KR20150036042A - Alkali development type resin, and photosensitive resin composition using same - Google Patents

Abstract

The present invention is characterized in that a saturated and / or unsaturated polybasic acid anhydride (c) is further reacted with a hydroxyl group in a reaction product X obtained by reacting a hydroxyl group of a phenol resin (a) with a compound (b) having an alcoholic hydroxyl group and an epoxy group in a molecule (B) an epoxy resin, (C) a photopolymerization initiator, and (D) a diluent, wherein the resin composition has a dryness and an alkali The coating film having excellent developability and cured has excellent properties such as adhesion, solder heat resistance, electroless gold plating resistance, PCT resistance, flexibility, cold and heat shock resistance and HAST characteristics, and is excellent in solder resist , An etching resist, a plating resist, an interlayer insulating material, and the like.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an alkali developing resin and a photosensitive resin composition using the same,

The present invention relates to an alkali-developable resin and a photosensitive resin composition containing the same. More particularly, the present invention relates to an alkali developing resin and a photosensitive resin composition used in electronic materials such as a printed wiring board solder resist, a high density multilayered interlayer insulating film, and a semiconductor package solder resist.

Conventionally, a permanent mask resist in the production of a printed wiring board has been produced by a method of screen printing a thermal or ultraviolet curing type resist ink. From the productivity point of view, however, the transition from a liquid developer to a liquid type solder photoresist has been made.

However, in the conventional printed wiring board on which the alkali developing type solder resist is applied, resistance to PCT (Pressure Cooker Test), which is a long term reliability test of the package, is poor and peeling of the cured product occurs.

In addition, due to the moisture absorption of the solder resist, so-called popcorn phenomenon, in which the moisture absorbed into the package during the reflow of the package is boiled, and cracks are generated in the solder resist film and its surroundings. The problems of moisture absorption resistance and long term reliability are not limited only to the case of the above mounting technique, but may be applied to a solder resist of a general printed wiring board, a multilayer wiring board such as a solder resist used for manufacturing a flexible printed wiring board or a tape carrier package, But also for other applications such as an interlayer insulating layer of a dielectric layer.

As described above, according to recent developments of the electric industry and the semiconductor industry, it is required to improve the properties of one layer such as heat resistance, toughness, flexibility, water resistance and chemical resistance. Is being developed.

Conventionally, photosensitive resins using novolak-type epoxy resins as starting materials have been widely used in many fields of electronic materials such as solder resists and etching resists for their excellent adhesiveness, heat resistance, chemical resistance, electrical insulation and the like. Particularly, a resin obtained by reacting a reaction product of a cresol novolak type epoxy resin and an unsaturated group-containing monocarboxylic acid with a polybasic acid anhydride is widely used as a photosensitive resin containing a carboxyl group excellent in heat resistance (Patent Document 1). However, this resin is excellent in heat resistance, but has a drawback that it is liable to cause cracks due to heat shock because it shrinks at the time of curing, is small in elongation, and lacks toughness. As a photosensitive resin for solving this problem, a photosensitive prepolymer (Patent Document 2) which is a reaction product of a resin obtained by partially epoxidizing a branched chain hydroxyl group of a bisphenol-type epoxy resin, a (meth) acrylic acid and a polybasic acid anhydride (Patent Document 2), a cresol novolak- Unsaturated group-containing polycarboxylic acid resin obtained by reacting a reaction product of hydroxyphenethyl alcohol with tetrahydrophthalic anhydride (Patent Document 3) and the like have been proposed. However, these resins are still insufficient to satisfy both heat resistance and toughness.

Further, as a resin having excellent long-term reliability, there has been proposed a photosensitive resin containing a carboxyl group (hereinafter referred to as patent document 4) in which a novolac resin is modified with an alkylene oxide and then a (meth) acrylic acid is added and a polybasic acid anhydride is added. However, there was room for improvement in drying property after ink application. That is, in these compositions, it is necessary to increase the acid value in order to perform development with a dilute aqueous alkali solution. For this reason, in a series of processes in which the drying time must be shortened in the drying step of the solvent after coating the ink-blended material on the substrate, or in the series of steps of drying and exposing, The unexposed portion of the photoreceptor can not be removed quickly.

Japanese Unexamined Patent Publication No. Hei 1-54390 Japanese Patent Application Laid-Open No. 9-54434 Japanese Patent Laid-Open No. 11-288091 Japanese Patent No. 3964326

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a carboxyl group-containing resin which can obtain an ink composition excellent in dryness and various physical properties such as good developing properties, heat resistance, moisture resistance and adhesiveness.

It is another object of the present invention to provide a cured film which is capable of forming a cured film excellent in various properties required for various uses as described below and capable of coping with high density and cotton boom of a printed wiring board, And it is an object of the present invention to provide a curable resin composition. That is, the solder resist of a general printed wiring board, the solder resist used for manufacturing a flexible printed wiring board or a tape carrier package, and the interlayer insulating layer of a multilayer wiring board such as a build-up board have excellent developability, adhesiveness, solder heat resistance, , PCT resistance, electrical insulation, and the like. In particular, a cured film excellent in properties such as moisture absorption resistance and PCT (pressure cooker test) resistance is required in an IC package. In the present invention, it is an object of the present invention to provide a curable resin composition capable of forming a cured film excellent in various properties required for various uses thereof and having the above-mentioned properties.

In order to solve these problems of the prior art, the present inventors have proposed an alkali developing type resin in which a carboxyl group is further introduced as a functional group into a reaction product obtained by introducing a primary hydroxyl group and a reactive functional group into a skeleton of a phenol resin, (C) is reacted with a hydroxyl group in a reaction product X (resin) obtained by reacting a hydroxyl group of the phenol resin (a) with a compound (b) having an alcoholic hydroxyl group and an epoxy group in the molecule, , That is, the alkali developing resin can achieve the above object, and have completed the present invention.

The term " alkali-developing resin " in the present specification means a resin capable of imparting alkali developability to the resin composition, that is, an alkali developable resin. Therefore, the alkali-developing resin of the present invention is most suitable for the alkali developing photosensitive resin composition, but can be used for other purposes.

The term (meth) acrylic acid is used in the meaning of at least one of acrylic acid and methacrylic acid, and (meth) acrylate (at least one of acrylate and methacrylate) is used in the same meaning.

More particularly, the present invention relates to the invention described in the following (1) to (21).

(Hereinafter, simply referred to as "intermediate X") obtained by reacting (1) a compound (b) having an alcoholic hydroxyl group and an epoxy group in the molecule in the hydroxyl group of the phenol resin (a) (Hereinafter also referred to as the resin Y or the resin Y of the present invention) obtained by reacting the above polybasic acid anhydride (c) (hereinafter also simply referred to as "polybasic acid anhydride (c)") ).

(2) The alkali-developing resin according to (1) above, wherein the amount of the compound (b) is 0.1 to 0.9 mol based on 1 equivalent of the phenolic hydroxyl group of the phenol resin (a).

(3) The alkali-developing resin according to (1) or (2) above, wherein the polybasic acid anhydride (c) is reacted at a rate of 0.05 to 0.9 mol based on 1 equivalent of the hydroxyl group of the reaction product X.

(4) The alkaline developer according to any one of (1) to (3), wherein the proportion of the phenolic hydroxyl groups remaining in the alkali-developable resin is 10 to 90% based on the total number of phenolic hydroxyl groups in the phenolic resin (a) Type resin.

(5) The alkali-developable resin according to any one of (1) to (4), wherein the phenol resin (a) is a phenol resin (a) containing a biphenyl skeleton.

(6) The alkali-developable resin according to any one of (1) to (5), wherein the phenolic resin (a) is a phenolic resin (a1) represented by the following general formula (1).

M1, m2 and m3 each independently represent an integer of 1 or 2 and n represents an integer of 0 to 10,

(7) The alkali-developable resin according to (6), wherein the phenol resin (a1) is a phenol resin containing a resorcin structure.

(8) The alkali-developable resin according to (7), wherein the phenolic resin having a resorcin structure has a hydroxyl equivalent of 70 to 170 g / eq.

(9) The alkali-developable resin according to any one of (1) to (8), wherein the compound (b) is glycidol.

(10) The alkali-developing resin according to any one of (1) to (9), wherein the polybasic acid anhydride (c) is an anhydride of a polybasic acid having two or three carboxyl groups.

(11) A photosensitive resin composition comprising (A) the alkali-developable resin according to any one of (1) to (10)

(B) an epoxy resin,

(C) a photopolymerization initiator, and

(D) a diluent.

(12) The photosensitive resin composition according to (11), wherein the diluent is a polymerizable unsaturated compound and / or a solvent.

(13) A positive resist composition comprising (A) 10 to 80% by weight, based on the total amount of the composition,

(B) an epoxy resin in an amount of 1 to 50% by weight,

(C) a photopolymerization initiator in an amount of 0.5 to 20% by weight based on the total amount of the composition, and

The photosensitive resin composition according to (11) or (12) above, wherein the diluent (D) is 10 to 200 parts by weight based on 100 parts by weight of the alkali developing resin.

(14) The photosensitive resin composition according to any one of (11) to (13), wherein as the diluent, the polymerizable unsaturated compound is contained in an amount of 5 to 200% by weight based on 100 parts by weight of the alkali developing resin.

(15) The photosensitive resin composition according to (14), wherein the polymerizable unsaturated compound is a (meth) acrylate compound.

(16) A cured product of the photosensitive resin composition according to any one of (11) to (15).

(17) A cured product of the photosensitive resin composition described in (16), which is a patterned cured product by using a photolithographic method capable of ultrafine processing by light.

(18) A substrate having a layer of the cured product according to (16) or (17).

(19) An article having a substrate according to (18) above.

(20) The photosensitive resin composition according to any one of (11) to (15) above is applied to a printed wiring board to form a coating film, exposed and developed, and then cured by irradiation with ultraviolet light and / To form a cured coating film.

(21) A process for producing the alkali-developable resin as described in (1) above, which comprises reacting a phenolic resin (a) with a compound (b) having an alcoholic hydroxyl group and an epoxy group in the molecule, Use of the reaction product X with both of the hydroxyl groups.

(Effects of the Invention)

The photosensitive resin composition of the present invention is excellent in dryness and alkali developability, and the coated film after curing has excellent properties such as adhesion, solder heat resistance, electroless gold plating resistance, PCT resistance, flexibility, cold shock resistance and HAST characteristics Do. Since the cured film can be formed at a low cost with good productivity, it can be used for an ultraviolet curable printing ink application for curing using an active energy ray, and the like. In addition, the solder resist, etching resist, It is useful for insulation materials and so on.

Hereinafter, the present invention will be described in more detail.

First, in the resin Y of the present invention, a phenol resin (a) is used as a skeleton resin. The phenol resin (a) in the present invention means a phenol resin in a broad sense, and means a resin having at least two phenolic hydroxyl groups in one molecule. Therefore, as the phenol resin (a), a phenol resin having at least two phenolic hydroxyl groups in one molecule is used. The phenol resin (a) may be any phenol resin such as a resol-based, novolac-based, or cresol-based resin. Further, it is also possible to use an epoxy-modified type in which a polyfunctional phenol compound is modified with an epoxy compound, a phenol-modified butadiene (co) polymer in which a phenol is added to a butadiene (co) polymer, a polymerization resin of a phenol and dicyclopentadiene, Resin can also be used.

Specific examples thereof include novolak type phenol resins such as phenol novolac resins, cresol novolak resins and biphenyl novolac type resorcin resin, paraxylylene modified novolak resins, meta-xylylene modified novolak resins, Modified novolac phenolic resins such as phenol-modified novolac resins; Bisphenol compounds such as bisphenol A and bisphenol F; Biphenyl-type phenolic resins; Resol type phenolic resin; Phenolic aralkyl resins, biphenyl aralkyl type phenol resins; Alkane type phenol resins such as triphenol alkane type resins and polymers thereof; Naphthalene ring-containing phenol resin, dicyclopentadiene-modified phenol resin, alicyclic phenol resin, and heterocyclic phenol resin. These phenolic resins may be used alone or in combination of two or more.

The phenol resin (a) has a molecular weight of about 300 to 30,000, preferably about 400 to 15,000. As the molecular weight of the resin, a number average molecular weight or a weight average molecular weight is used, but any one of them may fall within the above range.

A preferred resin of the phenol resin (a) is a novolak type phenol resin, more preferably a phenol resin having a cresol skeleton or biphenyl skeleton in its structure, more preferably a biphenyl skeleton And the like. Specifically, cresol type novolak resins having a cresol skeleton include bresyl phenol resins, biphenyl aralkyl type phenol resins and biphenyl novolac type phenol resins as a phenol resin having a biphenyl skeleton.

More preferred is a biphenyl skeleton-containing novolak-type phenol resin, more preferably a phenol resin (a1) represented by the following general formula (1).

 (Wherein m1, m2 and m3 are each independently an integer of 1 or 2 and n is an integer of 0 to 10)

In the phenol resin (a1) of the general formula (1) (hereinafter also simply referred to as the phenol resin (a1)), a benzene ring having two hydroxyl groups Is a phenol resin having a resorcin structure).

The ratio of the number of hydroxyl groups in the two benzene rings having a hydroxyl group (preferably a resorcin structure) to the total number of phenolic hydroxyl groups in the phenol resin (a1) is preferably 5 to 100%. This ratio is calculated from the molar ratio of phenol to dihydroxybenzene (preferably resorcinol) used in the synthesis of the phenol resin (a1). The molar ratio d1 of the phenol used, the dihydroxybenzene Resorcin) is d2, it is calculated by the following equation.

{(d2x2) / (d1 + d2x2)} x100

As the phenol resin (a1), it is preferable to use a phenol resin having an average molecular weight of about 500 to 15,000.

The phenol resin (a1) of the general formula (1) can be obtained by producing the phenol resin (a1) according to the methods described in the known documents, and examples thereof include those disclosed in Japanese Patent Application Laid-Open Nos. 8-143648 and 7-292066 And the like, or can be easily obtained therefrom. That is, it can be obtained by reacting phenol or / and resorcin with bis (methoxymethyl) biphenyl or bis (chloromethyl) biphenyl.

The preferred range of the hydroxyl group equivalent of the phenol resin (a1) is about 70 to 170 g / eq, and in some cases about 102 to 140 g / eq. The hydroxyl group equivalent of the phenol resin can be measured by a conventional method.

As the compound (b) having an alcoholic hydroxyl group and an epoxy group in the molecule to be reacted with the phenol resin (a), any known compound may be used as long as it is a compound having an alcoholic hydroxyl group and an epoxy group in the molecule, And monoglycidyl ethers of glycols having 2 to 4 carbon atoms such as glycidol or ethylene glycol monoglycidyl ether. In the present invention, glycidol is particularly preferable.

In the reaction of the phenol resin (a) with the compound (b), the compound (b) is preferably used in an amount of 0.1 to 0.9 mol, more preferably 0.1 to 0.8 mol, per mol of the phenolic hydroxyl group of the phenol resin (a) , And more preferably 0.2 to 0.8 mol. In some cases, the compound (b) may be reacted at a ratio of 0.1 to 0.7 mol, or 0.1 to 0.6 mol, and preferably 0.2 to 0.6 mol, based on 1 equivalent of the phenolic hydroxyl group of the phenol resin (a) Very desirable.

If the amount of the compound (b) is excessively high, the water-solubility of the resin X of the present invention obtained by reacting the polybasic acid anhydride (c) is excessively high, and the water resistance of the cured product of the resin composition containing the resin X may be lowered .

In this reaction, the epoxy group of the compound (b) is ring-opened to the phenolic hydroxyl group of the phenol resin (a) to form an ether bond, and a secondary alcoholic hydroxyl group is formed.

In the reaction between the phenol resin (a) and the compound (b), not all of the phenolic hydroxyl groups of the phenol resin (a) react with the compound (b) (hereinafter also referred to as alcohol denaturation) Is left to remain. As a result, the preferred intermediate X includes both an unreacted phenolic hydroxyl group and an alcoholic hydroxyl group. The ratio of the phenolic hydroxyl groups remaining in the intermediate X is 1 when the total amount of the phenolic hydroxyl groups of the phenolic resin (a) of the starting material (the total amount of the alcohol-modified phenolic hydroxyl group and the residual phenolic hydroxyl group in the intermediate X) And the ratio thereof is about 0.1 to 0.9, preferably about 0.2 to 0.9, and more preferably about 0.3 to 0.9.

In addition, the remaining phenolic hydroxyl group of the intermediate X is retained in the resin Y as it is. This is because the polybasic acid anhydride (c) reacts with the alcoholic hydroxyl group in the intermediate X and does not react with the phenolic hydroxyl group in the reaction of the intermediate X with the polybasic acid anhydride (c) which is subsequently reacted.

In the preparation of the intermediate X, a solvent may be used for the reaction of the phenol resin (a) and the compound (b). As the solvent to be used, known solvents can be used, and examples thereof include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Glycol ethers such as dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol diethyl ether; But are not limited to, ethyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, Esters such as rosorb acetate and carbitol acetate; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated naphtha and solvent naphtha; And the like.

Further, it is also possible to use at least one monomer selected from the group consisting of carbitol (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate can also be used.

Further, it is preferable to use a catalyst in order to accelerate the reaction between the phenol resin (a) and the compound (b), and in this case, a known catalyst for reaction between the epoxy group and the phenolic hydroxyl group can be used. Examples of such catalysts include triethylamine, benzyldimethylamine, methyltriethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, chromium octanoate, zirconium octanoate And the like. The amount of such a catalyst to be used is preferably 0.01 to 1% by weight based on the reaction mixture. The reaction temperature is preferably 60 to 150 占 폚. The reaction time is preferably 5 to 24 hours. In this way, intermediate X can be obtained.

Resin Y is obtained by further reacting the polybasic acid anhydride (c) with the hydroxyl group (alcoholic hydroxyl group) of the intermediate X obtained as described above. Examples of the polybasic acid anhydride (c) include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Polybasic acid anhydrides such as dibasic acid anhydride, anhydrous trimellitic acid, anhydrous pyromellitic acid, benzophenonetetracarboxylic acid anhydride, and biphenyltetracarboxylic acid anhydride. In general, monoanhydrides are preferable, and anhydrides of polybasic acids having two or three carboxyl groups such as trimellitic anhydride, tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride are preferable, and more preferred are anhydrides of 2 Is a monobutic acid of a polybasic acid having 2 or 3 carboxyl groups on 6 hydrocarbons, and more preferably a monobutic acid of a polybasic acid having 2 or 3 carboxyl groups on a 6-membered carbon ring. The carbon 6-membered ring may be an aromatic ring or an aliphatic ring. Most preferably trimellitic anhydride or tetrahydrophthalic anhydride.

In the production of Resin Y, a saturated or unsaturated polybasic acid anhydride (c) is usually reacted at a ratio of 0.05 to 0.9 mol based on 1 equivalent of the hydroxyl group (alcoholic hydroxyl group) in the intermediate X.

Preferably, the saturated or unsaturated polybasic acid anhydride (c) is reacted at a ratio of 0.1 to 0.8 mol, more preferably 0.1 to 0.7 mol, per 1 equivalent of the hydroxyl group (alcoholic hydroxyl group) in the intermediate X. If the amount (added amount) of the polybasic acid anhydride (c) to be reacted is too small, the solubility in alkali is deteriorated due to the small proportion of the acidic groups, and sufficient alkali developability may not be obtained in some cases. The electrical characteristics of the semiconductor device may be deteriorated.

Further, in the obtained resin Y, the phenolic hydroxyl group remaining in the intermediate X usually remains as it is. The ratio of the phenolic resin (a) to the phenolic hydroxyl group (the total number of phenolic hydroxyl groups) of the phenolic hydroxyl group remaining in the resin Y is usually about 10 to 90%, preferably 20 to 90% , And more preferably 30 to 80%.

The ratio of the phenolic resin (a) of the raw phenolic hydroxyl group remaining in the resin Y to the phenolic hydroxyl group (total phenolic hydroxyl group number) of the resin Y is such that the reaction proceeds approximately quantitatively, Can be calculated.

When the resin Y was used in the photosensitive resin composition, it was judged that the resin Y having a large amount of phenolic hydroxyl groups remained favorable for improving the heat resistance of the cured product.

In addition, in the resin Y, there is a carboxyl group introduced in the reaction with the above polybasic acid anhydride (c). As a result, the preferred resin Y of the present invention is a resin containing the remaining three alcoholic hydroxyl groups without reacting with the residual phenolic hydroxyl group, carboxyl group and polybasic acid anhydride (c).

Preferred examples of the resin Y of the present invention are as follows.

(Hydroxyl group) in the reaction product X obtained by reacting the compound (b) having an alcoholic hydroxyl group and an epoxy group in the molecule in a ratio of 0.1 to 0.9 mole based on 1 equivalent of the hydroxyl group of the phenol resin (a) (C) in an amount of 0.05 to 0.9 mol based on 1 equivalent of the hydroxyl group (alcoholic hydroxyl group) in the reaction product X. The alkali developing resin is obtained by reacting the unsaturated polybasic acid anhydride (c)

(II) The alkali-developing resin according to (I), wherein the compound having an alcoholic hydroxyl group and an epoxy group in the molecule (b) is a glycidol or a monoglycidyl ether of a glycol having 2 to 4 carbon atoms.

(III) The alkali-developable resin according to (II), wherein the compound (b) is glycidol.

IV. The alkali-developable resin according to any one of the above-mentioned I to III, wherein the phenol resin (a) is a phenol resin containing a cresol skeleton or a biphenyl skeleton.

V. The alkali-developable resin according to the above IV, wherein the phenol resin containing a biphenyl skeleton is the phenol resin (a1) represented by the general formula (1).

VI. The alkali-developable resin according to the above V, wherein the phenolic resin (a1) comprises a resorcin structure and the hydroxyl equivalent is 70 to 140 g / eq.

VII. The alkali-developing resin according to any one of the above-mentioned I-VI, wherein the polybasic acid anhydride (c) is an anhydride of a polybasic acid having two or three carboxyl groups.

VIII The alkali-developable resin according to the above VII, wherein the anhydride of the polybasic acid having two or three carboxyl groups is at least one selected from the group consisting of trimellitic anhydride, tetrahydrophthalic anhydride, succinic anhydride and hexahydrophthalic anhydride.

IX An alkali developing resin as described in VIII above, wherein the anhydride of a polybasic acid having two or three carboxyl groups is an anhydride of a polybasic acid having two or three carboxyl groups on a carbon six-

X. The alkali-developable resin according to the above IX wherein the anhydride of the polybasic acid having two or three carboxyl groups on the carbon 6-membered ring is trimellitic anhydride or tetrahydrophthalic anhydride.

The present invention also relates to a photosensitive resin composition comprising (A) the resin Y of the present invention, (B) an epoxy resin, (C) a photopolymerization initiator, and (D) a diluent. As the diluent, a form containing a polymerizable unsaturated compound such as a (meth) acrylate compound is particularly preferable.

The amount of the resin Y contained in the photosensitive resin composition of the present invention is preferably about 10 to 80% by weight, more preferably about 15 to 60% by weight, and still more preferably 30 to 60% by weight based on the total amount of the photosensitive resin composition Weight%.

As the epoxy resin (B) used in the photosensitive resin composition of the present invention, those having two or more epoxy groups in one molecule are usually used.

Examples of the epoxy resin include biphenyl novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, phenol aralkyl type epoxy resin , Dicyclopentadiene-phenol novolak type epoxy resin, phenol-cresol novolac co-condensation type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin or halogenated epoxy compound thereof, triphenylol methane type Epoxy resins obtained by reacting polyfunctional phenols such as epoxy resins, alkyl-substituted trimethylolmethane type epoxy resins and tetraphenylol ethane type epoxy resins with epichlorohydrin, polyfunctional hydroxy naphthalenes are reacted with epichlorohydrin Epoxy resin obtained, silicone-modified epoxy resin,? -Caprolactone-modified epoxy resin, This gave Lorient and primary or glycidyl amine-type epoxy resin obtained by the reaction of a secondary amine, such as triglycidyl heterocyclic epoxy resins such as glycidyl isocyanates are exemplified. One or more of these epoxy resins may be used in combination. It is also effective to use an isocyanate-modified epoxy resin for the purpose of improving the toughness at which the glass transition point (Tg) is ensured or to use a phosphorus-containing epoxy resin or the like from the viewpoint of imparting flame retardancy.

The epoxy resin (B) is blended in the composition as a thermosetting component in order to improve various properties as a solder resist such as adhesion, heat resistance and resistance to electrolysis, and after development with a dilute aqueous alkali solution in the production of a printed wiring board and the like, The resin is cured by the adhesive agent to give a more excellent adhesion to the wiring board, heat resistance, and resistance to electrolysis.

The epoxy resin (B) is used alone or as a mixture of two or more kinds. The amount of the epoxy resin contained in the photosensitive resin composition of the present invention is usually about 1 to 50% by weight, preferably 3 to 45% , More preferably about 5 to 45 wt%.

In the case of using the epoxy resin (B) as the thermosetting component, it is preferable to use an epoxy resin curing agent in combination in order to further improve the properties such as adhesion, chemical resistance and heat resistance. Examples of such epoxy resin curing agents include imidazole derivatives, phenol derivatives, dicyandiamide, dicyandiamide derivatives, hydrazide derivatives, amines, and acid anhydrides. These curing agents may be used alone or in combination of two or more. The amount of the curing agent to be used is preferably such that the amount of active hydrogen of the curing agent is 0.5 to 1.2 equivalents based on 1 equivalent of the epoxy group of the epoxy resin.

Specific examples of the photopolymerization initiator (C) used in the photosensitive resin composition of the present invention include benzoins, acetophenones, anthraquinones, thioxanthones and benzophenones, and, for example, benzoin, Benzoin methyl ether, benzoin isopropyl ether and the like, acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy- -Dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, N, N- Derivatives such as 2-methyl anthraquinone, 2-chloro anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 2-amylanthraquinone and 2-amino anthraquinone in the case of anthraquinones, In the acid type, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioic acid 2-isopropylthioxanthone, and 2,4-diisopropylthioxanthone; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 4,4'-dichloro Derivatives such as benzophenone, N, N-dimethylaminobenzophenone, methylbenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone and 4-benzoyl-4'-methyldiphenyl sulfide, 4,6-trimethylbenzoyldiphenylphosphine oxide, and the like, which may be used alone or in combination of two or more.

A known photosensitizer such as tertiary amines may be used in combination with the photopolymerization initiator (C). Specific examples thereof include triethanolamine, tripropanolamine, triethylamine, N, N-dimethylamino benzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate and the like.

The above-mentioned photopolymerization initiator (C) may be used alone or in combination of two or more, and a known photosensitizer may be used in combination. The use ratio of the photopolymerization initiator (C) is about 0.5 to 20% by weight, preferably about 1.0 to 15% by weight, based on the total amount of the photosensitive resin composition.

A polymerizable unsaturated compound and / or a solvent is used as the diluent (D) in the photosensitive resin composition of the present invention. The polymerizable unsaturated compound and / or the solvent used as the diluent (D) is used for the purpose of improving the curability against the active energy ray and / or improving the applicability in the case of using the photosensitive resin composition as a resist ink.

As such polymerizable unsaturated compounds, monomers having an active energy ray-curable property are preferable, and 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-pyrrolidone, N-acryloylmorpholine, N, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropylacrylate, methoxypolyethylene glycol acrylate, ethoxypolyethylene glycol acrylate, melamine Acrylate, phenoxyethyl acrylate, phenoxypropyl acrylate, ethylene glycol diacrylate, dipropylene glycol diacrylate, polydipropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, penta Erythritol tetraacrylate, dipentaerythritol hexaacrylate, glycerin diacrylate (Meth) acrylate compounds such as isobornyl acrylate, dicyclopentenyloxyethyl acrylate, and various methacrylates corresponding thereto. One or more of these polymerizable unsaturated compounds may be used in combination.

The (meth) acrylate compound is preferably the above, and among the (meth) acrylate compounds, a polyfunctional (meth) acrylate compound is preferable, and a 2- to 6-functional (meth) acrylate compound is more preferable.

In the present invention, a form containing a polymerizable unsaturated compound is preferable in order to form a photosensitive resin composition.

The blending amount of the polymerizable unsaturated compound is usually 3 to 200 parts by weight, preferably 5 to 200 parts by weight, more preferably 5 to 100 parts by weight, still more preferably 7 To 50 parts by weight.

Examples of the solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, carbitols such as ethyl cellosolve, butyl cellosolve, carbitol and butyl carbitol, Examples of the solvent include ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, ethylcarbitol acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate , Propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol monomethyl ether acetate, and the like. These solvents may be used alone or in combination of two or more.

The polymerizable unsaturated compound or solvent used as the diluent (D) may be used alone or as a mixture of two or more thereof. The amount of the polymerizable unsaturated compound and / or solvent used is about 10 to 200 parts by weight, preferably about 20 to 150 parts by weight, based on 100 parts by weight of the resin Y, based on the total amount of the polymerizable unsaturated compound and / Respectively. In particular, the polymerizable unsaturated compound contributes to imparting the curing property of the resin to the active energy ray. The amount of the polymerizable unsaturated compound to be used is usually 3 parts by weight or more, preferably 5 parts by weight or more, More preferably not less than 7 parts by weight and most preferably not less than 10 parts by weight. When the amount is too small, the photosensitivity may be excessively low. On the other hand, when the amount of the photosensitive resin composition is more than 200 parts by weight, The viscosity becomes too low and the properties as a cured coating film may become insufficient. Therefore, in the present invention, a suitable amount of a polymerizable unsaturated compound and a solvent are preferably used in combination so as to obtain, for example, a good coating property and a cured coating film characteristic as a liquid composition.

The photosensitive resin composition of the present invention may further contain additives such as amorphous silica, calcium carbonate, magnesium carbonate, barium sulfate, clay, talc, silicon oxide powder, mica powder and the like for the purpose of improving properties such as adhesion and hardness And various additives such as coloring pigments such as phthalocyanine green, phthalocyanine blue, titanium oxide and carbon black, antifoaming agents and leveling agents, as well as various additives such as hydroquinone, resorcin (resorcinol), catechol, pyrogallol, hydroquinone mono A polymerization inhibitor such as methyl ether, t-butyl catechol, or phenothiazine may be used.

The photosensitive resin composition of the present invention is obtained by blending each of the above-mentioned respective blending components, preferably in the above-mentioned ratio, and uniformly mixing the blend with three roll mills or the like.

Examples of the preferable photosensitive resin composition of the present invention include the following resin compositions.

I. The alkali developing resin according to any one of (1) to (9) of the present invention for solving the problem (A), or the alkali developing agent described in any one of I to X described as the preferable resin Y of the present invention Type resin is 10 to 80% by weight based on the total amount of the composition,

(B) an epoxy resin in an amount of 1 to 50% by weight,

(C) a photopolymerization initiator in an amount of 0.5 to 20% by weight based on the total amount of the composition, and

(D) the diluent is 10 to 200 parts by weight based on 100 parts by weight of the alkali developing resin.

(II) The photosensitive resin composition according to (I), wherein the epoxy resin is a novolak type epoxy resin or an aralkyl type epoxy resin.

III. The photosensitive resin composition according to the above I or II, wherein the epoxy resin is an epoxy resin containing a biphenyl skeleton.

(IV) The photosensitive resin composition according to any one of (I) to (III), wherein the diluent comprises 3 to 200 parts by weight of a polymerizable unsaturated compound per 100 parts by weight of the alkali developing resin.

V. The photosensitive resin composition according to the above IV, wherein the content of the polymerizable unsaturated compound is 5 to 100 parts by weight based on 100 parts by weight of the alkali developing resin.

VI. The photosensitive resin composition according to the above IV or V, wherein the polymerizable unsaturated compound is a (meth) acrylate compound.

(VII) The photosensitive resin composition according to any one of (IV) to (VI) above, wherein the diluent is a solvent and the total amount of the polymerizable unsaturated compound and the solvent is 10 to 200 parts by weight based on 100 parts by weight of the alkali developing resin.

VIII. The photosensitive resin composition according to any one of the above I to VII, wherein the inorganic filler is contained in an amount of 1 to 100 parts by weight based on 100 parts by weight of the alkali developing resin.

Further, the photosensitive resin composition of the present invention is usually a liquid composition, and for example, a cured product is obtained by curing as follows. That is, the composition of the present invention is applied to the printed wiring board by a screen printing method, a spraying method, a roll coater method, an electrostatic coating method, a curtain coating method or the like to a thickness of 10 to 160 탆 and the coated film is dried at 60 to 110 캜 And then the negative film is brought into direct contact with the coating film (or placed on the coating film in a state where it is not contacted), followed by exposure to ultraviolet light to expose the composition, dissolving the unexposed light portion in a diluted aqueous alkaline solution, , Curing is further performed by ultraviolet irradiation and / or heating (for example, at 100 to 200 DEG C for 0.5 to 1.0 hour) for further improvement of various physical properties to obtain a cured coating film.

The photosensitive resin composition of the present invention may be used in the form of a dry film having a solder resist layer formed by applying and drying a solder resist to a film such as polyethylene terephthalate in advance, The dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film, which is used as needed, are laminated in this order.

In order to manufacture a protective film on a printed wiring board using a dry film, the cover film is peeled off, the solder resist layer and the substrate on which the circuit is formed are superimposed and bonded together using a laminator or the like, . The cured coating film can be formed on the formed solder resist layer by exposure, development, and heat curing in the same manner as described above.

Example

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples, "parts" and "%" mean "parts by weight" and "% by weight", respectively, unless otherwise specified.

Synthesis Example 1 (Synthesis Example of Resin Y-1):

Cresol novolak resin [Shonol CRG-951, SHOWA KOBUNSHI K.K. 118 parts (1.0 equivalent) and 124.71 parts of propyleneglycol monomethyl ether acetate were charged and heated at 80 占 폚 to dissolve the mixture uniformly. After confirming the dissolution, 37.04 parts (0.5 mol) of glycidol and 0.47 part of triphenylphosphine were added thereto, and the mixture was reacted for about 8 hours by heating at 120 DEG C to obtain reaction product X (resin: Intermediate X). The reaction rate was determined by GPC (Gel Permeation Chromatography) measurement, and the reaction rate of glycidol was 98%. Subsequently, 32.03 parts (0.17 mol) of trimellitic anhydride was added to the reaction solution containing the reaction product X and reacted at 100 ° C for about 6 hours to obtain the curable resin (Y-1) of the present invention 100 mg KOH / g, solids concentration 60%). The average molecular weight Mw of the resin Y-1 was 3,200.

Synthesis Example 2 (Synthesis Example of Resin Y-2):

Biphenyl aralkyl type phenol resin [GPH-103, product of Nippon Kayaku Co., Ltd., hydroxyl equivalent weight 239, softening point 103 캜, all of phenolic hydroxyl groups resorcinol hydroxyl group (resorcinol hydroxyl group 100%), weight average molecular weight 3220] 239 (1.0 equivalent) and 222.04 parts of propylene glycol monomethyl ether acetate were charged and heated at 80 DEG C to dissolve the mixture uniformly. After confirming the dissolution, 37.04 parts (0.5 mol) of glycidol and 0.83 part of triphenylphosphine were added thereto, and the mixture was reacted for about 8 hours by heating at 120 ° C to obtain a reaction product X (resin: Intermediate X). When the reaction rate was determined by GPC measurement, the reaction rate of glycidol was 98%. Then, 57.02 parts (0.3 mol) of trimellitic anhydride was added to the reaction solution containing the reaction product X and reacted at 100 DEG C for about 6 hours to obtain the curable resin (Y-2) of the present invention 100 mg KOH / g, solids concentration 60%). The average molecular weight (Mw) of the resin Y-2 was 15,000.

Comparative Synthesis Example 1 (Synthesis Example of Curable Resin Z):

219 parts (1.0 equivalent) of cresol novolac epoxy resin [EOCN-104s, epoxy equivalent of 219, product of Nippon Kayaku Co., Ltd., softening point 90 캜], 72 parts (1.0 mol) of acrylic acid, 3-butyl-p-cresol and 216.65 parts of propylene glycol monomethyl ether acetate were charged and heated at 95 占 폚 to dissolve the mixture uniformly. After confirming the dissolution, 1.3 parts of triphenylphosphine was added thereto, and the mixture was heated at 100 占 폚 and allowed to react for about 24 hours to obtain a reaction product (solid acid value of 3.0 mg KOH / g or less). 109.10 parts (0.72 mol) of tetrahydrophthalic anhydride was added to the mixture, and the mixture was heated at 98 占 폚 and reacted for about 6 hours to obtain a comparative curable resin Z (solid content: 100 mg KOH / g, solid content: 65%). The average molecular weight (Mw) of this curable resin Z was 6,500.

Examples 1 to 3 and Comparative Example 1:

The photosensitive resin and the polymer obtained in the above Synthesis Examples 1 and 2 and Comparative Synthesis Example 1 were used and kneaded by a three roll mill according to the mixing ratio shown in Table 1 to obtain a photosensitive resin composition of Examples and Comparative Examples It was prepared. Each of the compositions of Examples 1 to 3 and Comparative Example 1 prepared as shown in Table 1 was diluted with methyl ethyl ketone and applied on a PET film and dried at 80 DEG C for 30 minutes to obtain a photosensitive resin To prepare a composition layer. Further, preliminary drying was performed at 80 캜 for 30 minutes, and the resultant was cooled to room temperature to obtain a dried coating film. The negative film having a resist pattern was closely adhered to the coating film and exposed at 350 mJ / cm ² using an ultraviolet ray exposure apparatus. The negative film was peeled off, and then a 1% aqueous solution of sodium carbonate was used at a spray pressure of 2.0 kgf / cm ² And developed for 60 seconds to dissolve and remove the unexposed portion. Thereafter, a hot-air dryer was used and heated and cured at 150 DEG C for 60 minutes to prepare a cured coating film having a resist pattern.

* 1 NC-3000H CA75: biphenyl novolak type epoxy resin [product of Nippon Kayaku Co., Ltd.]

* 2 Irg.907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 [Irgacure 907, Chib. product]

* 3 DETEX-S: 2,4-diethylthioxanthone (KAYACURE DETEX-S, product of Nippon Kayaku Co., Ltd.)

* 4 TMPTA: trimethylolpropane triacrylate [light acrylate TMP-A, manufactured by Kyoeisha Chemical Co., LTD. product]

Each test piece of the present invention and the comparative test piece having the cured coatings obtained as described above was tested for developing properties, adhesion, solder heat resistance, electroless gold plating resistance, PCT resistance, flexibility test, An impact resistance test, and an HAST characteristic test were conducted to evaluate various properties of the coating film. The results of the test evaluation are shown in Tables 2 and 3. However, the developability was evaluated as a specimen in which the preliminary drying time at 80 캜 was changed to several times other than 30 minutes.

<Developability>

Each dry film having the preliminary drying time of 20 minutes, 40 minutes, 60 minutes, 80 minutes and 100 minutes was subjected to development for 60 seconds at a spray pressure of 2.0 kgf / cm ² using an aqueous 1% sodium carbonate solution, The presence or absence of a coating film was observed and evaluated according to the following criteria.

○: The coating film was completely removed after development, and it was able to completely develop.

X: The coating film which has not been removed even after development is left incomplete.

&Lt; Adhesion >

A cross-cut was placed on the cured film of each test piece as a checkerboard in accordance with the test method of JIS D 0202, followed by peeling test with a cellophane tape, and the state of peeling after the test was visually judged.

The evaluation was made based on the following criteria.

○: No peeling at all.

B: The crosscut portion was slightly peeled off.

X: The coating film is peeled off.

&Lt; Soldering heat resistance &

According to the test method of JIS C 6481, each test piece was immersed in a soldering bath at 280 占 폚 for 10 seconds for 3 times, and after the withdrawal, a change in appearance was observed. The evaluation was made based on the following criteria.

?: No change in appearance of the cured film.

?: Discoloration was confirmed on the cured film.

X: Cured film peeling, peeling, solder dipping.

<Electroless gold plating resistance>

As the pretreatment of the test pieces, the test pieces were immersed in an acidic degreasing solution at 30 ° C, immersed in water, soft-etched, immersed in water, applied with a catalyst (immersed in a nickel plating catalyst solution at 30 ° C for 7 minutes) I did. Next, as the electroless nickel plating process, each of the test pieces was immersed in a nickel plating solution (85 ° C, pH 4.6) for 20 minutes, followed by acid immersion for 1 minute (10 vol% sulfuric acid aqueous solution at room temperature → immersion water washing and finally as an electroless gold plating process Immerse each specimen in gold plating solution (95 ° C, pH 6, 3vol% aqueous solution of potassium cyanide gold) for 10 minutes → Immersion water → Immerse the immersion water in 60 ° C hot water → Sufficiently wash water → Remove water well → Electrolize in drying process Gold plating was carried out and the test piece was observed for appearance change and peeling test was performed using a cellophane tape to evaluate the coating film.

&Amp; cir &amp;: No appearance change and no peeling of the resist at all.

?: There is no change in appearance, but the resist peeling is slightly visible.

X: Exfoliation of resist or plating dipping is observed, and peeling of resist is large in peeling test.

<PCT test>

Each test piece was allowed to stand at 121 DEG C and 2 atm in a saturated steam atmosphere for 100 hours, and then the appearance of the coated film was visually observed. The evaluation was made based on the following criteria.

○: The coating film is free from swelling and peeling.

X: Swelling and peeling.

&Lt; Flexibility test >

Each of the above-mentioned photosensitive resin compositions was coated on a bond steel sheet by using an Ericsson tester specified in JIS B7729A according to JIS K5400, followed by drying, light exposure, development, and heating to prepare test pieces. Each of the obtained test specimens was extruded from the back surface thereof to measure the extrusion distance until the collapse and peeling of the coating film occurred when the specimen was deformed. The evaluation was made based on the following criteria.

?: The coating film was not collapsed or peeled with a distance of 4 mm or more when the steel ball was extruded.

?: No collapse or peeling of the coating film occurred when the distance at which the steel ball was extruded was 2 mm or more and less than 4 mm.

X: The distance of the extrusion of steel balls was less than 2 mm, and the coating film collapsed and peeled.

<Resistance to cold and heat shock>

An evaluation board having a solder resist cured coating film on which no pattern was formed was prepared. The resulting evaluation substrate was subjected to an immunity test for 1000 cycles with a cold / impact tester (manufactured by Etac Co.) at -55 ° C / 30 minutes to 150 ° C / 30 minutes as one cycle. After the test, the cured film after the treatment was visually observed, and the occurrence of cracks was judged based on the following criteria.

○: Less than 30% of crack occurrence rate

DELTA: Crack occurrence rate 30 to 50%

×: Crack occurrence rate 50% or more

<HAST characteristics>

A solder resist cured coating film was formed on a BT substrate on which interdigital electrodes (line / space = 30 占 퐉 / 30 占 퐉) were formed to prepare evaluation substrates. The evaluation board was placed in a high-temperature and high-humidity bath under an atmosphere at 130 캜 and a humidity of 85%, charged at a voltage of 5.5 V, and subjected to a HAST test (insulation test) in the bath for various times. The in-house insulation resistance value at various time passes was evaluated according to the following criteria.

?: After 240 hours, 108?

X: 108 hours or less after elapse of 240 hours

As apparent from the evaluation results of Tables 2 and 3, the alkali-developable resin of the present invention is superior to the conventionally known epoxy-based photosensitive resin in dryness and alkali developability, and the cured product has adhesiveness, , Electroless gold plating resistance, PCT resistance, flexibility, resistance to cold and heat shock, and HAST characteristics.

Synthesis Example 3 (Synthesis Example of Resin Y-3):

A phenol resin having a biphenyl novolac type resorcinol-containing phenol resin prepared by using phenol and resorcin in a ratio of 1 mole of resorcin to 9 mole of phenol as a phenol compound in accordance with the description of JP-A-8-143648 (Hydroxyl group equivalent: 134 g / eq; softening point: 93.4 DEG C; ratio of resorcinol hydroxyl group (number of resorcinol hydroxyl groups / total number of phenolic hydroxyl groups in phenol resin (a1) x 100) = about 20%] 134 parts : 1.0 equivalent) and 179.56 parts of propylene glycol monomethyl ether acetate were charged, and the mixture was uniformly dissolved by heating at 80 占 폚. After confirming the dissolution, 14.82 parts (0.2 mol) of glycidol and 0.45 part of triphenylphosphine were added thereto, and the mixture was heated at 120 캜 for about 8 hours to obtain a reaction product X (resin, intermediate X). When the reaction rate was determined by GPC measurement, the reaction rate of glycidol was 98%. Then, 30.74 parts (0.16 mol) of trimellitic anhydride was added to the reaction solution containing the reaction product X and reacted at 100 DEG C for about 6 hours to obtain a curable resin (Y-3) of the present invention 50%, solid acid value of 100 mg KOH / g). The average molecular weight (Mw) of this resin Y-3 was 1,900.

Synthesis Example 4 (Synthesis Example of Resin Y-4):

102 parts (1.0 equivalent) of biphenyl novolak type resorcin resin (hydroxyl group equivalent 102, softening point 85.2 占 폚) synthesized according to Example 1 of Japanese Patent Application Laid-Open No. 7-292066 and 192.09 parts of propylene glycol monomethyl ether acetate were charged, And the mixture was uniformly dissolved by heating at 80 占 폚. After confirming the dissolution, 37.04 parts (0.5 mol) of glycidol and 0.42 part of triphenylphosphine were added thereto, and the mixture was reacted for about 8 hours by heating at 120 DEG C to obtain a reaction product X (resin: Intermediate X). When the reaction rate was determined by GPC measurement, the reaction rate of glycidol was 98%. Subsequently, 51.05 parts (0.34 mol) of tetrahydrophthalic anhydride was added to the reaction solution containing the reaction product X and reacted at 100 DEG C for about 6 hours to obtain a curable resin (Y-4) of the present invention (solid content concentration 50%, solid acid value of 100 mg KOH / g). The average molecular weight (Mw) of the resin Y-4 was 1,200.

Examples 4 to 7 and Comparative Example 2:

Using each of Resins Y-2, Y-3, Y-4 and Resin Z obtained in Synthesis Examples 2, 3 and 4 and Comparative Synthesis Example 1 described above, Kneaded with a mill to prepare photosensitive resin compositions of Examples and Comparative Examples of the present invention. Each of the compositions of Examples 4 to 7 and Comparative Example 2 prepared in the formulation ratios shown in Table 4 was diluted with methyl ethyl ketone and applied on a PET film and dried at 80 DEG C for 30 minutes to obtain a photosensitive To prepare a resin composition layer. Further, preliminary drying was conducted at 80 캜 for 30 minutes, and the resultant was cooled to room temperature to obtain a dried coating film. The negative film having a resist pattern was closely adhered to the coating film and exposed at 350 mJ / cm ² using an ultraviolet ray exposure apparatus. The negative film was peeled off, and then a 1% aqueous solution of sodium carbonate was used at a spray pressure of 2.0 kgf / cm ² And developed for 60 seconds to dissolve and remove the unexposed portion. Thereafter, a hot-air dryer was used and cured by heating at 150 DEG C for 60 minutes to produce a cured coating film having a resist pattern (a test piece of the present invention and a test piece for comparison).

* 1 NC-3000H CA75: biphenyl novolak type epoxy resin [product of Nippon Kayaku Co., Ltd.]

* 2 Irg.907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 [Irgacure 907, Chib. product]

* 3 DETEX-S: 2,4-diethylthioxanthone (KAYACURE DETEX-S, product of Nippon Kayaku Co., Ltd.)

* 4 DPHA: dipentaerythritol hexaacrylate [KAYARAD DPHA, product of Nippon Kayaku Co., Ltd.]

The developability, adhesion, solder heat resistance, electroless gold plating resistance, PCT resistance, and flexibility test were carried out using the test pieces having the cured coatings obtained as described above and the comparative test pieces according to the test methods described above , And various properties of the coated film were evaluated. The evaluation results of these tests are shown in Tables 5 and 6. However, the developability was evaluated as a specimen in which the preliminary drying time at 80 캜 was changed to various conditions other than 30 minutes. The evaluation criteria are the same as in Table 2.

As apparent from the evaluation results of Tables 5 and 6, the alkali-developable resin of the present invention is superior in drying property and alkali development property to the conventionally known epoxy-based photosensitive resin, and the cured product is excellent in adhesiveness, Resistance to electroless gold plating, resistance to PCT, flexibility, resistance to cold and heat shock, and HAST characteristics.

In particular, the alkali-developing resin of the present invention containing a biphenyl novolac-type resorcinol-containing phenol resin is superior to the others in dryability and alkali developability among the alkali-developable resins of the present invention.

(Industrial applicability)

The photosensitive resin composition of the present invention is excellent in dryness and alkali developability, and the cured film has various properties such as adhesion, solder heat resistance, electroless gold plating resistance, PCT resistance, flexibility, cold shock resistance and HAST characteristics great. The cured film can be formed at a low cost with good productivity. Therefore, the curable film can be used for an ultraviolet curable printing ink application for curing using an active energy ray, and the like. In addition to the use of a solder resist, an etching resist, It is useful for insulation materials and so on.

Claims (21)

Is obtained by further reacting a saturated and / or unsaturated polybasic acid anhydride (c) with a hydroxyl group in a reaction product X obtained by reacting a hydroxyl group of the phenol resin (a) with a compound (b) having an alcoholic hydroxyl group and an epoxy group in the molecule By weight. The method according to claim 1,
Wherein the amount of the compound (b) is 0.1 to 0.9 mol based on 1 equivalent of the phenolic hydroxyl group of the phenol resin (a). 3. The method according to claim 1 or 2,
Reacting the polybasic acid anhydride (c) in an amount of 0.05 to 0.9 mol based on 1 equivalent of the alcoholic hydroxyl group of the reaction product X. 4. The method according to any one of claims 1 to 3,
Wherein the proportion of the phenolic hydroxyl groups remaining in the alkali-developable resin is 10 to 90% based on the total number of phenolic hydroxyl groups in the phenolic resin (a). 5. The method according to any one of claims 1 to 4,
The phenolic resin (a) is a phenol resin (a) containing a biphenyl skeleton. 6. The method according to any one of claims 1 to 5,
The phenolic resin (a) is a phenol resin (a1) represented by the following general formula (1).

M1, m2 and m3 each independently represent an integer of 1 or 2 and n represents an integer of 0 to 10, The method according to claim 6,
The phenolic resin (a1) is a phenolic resin containing a resorcin structure. 8. The method of claim 7,
Wherein the phenolic resin having a resorcin structure has a hydroxyl group equivalent of 70 to 170 g / eq. 9. The method according to any one of claims 1 to 8,
Wherein the compound (b) is a glycidol. 10. The method according to any one of claims 1 to 9,
Wherein the polybasic acid anhydride (c) is an anhydride of a polybasic acid having two or three carboxyl groups. (A) an alkali developing resin according to any one of claims 1 to 10,
(B) an epoxy resin,
(C) a photopolymerization initiator, and
(D) a diluent. 12. The method of claim 11,
Wherein the diluent is a polymerizable unsaturated compound and / or a solvent. 13. The method according to claim 11 or 12,
(A) the alkali-developing resin is contained in an amount of 10 to 80% by weight,
(B) the epoxy resin is contained in an amount of 1 to 50% by weight,
(C) the photopolymerization initiator is used in an amount of 0.5 to 20% by weight based on the total amount of the composition, and
(D) the diluent is 10 to 200 parts by weight based on 100 parts by weight of the alkali developing resin. 14. The method according to any one of claims 11 to 13,
Wherein the polymerizable unsaturated compound as a diluent is contained in an amount of 5 to 200% by weight based on 100 parts by weight of the alkali developing resin. 15. The method of claim 14,
Wherein the polymerizable unsaturated compound is a (meth) acrylate compound. A cured product of the photosensitive resin composition according to any one of claims 11 to 15. 17. The method of claim 16,
A cured product of a photosensitive resin composition characterized by being patterned using a photolithographic method capable of ultrafine processing by light. A substrate comprising a layer of a cured product of the photosensitive resin composition according to claim 16 or 17. An article characterized by having the substrate according to claim 18. A cured coating film characterized by coating the printed wiring board with the photosensitive resin composition described in any one of claims 11 to 15 to form a coating film, exposing it to light, developing it and then curing it by irradiation with ultraviolet rays and / / RTI &gt; A process for producing the alkali-developable resin according to any one of claims 1 to 5, wherein the phenolic hydroxyl group and the alcoholic hydroxyl group obtained by reacting the hydroxyl group of the phenol resin (a) with a compound (b) having an alcoholic hydroxyl group and an epoxy group in the molecule are reacted Lt; RTI ID = 0.0 &gt; X. &Lt; / RTI &gt;