerizable unsaturated compound and / or a solvent. . 2. The phenol novolac and / or cresol novolac-modified bisphenol type epoxy resin in the component (A) has a hydroxyl group of 0.05 to 0.5 equivalent of a hydroxyl group of phenol novolac with respect to 1 equivalent of an epoxy group of the bisphenol type epoxy resin. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is reacted at a ratio. 3. The bisphenol type epoxy resin modified with phenol novolac and / or cresol novolac in the component (A) is obtained by reacting with a phosphorus-based catalyst, according to claim 1 or 2. Photosensitive resin composition. 4. The bisphenol-type epoxy resin in the component (A) is an isocyanate-modified epoxy resin which is a reaction product of a bisphenol-type epoxy resin and a diisocyanate compound. The photosensitive resin composition described. 5. In the component (A), 0.1 to 0.8 equivalent of a saturated and / or unsaturated polybasic acid anhydride is reacted with 1 equivalent of the hydroxyl group in the reaction product (I). It exists, The photosensitive resin of any one of Claim 1 thru | or 4 characterized by the above-mentioned. 6. The photosensitive resin composition according to claim 1, wherein the epoxy resin (B) is blended in an amount of 1 to 50% by weight based on the composition. 7. The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (C) is blended in an amount of 0.5 to 20% by weight based on the composition. 8. The photosensitive resin composition according to claim 1, wherein (D) the polymerizable unsaturated compound and / or the solvent is blended in an amount of 5 to 80% by weight based on the composition. .