TWI535775B - Alkali developing type resin and photosensitive resin composition using the same - Google Patents

Description

Alkaline developing type resin, photosensitive resin composition using the resin

The present invention relates to an alkali developing type resin and a photosensitive resin composition containing the developing type resin. More specifically, it relates to an alkali-developing resin and a photosensitive resin in the field of electronic materials such as a solder resist for a printed circuit board, an insulating film between high-density multilayer boards, and a solder resist for semiconductor packaging. Composition.

Conventionally, a permanent mask photoresist in the manufacture of printed circuit boards can be manufactured by screen printing using a thermosetting or ultraviolet curing type resist ink (resistInk), but at the production level It is gradually moving toward the development of alkaline development type liquid solder resist.

However, in the conventional printed circuit board which is applied to the alkaline development type solder resist, the resistance to the PCT (Pressure Cooker Test) of the long-term reliability test of the package is poor, and peeling of the cured product occurs.

Moreover, due to the moisture absorption of the solder resist, in the reflow during assembly and packaging, the moisture absorbed inside the package may boil, causing cracks in the solder mask inside the package and its periphery, and there may be cracks. See the problem of the so-called popcorn phenomenon. Such problems of moisture absorption resistance and long-term reliability are not limited to the above-mentioned assembly technology, and are used for solder resisting of general printed circuit boards. Other applications such as manufacturing a flexible printed circuit board or a solder resist used in a tape carrier package (TCP) or an interlayer insulating layer of a multilayer circuit board such as a build-up board (Build-up Board) In such products, problems such as hygroscopicity and long-term reliability are not expected to occur.

As mentioned above, with the recent development of the electrical industry and the semiconductor industry, it is required to improve the characteristics, such as heat resistance, toughness, flexibility, water resistance, and chemical resistance, so that development is being able to satisfy all of this. Various novel photosensitive resins.

Conventionally, a photosensitive resin containing a novolac type epoxy resin as a starting material is widely used for a solder resist and an anti-corrosion agent because of its excellent adhesion, heat resistance, chemical resistance, electrical insulation, and the like. Among various fields of electronic materials such as etchants. In particular, it is used as a photosensitive resin containing a carboxyl group which is excellent in heat resistance, and is used for a resin obtained by reacting a reaction product of a polyhydric anhydride p-cresol novolak type epoxy resin and an unsaturated group-containing monocarboxylic acid (patent Document 1). However, since the resin is excellent in heat resistance, it has a large shrinkage during curing, a small elongation, and a lack of toughness, so that there is a problem that cracks easily occur due to heat shock. As a photosensitive resin that solves this problem, there are proposals for a epoxidized resin of a side chain hydroxyl group of a bisphenol type epoxy resin, a photosensitive prepolymer of a reaction product of (meth)acrylic acid and a polybasic acid anhydride ( Patent Document 2), a polycarboxylic acid resin containing an unsaturated group obtained by reacting tetrahydrophthalic anhydride with a reaction product of a cresol novolac type epoxy resin, acrylic acid, and p-hydroxyphenylethanol (Patent Document) 3) Wait. However, these resins are not yet able to satisfy both heat resistance and toughness.

Further, it has been proposed to use a photosensitive resin containing a carboxyl group as a resin having excellent long-term reliability, which is to use a novolac resin as an alkylene oxide resin. After (alkylene oxide) is modified, addition of (meth)acrylic acid and addition of a polybasic acid anhydride (Patent Document 4). However, there is still room for improvement in the drying property after application of the ink. That is, since the composition is developed by using an aqueous solution of a rare base (rarealkali), it is necessary to increase the acid value. For this reason, it is necessary to shorten the drying time in the solvent drying step after applying the formulated ink to the substrate, and in a series of steps from drying to exposure and development, in the case where it takes a long time after drying, There is a problem that the unexposed portion of the coating film cannot be quickly removed.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 1-54390

Patent Document 2: Japanese Patent Laid-Open No. Hei 9-54434

Patent Document 3: Japanese Patent Laid-Open No. Hei 11-288091

Patent Document 4: Japanese Patent No. 3964326

The present invention has been made in view of the above problems, and an object thereof is to provide a resin containing a carboxyl group which has excellent physical properties such as developability, heat resistance, moisture resistance, and adhesion, and can provide an ink excellent in drying property. Composition.

Still another object of the present invention is to provide a liquid curable resin composition which can form a cured film excellent in various properties required for various applications described below, and which can correspond to high density and surface assembly of a printed circuit board ( Surface mount), and has the characteristics of being developed by an aqueous solution of a rare alkali. That is, the solder resist of a general printed circuit board, the solder resist for manufacturing a flexible printed circuit board or a tape carrier package For the interlayer insulating layer of a multilayer circuit board such as a coating or a build-up substrate, it is required to have excellent properties such as developability, adhesion, solder heat resistance, moisture absorption resistance, PCT resistance, electrical insulation, and the like. The film, in particular, is an cured film which is excellent in properties such as moisture absorption resistance and PCT (Pressure Cooker Test) resistance. An object of the present invention is to provide a curable resin composition which can form a cured film excellent in various properties required for such various applications and which has the above characteristics.

In order to solve the above-mentioned conventional problems, the inventors of the present invention have found an alkali-developing resin which is obtained by using a phenol resin as a backbone and introducing a hydroxyl group and a reactive functional group therein to obtain a reactant. In the reaction product, an alkali-developing resin in which a carboxyl group as a functional group is introduced, that is, "reacts a hydroxyl group of the phenol resin (a) with a compound (b) having an alcoholic hydroxyl group in the molecule and one epoxy group) The reaction product X (resin) is obtained, and the hydroxyl group in the reaction product X (resin) is reacted with a saturated and/or unsaturated polybasic acid anhydride (c) to obtain a carboxyl group-containing resin. The present invention has been completed.

In addition, the term "alkaline developing type resin" as used herein means "a resin which can impart alkali developability to a resin composition", that is, a resin which is intended to impart alkali developability. Therefore, the alkali-developable resin of the present invention is most suitably used for an alkali-developing photosensitive resin composition, and can also be used for purposes other than this use.

In addition, (meth)acrylic acid is used to mean at least one of acrylic acid and methacrylic acid, and (meth)acrylate (at least one of acrylate or methacrylate) is also used. Refer to the same meaning.

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

(1) An alkali developing type resin (hereinafter also referred to as "resin Y of the present invention or simply referred to as resin Y") which has a hydroxyl group of the phenol resin (a) and an alcoholic hydroxyl group in the molecule, and one ring The oxy compound (b) (hereinafter also referred to simply as the compound b) is reacted to obtain a reaction product X, and the obtained reaction product X (hereinafter simply referred to as "intermediate X") is further added to the above polybasic acid anhydride. (c) (hereinafter referred to as "polybasic acid anhydride (c)").

(2) The alkaline developing type resin according to the above (1), wherein the compound (b) is reacted at a ratio of 0.1 to 0.9 mol per 1 equivalent of the phenolic hydroxyl group of the phenol resin (a). .

(3) The alkaline developing type resin according to the above (1) or (2), wherein the polybasic acid anhydride (c) is in a ratio of 0.05 to 0.9 mol with respect to 1 equivalent of the hydroxyl group of the reaction product X. To react.

(4) The alkali-developable resin according to any one of the above-mentioned (1) to (3), which remains in the alkali-developing resin with respect to the total number of phenolic hydroxyl groups in the phenol resin (a) The ratio of phenolic hydroxyl groups is from 10 to 90%.

(5) The alkaline developing type resin according to any one of the above (1), wherein the phenol resin (a) is a biphenyl backbone.

(6) The alkali-developable resin according to any one of the above-mentioned (1), wherein the phenol resin (a) is a phenol resin (a1) represented by the following formula (1): (wherein m1, m2, and m3 are integers each independently representing 1 or 2; n represents an integer of 0 to 10).

(7) The alkaline developing type resin according to the above (6), wherein the phenol resin (a1) is a phenol resin having a resorcin structure therein.

(8) The alkaline developing type resin according to the above (7), wherein the phenol resin having a resorcinol structure has a hydroxyl equivalent of 70 to 170 g/eq.

The alkaline developing type resin according to any one of the above (1), wherein the compound (b) is glycidol.

(10) The alkaline developing type resin according to any one of the above (1), wherein the polybasic acid anhydride (c) is a group 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) above, (B) an epoxy resin, and (C) light a polymerization initiator, and (D) a diluent.

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

(13) The photosensitive resin composition according to the above (11) or (12), wherein: (A) is from 10 to 80% by weight based on the total amount of the composition; (B) The epoxy resin is from 1 to 50% by weight based on the total amount of the composition; (C) the photopolymerization initiator is from 0.5 to 20% by weight based on the total amount of the composition; and (D) is relative to the alkali development The resin is 100 parts by weight and the diluent is 10 to 200 parts by weight.

The photosensitive resin composition of any one of the above-mentioned (11) to (13) containing 5 to 200 weight% of the range of 100 parts by weight of the alkali-developing resin. The polymeric unsaturated compound is used as a diluent.

(15) The photosensitive resin composition according to the above (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 the above (11) to (15), which is a cured product of the photosensitive resin composition.

(17) The cured product of the photosensitive resin composition according to the above (16), which is a cured product which is patterned by photolithography which can perform ultrafine processing by light.

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

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

(20) A method of forming a cured coating film, comprising applying the photosensitive resin composition according to any one of the above (11) to (15) on a printed circuit board, forming a coating film, and exposing it, after developing It is hardened by irradiation and/or heating of ultraviolet rays.

(21) Use of a reaction product X having both a phenolic hydroxyl group and an alcoholic hydroxyl group, which is used for producing the alkali-developing type resin described in the above (1), wherein the reaction product X is a phenol resin ( The hydroxyl group of a) is obtained by reacting a compound (b) having an alcoholic hydroxyl group and one epoxy group in the molecule.

The photosensitive resin composition of the present invention is excellent in drying property and alkali developability, and the coating film after curing has excellent adhesion, solder heat resistance, electroless gold plating resistance, PCT resistance, flexibility, hot and cold Impact resistance, HAST characteristics and other characteristics. Since the cured film can be formed with good productivity at low cost, in addition to the use of the ultraviolet curable printing ink which can be used for curing with active energy rays, there are also solder resists used in the manufacture of printed circuit boards, Resist, Anti-plating agent, interlayer insulation, etc.

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

First, in the resin Y of the present invention, the phenol resin (a) is used as the backbone 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, a phenol resin having at least two or more phenolic hydroxyl groups in one molecule is used as the phenol resin (a). As the phenol resin (a), all phenol resins such as a resole system, a novolak system, and a cresol system can be used. Further, an epoxy-modified type in which a polyfunctional phenol compound is modified with an epoxy compound, a phenol-added butadiene (co)polymer in which a phenol is added to a butadiene (co)polymer, or a phenol may be used. A polymer resin of phenols and dicyclopentadiene or a polymer resin of phenols and biphenyl.

Specifically, a novolac type phenol resin such as a phenol novolak resin, a cresol novolak resin, a biphenol novolak type resorcin resin, a para-phenylene modified novolac resin, and a meta-phenylene modification can be exemplified. a phenolic phenolic resin such as a phenolic varnish resin, a phthalic modified phenolic varnish resin, a phenolic phenol resin such as bisphenol A or a bisphenol F; a biphenyl type phenol resin; a resol type phenol resin; Aralkyl phenol resin such as aralkyl phenol resin or biphenyl aralkyl phenol resin; alkane type phenol resin such as trisphenol alkane type resin and polymer thereof; phenol resin containing naphthalene ring and dicyclopentadiene A phenol resin, an alicyclic phenol resin, a heterocyclic phenol resin, or the like. These phenol resins may be used alone or in combination of two or more.

As the molecular weight of the phenol resin (a), a phenol resin having a molecular weight of about 300 to 30,000 is used, and a desired molecular weight is about 400 to 15,000. Molecular weight of resin The number average molecular weight or the weight average molecular weight is used, and any one may be within the above range.

A preferred example of the phenol resin (a) is a novolac type phenol resin, and a phenol resin having a cresol backbone or a biphenyl backbone in the structure thereof is preferable, and a biphenyl group is more preferable. The phenolic resin of the backbone. Specific examples thereof include a cresol novolak resin as a novolac type phenol resin having a cresol backbone, a biphenyl aralkyl type phenol resin, a biphenol novolak type phenol resin, and the like as a phenol resin having a biphenyl backbone. .

More preferably, the novolac type phenol resin containing a biphenyl backbone is more preferably a phenol resin represented by the following formula (1) (a1)

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

Further, a more preferable phenol resin is the phenol resin (a1) of the above formula (1) (hereinafter also referred to simply as phenol resin (a1)), and at least a part of the backbone of the phenol resin (a1) has 2 A hydroxy ring of a benzene ring (ideally a resorcinol structure).

The ratio of the number of hydroxyl groups in the benzene ring (preferably resorcin structure) having two hydroxyl groups is preferably from 5 to 100% based on the total number of phenolic hydroxyl groups in the phenol resin (a1). This ratio is calculated from the ratio of the molar ratio of the phenol used in the synthesis of the phenol resin (a1) to the dihydroxybenzene (ideally resorcinol), and the number of phenolic moles used is set to d1, dihydroxybenzene. When the number of moles of (preferably resorcin) is set to d2, it is calculated by the following formula.

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

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

Further, the phenol resin (a1) of the above formula (1) can be produced by a method described in a publicly known document. For example, it can be easily obtained based on the descriptions of Japanese Laid-Open Patent Publication No. Hei 8-143648, and the Japanese Patent Publication No. Hei 7-292066. That is, it can be obtained by reacting bis(methoxymethyl)biphenyl or bis(chloromethyl)biphenyl with phenol or/and resorcin.

The hydroxyl equivalent of the phenol resin (a1) desirably ranges from about 70 to 170 g/eq, and is optionally from about 102 to 140 g/eq. The determination of the hydroxyl equivalent of the phenol resin can be carried out according to a usual method.

The compound (b) having an alcoholic hydroxyl group and one epoxy group in the molecule, which is reacted with the phenol resin (a), may be a compound having an alcoholic hydroxyl group and one epoxy group in the molecule. As the various known compounds, examples thereof include glycidol or a monoglycidyl ether of an alcohol having 2 to 4 carbon atoms such as ethylene glycol monoglycidyl ether. In particular, glycidol is preferred in the present invention.

In the reaction of the phenol resin (a) with the compound (b), the compound (b) is preferably 0.1 to 0.9 mol, more preferably 0.1 to 0.8, based on 1 equivalent of the phenolic hydroxyl group of the phenol resin (a). Mohr, more desirably a ratio of 0.2 to 0.8 moles. Further, the compound (b) is made to have a ratio of 0.1 to 0.7 mol or a ratio of 0.1 to 0.6 mol, or further to 0.2 to 0.6 mol, per equivalent of the phenolic hydroxyl group of the phenol resin (a). The ratio of the ear to react is very desirable.

When the amount of the compound (b) is too large, the water solubility of the resin X of the present invention which is obtained by the reaction with the polybasic acid anhydride (c) becomes too high, and the resin composition of the resin X is hard. The water resistance of the compound will decrease.

In this reaction, the epoxy group of the compound (b) is subjected to ring-opening addition to the phenolic hydroxyl group of the phenol resin (a), and forms a secondary alcoholic hydroxyl group at the same time as bonding with the ether.

In the reaction between the phenol resin (a) and the compound (b), it is preferred that the phenol resin (a) is not all phenolic hydroxyl groups reacted with the compound (b) (hereinafter also referred to as alcohol modification), but a part remains. The reaction is carried out in the form of an unreacted phenolic hydroxyl group. This result is an ideal intermediate X which contains both an unreacted phenolic hydroxyl group and an alcoholic hydroxyl group. The total amount of the phenolic hydroxyl group of the phenol resin (a) of the starting material (in the intermediate X, the total amount of the alcohol-modified phenolic hydroxyl group and the residual phenolic hydroxyl group) is regarded as 1, in contrast, in the middle The ratio of the residual phenolic hydroxyl group in the body X is from about 0.1 to 0.9, more preferably from about 0.2 to about 0.9, still more preferably from about 0.3 to about 0.9.

Further, the residual phenolic hydroxyl group of the intermediate X remained as it is in the resin Y. This is because the polybasic acid anhydride (c) reacts with the alcoholic hydroxyl group in the intermediate X in the reaction in which the intermediate X is subsequently reacted with the polybasic acid anhydride (c), rather than reacting with the phenolic hydroxyl group.

When the intermediate X is produced, a solvent can be used in the reaction of the phenol resin (a) with the compound (b). A known solvent can be used as the solvent to be used, and examples thereof include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; and dipropylene glycol dimethyl ether. Alcohol ethers such as dipropylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether; 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, butyl sulphate acetate, Esters such as carbinol acetate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum brain, solvent naphtha; etc. Organic solvents.

Further, carbitol (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane (meth) acrylate, hexahydroxyethyl isocyanate tri(meth) acrylate may also be used. Reactive monomer such as dipentaerythritol hexa(meth) acrylate.

Further, it is preferred to use a catalyst to promote the reaction between the phenol resin (a) and the compound (b), and a reaction catalyst for the epoxy group and the phenolic hydroxyl group in this case can be used. As such a catalyst, for example, triethylamine, benzyldimethylamine, methyltriethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide may be mentioned. , triphenylphosphine, triphenylphosphonium, chromium octoate, zirconium octoate, and the like. Such a catalyst is preferably used in an amount of from 0.01 to 1% by weight based on the reaction raw material mixture. The reaction temperature is preferably 60 to 150 °C. Further, the reaction time is preferably from 5 to 24 hours. In this way, the intermediate X can be obtained.

The resin Y is obtained by further reacting a hydroxyl group (alcoholic hydroxyl group) of the intermediate X obtained in the above manner with the polybasic acid anhydride (c). Examples of the polybasic acid anhydride (c) include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and endoisyltetrahydrophthalic anhydride. (didomethylene tetrahydrophthalic anhydride), methyltetrahydrophthalic anhydride, chlorendic anhydride and other dibasic acid anhydrides; trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, biphenyltetracarboxylic anhydride, etc. Anhydride. Usually, an anhydrous substance is preferable, and a polybasic acid anhydride having two or three carboxyl groups such as trimellitic anhydride, tetrahydrophthalic anhydride, succinic anhydride or hexahydrophthalic anhydride is preferable, and it is preferable that the number of carbon atoms is An anhydrate of a polybasic acid having 2 or 3 carboxyl groups on the hydrocarbon group of 2 to 6, more preferably an anhydrate of a polybasic acid having 2 or 3 carboxyl groups on a carbon number 6 member ring. The 6-member ring can be an aromatic ring, and it can also It is an aliphatic ring. Most preferred is trimellitic anhydride or tetrahydrophthalic anhydride.

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

More 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 0.1 equivalent to the hydroxyl group (alcoholic hydroxyl group) in the above-mentioned intermediate X. 07 mole ratio response. When the amount (addition amount) of the polybasic acid anhydride (c) to be reacted is too small, since the ratio of the acidic group is small, the solubility to the alkali is deteriorated, and sufficient alkali developability cannot be obtained; This will result in a decrease in the electrical properties of the hardened film.

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

Further, since the reaction is carried out in a quantitative manner, the ratio of the number of phenolic hydroxyl groups (the total number of phenolic hydroxyl groups) of the raw material phenol resin (a) to the number of phenolic hydroxyl groups remaining in the above resin Y is It can be calculated from the amount of raw material placed.

When the resin Y is used for the photosensitive resin composition, it is judged that the resin Y having a large amount of residual phenolic hydroxyl groups is advantageous for improving the heat resistance of the cured product.

Further, in the resin Y, a carboxyl group introduced by reaction with the polybasic acid anhydride (c) is present. As a result, the resin Y of the present invention is a resin containing the above-mentioned remaining phenolic hydroxyl group, carboxyl group, and alcoholic hydroxyl group remaining without reacting with the polybasic acid anhydride (c).

An example of the ideal resin Y of the present invention is as follows.

I. An alkali developing type resin which makes phenol resin (a) and phenol resin (a) The compound (b) having an alcoholic hydroxyl group and one epoxy group in the molecule is reacted to obtain a reaction product X at a ratio of 0.1 to 0.9 mol, and the reaction product X is obtained. The hydroxyl group (alcoholic hydroxyl group) in the reaction with the hydroxyl group (alcoholic hydroxyl group) in the reaction product X is equivalent to 1 equivalent of the saturated and/or unsaturated polybasic acid anhydride (c) at a ratio of 0.05 to 0.9 mol. By.

The alkaline developing type resin according to the above 1, wherein the compound (b) having an alcoholic hydroxyl group and one epoxy group in the molecule is glycidol or a monoglycidyl alcohol having 2 to 4 carbon atoms. ether.

The alkaline developing type resin according to the above II, wherein the compound (b) is glycidol.

The alkaline developing type resin according to any one of the above aspects, wherein the phenol resin (a) is a phenol resin containing a cresol backbone or a biphenyl backbone.

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

The alkaline developing type resin according to the above V, wherein the phenol resin (a1) contains a resorcinol structure and the hydroxyl group is 70 to 140 g/eq.

The alkaline developing type resin according to any one of the above aspects, wherein the polybasic acid anhydride (c) is a polybasic acid anhydride having two or three carboxyl groups.

VIII. The alkaline developing type resin according to the above VII, wherein the polybasic acid anhydride having 2 or 3 carboxyl groups is selected from the group consisting of trimellitic anhydride, tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride. At least one of the groups.

IX. The alkaline developing type resin according to the above VIII, wherein the polybasic acid anhydride having 2 or 3 carboxyl groups is a polybasic acid anhydride having 2 or 3 carboxyl groups on a carbon 6 member ring.

X. The alkaline developing type resin according to the above IX, wherein the carbon 6 member ring The polybasic acid anhydride having 2 or 3 carboxyl groups is trimellitic anhydride or tetrahydrophthalic anhydride.

The present invention further 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. The diluent is a polymerizable unsaturated compound, and is particularly desirable in the form of a (meth) acrylate compound.

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

The epoxy resin (B) used in the photosensitive resin composition of the present invention is usually one having two or more epoxy groups in one molecule.

For example, a biphenol novolak type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac varnish may be mentioned. Type epoxy resin, phenol aralkyl type epoxy resin, dicyclopentadiene-phenol novolak type epoxy resin, phenol-cresol novolac co-condensation type epoxy resin, bisphenol A novolac type epoxy resin , bisphenol F novolak type epoxy resin, or such halogenated epoxy compound, triphenylolmethane type epoxy resin, alkyl substituted trisphenol methane type epoxy resin, tetraphenol ethane type An epoxy resin obtained by reacting a polyfunctional phenol such as an epoxy resin with epichlorohydrin, an epoxy resin obtained by reacting a polyfunctional hydroxynaphthalene with epichlorohydrin, and a silicone modified ring Oxygen resin, ε-caprolactone modified epoxy resin, heterocyclic ring such as glycidylamine epoxy resin or triglycidyl isocyanate obtained by reaction of epichlorohydrin with primary or secondary amine Oxygen resin, etc. These epoxy resins may be used alone or in combination of two or more. Further, an isocyanate-modified epoxy resin is used for the purpose of ensuring the glass transition point Tg and improving the toughness, or It is also effective to use a phosphorus-containing epoxy resin or the like in order to impart flame retardancy.

In order to improve various characteristics of the solder resist such as adhesion, heat resistance, and plating resistance, the epoxy resin (B) is blended as a thermosetting component in a composition, and when a printed circuit board or the like is manufactured, After development with an aqueous solution of a rare alkali, the resin is cured by heating to impart excellent adhesion, heat resistance, plating resistance, and the like to the wiring board.

The epoxy resin (B) may be used singly or as a mixture of two or more kinds, and the amount of the epoxy resin contained in the photosensitive resin composition of the present invention is usually from 1 to 50% by weight based on the total amount of the composition. It is preferably about 3 to 45 wt%, and more preferably about 5 to 45 wt%.

When the epoxy resin (B) is used as the thermosetting component, it is desirable to use an epoxy resin curing agent in combination to further improve properties such as adhesion, chemical resistance, and heat resistance. Examples of such an epoxy resin curing agent include an imidazole derivative, a phenol derivative, a dicyandiamide, a dicyandiamide derivative, an anthracene derivative, an amine, and an acid anhydride. These hardeners may be used alone or in combination of two or more kinds. The amount of the hardener to be used is preferably from 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 benzoin (beuzoin), acetophenone, anthraquinone, and oxazepine. Ketones (thioxanthone), benzophenones, etc., and for example: benzoin benzoin, benzoin methyl ether, benzoin isopropyl ether and other derivatives; Toluene, 2,2-dimethoxy-2-phenylethylbenzene, 2,2-diethoxy-2-phenylethylbenzene, 1,1-dichloroethylbenzene, 1-hydroxyl Cyclohexyl phenyl ketone, 2- Derivatives such as methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, N,N-dimethylaminoethyl benzene; Derivatives such as methyl hydrazine, 2-chloro hydrazine, 2-ethyl hydrazine, 2-tributyl fluorene, 2-pentyl hydrazine, 2-amino hydrazine; oxazetomone Oxythioxanthone, 2,4-dimethyloxazepinone, 2,4-diethyloxythiazepinone, 2-chlorooxazepinone, 2-isopropyloxy Derivatives such as thioxanthone and 2,4-diisopropyloxathioxanthone; benzophenone benzophenone, 4-benzoin-4'-methyldiphenyl sulfide, 4,4'-dichlorobenzophenone, N,N-dimethylaminobenzophenone, methylbenzophenone, 4,4'-bis(diethylamino)benzophenone , derivatives such as Michler's ketone, 4-benzoin-4'-methyldiphenyl sulfide; 2,4,6-trimethylbenzoin diphenylphosphorus oxide, etc. One type may be used alone or a combination of two or more types may be used.

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

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

In the photosensitive resin composition of the present invention, a polymerizable unsaturated compound and/or a solvent is used as the diluent (D). When a polymerizable unsaturated compound and/or a solvent is used as the diluent (D), the purpose is to improve the applicability when the active energy ray is used as a curable and/or photosensitive resin composition as a resist ink. .

Such a polymerizable unsaturated compound is preferably a monomer having active energy light curability, and examples thereof include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-pyrrolidone, and N-propene fluorene. Basomomorpholine, N,N-dimethylpropenylamine, N,N-diethylacrylamide, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate Base ester, methoxy polyethylene glycol acrylate, ethoxy polyethylene glycol acrylate, melamine acrylate, phenoxyethyl acrylate, phenoxy propyl acrylate, ethylene glycol diacrylate Ester, di(propylene glycol) diacrylate, polydi(propylene glycol) diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, glyceryl diacrylate, different A ketone acrylate, a dicyclopentenyl oxyethyl acrylate, and a (meth) acrylate compound such as various methacrylates. These polymerizable unsaturated compounds may be used alone or in combination of two or more.

Usually, it is preferably a (meth) acrylate compound as described above, and a (meth) acrylate compound is preferably a polyfunctional (meth) acrylate compound, usually 2 to 6 functional (methyl). The acrylate compound is more desirable.

In order to obtain a photosensitive resin composition, the present invention is preferably a composition containing a polymerizable unsaturated compound.

The compounding 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, more preferably 100 parts by weight based on the total amount of the resin Y. It is 7 to 50 parts by weight.

On the other hand, examples of the solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic diameters such as toluene and xylene; and ethyl acesulfame and butyl oxime Carbitol such as sulphate, carbitol, butyl carbitol, ethyl acetate, butyl acetate, cyproterone acetate, butyl cyproterone acetate, ethyl carbitol 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 the solvent which is the diluent (D) may be used singly or in combination of two or more kinds. Further, the amount of the polymerizable unsaturated compound and/or solvent used is from 10 to 200 parts by weight, preferably from 20 to 100 parts by weight based on 100 parts by weight of the resin Y. About 150 parts by weight. In addition, the polymerizable unsaturated compound is also required to impart curability to the active energy light to the resin, and is usually used in an amount of 3 parts by weight or more, preferably 5 parts by weight or more, based on 100 parts by weight of the resin Y. It is preferably 7 parts by weight or more, and most preferably 10 parts by weight or more. When the amount is too small, the photosensitivity is too low. On the other hand, when it exceeds 200 parts by weight, the photosensitive resin composition is used as a photoresist. In the case of the ink, the viscosity becomes too low, and there is a case where the characteristics as a hard coating film are insufficient. Therefore, in the present invention, it is preferred to use a suitable amount of the polymerizable unsaturated compound and a solvent in combination, and to prepare, for example, a coating composition having good coating properties and a cured coating film property.

In the photosensitive resin composition of the present invention, it is also possible to further improve properties such as adhesion and hardness, and it is required to be in the form of amorphous silica, calcium carbonate, magnesium carbonate, barium sulfate, clay, or the like. Inorganic fillers such as mica, cerium oxide powder, and mica powder: coloring pigments such as phthalocyanine green, phthalocyanine blue, titanium oxide, and carbon black; various additives such as defoamers and leveling agents Further using hydroquinone, resorcinol, catechol, pyrogallol, hydroquinone monomethyl ether, tertiary butyl catechol, and thiophene And other polymerization inhibitors.

The photosensitive resin composition of the present invention is obtained by blending each of the above-mentioned compounding components at a desired ratio and uniformly mixing them by a three-roll mill or the like.

The resin composition of the present invention preferably includes the following resin composition.

I. A photosensitive resin composition according to any one of (1) to (9), wherein: (A) is an alkali-developable resin according to any one of (1) to (9) above, Or the alkaline developing type resin according to any one of the above items I to X described in the above-mentioned preferred resin Y of the present invention is 10 to 80% by weight, and (B) the epoxy resin is 1 with respect to the total amount of the composition. To 50% by weight, (C) is 0.5 to 20% by weight based on the total amount of the composition, and (D) is 10 to 200 parts by weight relative to 100 parts by weight of the alkali developing type resin. Weight.

II. The photosensitive resin composition according to the above 1, wherein the epoxy resin is a novolac type epoxy resin or an aralkyl type epoxy resin.

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

The photosensitive resin composition according to any one of the above-mentioned, wherein the polymerizable unsaturated compound is contained as a diluent in an amount of from 3 to 200 parts by weight based on 100 parts by weight of the alkali-developable resin.

The photosensitive resin composition of the above-mentioned IV, wherein the content of the polymerizable unsaturated compound is from 5 to 100% by weight based on 100 parts by weight of the alkali developing type resin. Quantities.

The photosensitive resin composition of the above-mentioned IV or V, wherein the polymerizable unsaturated compound is a (meth) acrylate compound.

The photosensitive resin composition according to any one of the above-mentioned items, wherein the diluent contains a solvent, and the total amount of the polymerizable unsaturated compound and the solvent is 100 parts by weight with respect to the alkali developing type resin. 10 to 200 parts by weight.

VIII. The photosensitive resin composition according to any one of the above-mentioned, wherein the inorganic filler is contained in an amount of from 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 is cured by, for example, the following to obtain a cured product. That is, the composition of the present invention is applied to a film thickness of 10 to 160 μm on a printed circuit board by a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain coating method, or the like, and the coating is applied. The film is dried at 60 to 110 ° C, and secondly, a negative film is directly contacted with the coating film (or placed on the coating film in a non-contact state), and secondly, ultraviolet rays are irradiated to expose the composition, and an aqueous solution of a rare alkali is used. After the unexposed portion is dissolved and removed for development, in order to further improve the physical properties, it is sufficiently cured by irradiation with ultraviolet rays and/or heating (for example, heating at 100 to 200 ° C for 0.5 to 1.0 hour) to obtain a cured coating film.

The photosensitive resin composition of the present invention may be used in the form of a dry film in addition to a method of directly applying a liquid to a substrate, and the dry film is previously used in polyethylene terephthalate. The film of the ester or the like is coated with a solder resist and dried to form a solder resist layer. The dry film is a structure having a sequentially laminated carrier film, a solder resist layer, and a peelable cover film used as needed.

Using a dry film to form a protective film on a printed circuit board, the film is peeled off, and the solder resist is removed. The layer overlaps with the substrate on which the circuit has been formed, and is bonded by using a laminator or the like to form a solder resist layer on the substrate on which the circuit has been formed. The cured solder coating film can be formed by exposing, developing, and heat-hardening the formed solder resist layer in the same manner as described above.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to these examples. In addition, the "parts" and "%" in each case indicate "parts by weight" and "% by weight" unless otherwise stated.

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

A cresol novolac resin [Shonol CRG-951, manufactured by Showa Polymer Co., Ltd., hydroxyl equivalent 118, softening point 96 ° C, number average molecular weight 750] 118 parts (1.0 equivalent) and propylene glycol monomethyl ether acetate were prepared. 124.71 parts were heated at 80 ° C to uniformly dissolve the above mixture. After confirming the dissolution, 37.04 parts (0.5 mol) of glycidol and 0.47 parts of triphenylphosphine were added thereto, and the mixture was heated at 120 ° C for about 8 hours to obtain a reaction product X (resin: intermediate X). When the reaction rate was measured by GPC (gel permeation chromatography), the reaction rate of glycidol was 98%. Next, 32.03 parts (0.17 mol) of trimellitic anhydride was added to the reaction liquid containing the reaction product X, and the mixture was reacted at 100 ° C for about 6 hours to obtain a curable resin (Y-1) of the present invention. (solid content acid value 100 mg KOH / g, solid content concentration 60%). The average molecular weight Mw of this resin Y-1 was 3,200.

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

A biphenyl aralkyl type phenol resin [GPH-103, manufactured by Nippon Kayaku Co., Ltd., hydroxyl equivalent 239, softening point 103 ° C, all phenolic hydroxyl groups are resorcinol hydroxyl groups (resorcinol hydroxyl group 100%) ), weight average molecular weight 3220] 239 parts (1.0 equivalents) and 222.04 parts of propylene glycol monomethyl ether acetate, heated at 80 ° C, the above mixture is homogeneous Dissolved. After confirming dissolution, 37.04 parts (0.5 mol) of glycidol and 0.83 part of triphenylphosphine were added thereto, and the mixture was heated at 120 ° C 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%. Next, 57.02 parts (0.3 mol) of trimellitic anhydride was added to the reaction liquid containing the reaction product X, and the mixture was reacted at 100 ° C for about 6 hours to obtain a curable resin (Y-2) of the present invention (solid content) The acid value is 100 mg KOH/g, and the solid content is 60%). The average molecular weight Mw of the resin Y-2 was 15,000.

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

A cresol novolak resin [EOCN-104s, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 219, softening point 90 ° C], 219 parts (1.0 equivalent), and 72 parts of acrylic acid (1.0 mol) were placed as thermal polymerization. The inhibitor was made up of 1.3 parts of 2,6-di-t-butyl-p-cresol and 216.65 parts of propylene glycol monomethyl ether acetate, and the mixture was uniformly dissolved by heating at 95 °C. After confirming the dissolution, 1.3 parts of triphenylphosphine was added thereto, and the mixture was heated at 100 ° C for about 24 hours to obtain a reaction product (solid content acid value: 3.0 mg KOH/g or less). 109.10 parts (0.72 mol) of tetrahydrophthalic anhydride was added thereto, and the reaction was heated at 98 ° C for about 6 hours to obtain a comparatively curable resin Z (solid content acid value 100 mg KOH / g, solid content concentration 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 by the above-mentioned Synthesis Examples 1 and 2 and Comparative Synthesis Example 1 were kneaded by a three-roll mill according to the blending ratio shown in Table 1, and the photosensitive resins of the examples and comparative examples of the present invention were prepared. Composition. Each of the compositions of Examples 1 to 3 and Comparative Example 1 prepared at the mixing ratio shown in Table 1 was diluted with methyl ethyl ketone, coated on a PET film, and dried at 80 ° C for 30 minutes to prepare a dried glass having a thickness of 20 μm. A film-like photosensitive resin composition layer. Further, after drying at 80 ° C for 30 minutes, it was cooled to room temperature to obtain a dried coating film. The coating film was adhered to the negative film having the photoresist pattern, and exposed to 350 mJ/cm ² using an ultraviolet exposure apparatus, and after removing the negative film, development was carried out for 60 seconds at a spray pressure of 2.0 kgf/cm ² using a 1% aqueous sodium carbonate solution. The unexposed portion was dissolved and removed. Thereafter, the film was heat-cured at 150 ° C for 60 minutes using a hot air dryer to prepare a cured film having a photoresist pattern.

Table 1.

^* 1 NC-3000H CA75: Biphenyl phenol varnish type epoxy resin [made by Nippon Kayaku Co., Ltd.]

^* 2 Irg.907: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinone-1 [Irgacure 907, manufactured by Ciba Japan Co., Ltd.]

^* 3 DETEX-S: 2,4-Diethyloxythiazinone [Kayacure DETEX-S, manufactured by Nippon Kayaku Co., Ltd.]

^* 4 TMPTA: Trimethylolpropane triacrylate [Light acrylate TMP-A, manufactured by Kyoeisha Chemical Co., Ltd.]

Each of the test pieces of the present invention and the comparative product having the cured film obtained in the above manner was subjected to developability, adhesion, solder heat resistance, electroless gold plating resistance, and PCT resistance according to the test method shown below. , flexibility test, thermal shock resistance test, HAST characteristic test, various physical properties of the coating film were evaluated. The evaluation results of these tests are shown in Tables 2 and 3. However, the developability was evaluated by taking a coating film having various changes in addition to the preliminary drying time at 80 ° C for 30 minutes.

<developability>

Each of the dried coating films having a preliminary drying time of 20 minutes, 40 minutes, 60 minutes, 80 minutes, and 100 minutes was developed using a 1% sodium carbonate aqueous solution at a spray pressure of 2.0 kgf/cm ² for 60 seconds, and development was observed. There is no film after the test and it is evaluated by the following criteria.

○: The coating film was completely removed after development, and it was completely developed.

X: There is a slight coating film which remains without being removed after development, and is incompletely developed.

<Adhesion>

According to the test method of JIS D 0202, the cured film of each test piece was cut into a checkerboard shape, and a peeling test was performed by a transparent tape, and the peeling state after a test was visually judged. The evaluation is based on the following benchmarks.

○: All were not peeled off.

△: There is a slight peeling of the cross-cut portion.

X: The coating film is peeled off.

<Welding heat resistance>

Each test piece was placed in a solder bath at 280 ° C according to the test method of JIS C 6481. The mixture was immersed for 10 seconds, immersed three times, and after taking out, the change in appearance was observed. Use the following benchmarks for evaluation.

○: The appearance of the cured film did not change.

△: It was confirmed that the cured film had discoloration.

X: There is a floating, peeling, and soldering of the cured film.

<electroless gold plating resistance>

As a test piece pretreatment, each test piece was immersed in an acidic degreasing liquid at 30 ° C → immersion washing, soft etching treatment, immersion water washing, and a catalyst (immersion in a nickel plating catalyst solution at 30 ° C for 7 minutes). ) → the step of immersion washing. Next, as an electroless nickel plating step, each test piece was immersed in a nickel plating solution (85 ° C, pH 4.6) for 20 minutes → immersion acid (10 vol% aqueous sulfuric acid solution at room temperature) for 1 minute → immersion washing. Finally, as an electroless gold plating step, each test piece was immersed in a gold plating solution (95 ° C, pH 6, gold oxychloride potassium 3 vol% aqueous solution) for 10 minutes → immersion washing → immersion in warm water of 60 ° C for hot water washing → full After washing with water → appropriate water removal → electroless gold plating was performed in a drying step, and the appearance change of the test pieces was observed and a peeling test was performed using a transparent tape, and the coating film was evaluated. The evaluation is based on the following benchmarks.

○: There is no change in appearance, and there is no peeling off of the photoresist at all.

△: Although the appearance did not change, the peeling of the photoresist was slightly observed.

X: The floating or coating of the photoresist was observed, and the photoresist was peeled off in the peeling test.

<PCT Test>

The appearance of the coating film after placing each test piece at 121 ° C, 2 atm, in a saturated vapor atmosphere for 100 hours was visually judged. The evaluation is based on the following benchmarks.

○: The coating film has no swelling or peeling.

X: There are people who have swelling and peeling off.

<Flexibility Test>

According to JIS K5400, each of the above-mentioned photosensitive resin compositions is applied onto a phosphate-treated steel plate (drying→exposure→development→heating) using an Erichsen tester defined by the JIS B7729A method. Test piece. The steel ball was extruded from the inner surface of each of the obtained test pieces, and the extrusion distance from the time when the test piece was deformed to the time when the coating film was cut and peeled off was measured. The evaluation is based on the following benchmarks.

○: The distance between the steel ball and the peeling and peeling of the coating film was 4 mm or more.

△: The distance at which the steel ball was extruded without causing the coating film to be split and peeled off was 2 mm or more and less than 4 mm.

X: The distance between the steel ball and the peeling and peeling of the coating film was not less than 2 mm.

<Cold and thermal shock resistance test>

An evaluation substrate on which a solder resist-hardened coating film having a hollow pattern and a hollow pattern was formed was produced. The obtained evaluation substrate was subjected to a cycle test at a temperature of -55 ° C / 30 minutes to 150 ° C / 30 minutes using a thermal shock tester (manufactured by Etac Co., Ltd.), and subjected to a 1000-cycle resistance test after the test, by visual inspection. The cured film after the treatment was observed, and the occurrence of cracks was judged based on the following criteria.

○: The incidence of cracks is less than 30%

△: The incidence of cracks is 30% to 50%

X: The incidence of cracks is above 50%

<HAST Characteristics>

A solder resist-hardened coating film was formed on a BT substrate on which a comb-shaped electrode (line/space = 30 μm / 30 μm) was formed, and an evaluation substrate was prepared. The evaluation substrate was placed in a high-temperature and high-humidity bath at 130 ° C and a humidity of 85%, and the charging voltage was 5.5 V, and the in-tank HAST test (insulation test) was performed for various times. The insulation resistance values in the slots after various times were evaluated according to the following criteria.

○: After 240 hours, above 108 Ω

X: After 240 hours, below 108Ω

As is apparent from the evaluation results of Tables 2 and 3, the alkali-developing resin of the present invention has drying property and alkaline development as compared with the conventionally known epoxy-based photosensitive resin. The properties are excellent, and the cured product is excellent in adhesion, solder heat resistance, electroless gold plating resistance, PCT resistance, flexibility, thermal shock resistance, HAST characteristics, and the like.

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

According to the description of Japanese Patent Application Laid-Open No. Hei 8-143648, the phenol and the resorcinol which are both phenol compounds are prepared by the ratio of phenol 9 molar to resorcinol 1 mol. Varnish resorcinol phenolic resin [hydroxyl equivalent 134 g/eq, softening point 93.4 ° C, resorcinol hydroxyl group ratio {(resorcinol hydroxyl number / total phenolic hydroxyl group in phenol resin (a1)) ) x 100 } = about 20%] 134 parts (hydroxy equivalent: 1.0 equivalent), 179.56 parts of propylene glycol monomethyl ether acetate, and heated at 80 ° C to uniformly dissolve the above mixture. After confirming the dissolution, 14.82 parts (0.2 mol) of glycidol and 0.45 parts of triphenylphosphine were added thereto, and the mixture was heated at 120 ° C 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%. Next, 30.74 parts (0.16 mol) of trimellitic anhydride was added to the reaction liquid containing the reaction product X, and the reaction was carried out at 100 ° C for about 6 hours to obtain a curable resin (Y-3) of the present invention (solid content) The concentration is 50%, and the solid content is 100 mg KOH/g. The average molecular weight Mw of this resin Y-3 was 1,900.

Synthesis Example 4 (Synthesis Example of Resin Y4)

A biphenol novolak type resorcinol resin [hydroxyl group equivalent 102, softening point 85.2 ° C], 102 parts (1.0 equivalent) and propylene glycol monomethyl ether acetate synthesized in accordance with Example 1 of JP-A-H07-292066. The mixture was 192.09 parts and heated at 80 ° C to uniformly dissolve the above mixture. 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 heated at 120 ° C 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%. Next, in the reaction containing the reaction product X 51.05 parts (0.34 mol) of tetrahydrophthalic anhydride was added to the solution, and reacted at 100 ° C for about 6 hours to obtain a curable resin (Y-4) of the present invention (solid content concentration 50%, solid acid value) 100 mg KOH/g). The average molecular weight Mw of this resin Y-4 was 1,200.

Examples 4 to 7 and Comparative Example 2:

The resin Y-2, Y-3, Y-4 and the curable resin Z obtained in the above Synthesis Examples 2, 3, and 4 and the above Comparative Synthesis Example 1 were respectively kneaded by a 3-roll mill according to the blending ratio shown in Table 4. The photosensitive resin compositions of the examples and comparative examples of the present invention were prepared. Each of the compositions of Examples 4 to 7 and Comparative Example 2 prepared at the mixing ratio shown in Table 4 was diluted with methyl ethyl ketone, coated on a PET film, and dried at 80 ° C for 30 minutes to prepare a dried glass having a thickness of 20 μm. A film-like photosensitive resin composition layer. Further, after drying at 80 ° C for 30 minutes, it was cooled to room temperature to obtain a dried coating film. Here, the coating film is adhered to the negative film having the photoresist pattern, and exposed to 350 mJ/cm ² using an ultraviolet exposure apparatus, and after removing the negative film, using a 1% sodium carbonate aqueous solution and developing at a pressure of 2.0 kgf/cm ^{2 for} 60 seconds, The unexposed portion was dissolved and removed. Thereafter, the film was heat-cured at 150 ° C for 60 minutes using a hot air dryer to prepare a cured film having a photoresist pattern (the test piece of the present invention and the test piece for comparison).

^* 1 NC-3000H CA75: Biphenyl phenol varnish type epoxy resin [made by Nippon Kayaku Co., Ltd.]

^* 2 Irg.907: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinone-1 [Irgacure 907, manufactured by Ciba Japan Co., Ltd.]

^* 3 DETEX-S: 2,4-Diethyloxythiazinone [Kayacure DETEX-S, manufactured by Nippon Kayaku Co., Ltd.]

^* 4 DPTA: dipentaerythritol hexaacrylate [Kayrad DPHA, manufactured by Nippon Kayaku Co., Ltd.]

The test piece of the present invention and the comparative test piece having the cured film obtained by the above operation were subjected to developability, adhesion, solder heat resistance, electroless gold plating resistance, PCT resistance, and the like according to the test methods described above. Flexibility test, various physical properties of the coating film were evaluated. The evaluation results of these tests are shown in Tables 5 and 6. However, the developability was evaluated by taking a coating film having various changes in addition to the preliminary drying time at 80 ° C for 30 minutes. The evaluation criteria are the same as in Table 2.

As a result of the evaluation of Tables 5 and 6, the alkali-developing resin of the present invention is superior in drying property and alkali developability to the conventionally known epoxy-based photosensitive resin, and the cured product is in adhesion. It is excellent in solder heat resistance, electroless gold plating resistance, PCT resistance, flexibility, thermal shock resistance, and HAST characteristics.

In particular, the alkali-developing resin of the present invention containing a phenol resin containing a biphenyl novolak-type resorcinol is also preferable in terms of drying property and alkali developability in the alkali-developing resin of the present invention. The other is even better.

(industrial availability)

The photosensitive resin composition of the present invention is excellent in drying property and alkali developability, and the coating film after curing is in adhesion, solder heat resistance, electroless gold plating resistance, It is excellent in various properties such as PCT resistance, flexibility, thermal shock resistance, and HAST characteristics. Since the cured film can be formed with good productivity at a low cost, in addition to the ultraviolet curable printing ink used for curing using active energy rays, etc., there is a solder resist used for manufacturing a printed circuit board. , resist, anti-plating agent, interlayer insulation, etc.

Claims (20)

An alkali-developing resin obtained by reacting a hydroxyl group of a phenol resin (a) with a compound (b) having an alcoholic hydroxyl group and one epoxy group in a molecule, and obtaining the obtained product X The hydroxyl group of the reaction product X is further reacted with a saturated and/or unsaturated polybasic acid anhydride (c), which remains in the alkali-developing resin with respect to the total phenolic hydroxyl group number in the phenol resin (a). The ratio of phenolic hydroxyl groups is 30 to 80%. The alkali-developing type resin according to the first aspect of the invention, wherein the compound (b) is reacted at a ratio of 0.1 to 0.9 mol per 1 equivalent of the phenolic hydroxyl group of the phenol resin (a). The alkaline developing type resin according to the first or second aspect of the invention, wherein the polybasic acid anhydride (c) is 0.05 to 0.9 mol per 1 equivalent of the alcoholic hydroxyl group of the reaction product X. Rate to react. The alkali-developable resin according to the first or second aspect of the invention, wherein the phenol resin (a) is a biphenyl backbone. The alkali-developing resin according to the first or second aspect of the invention, wherein the phenol resin (a) is a phenol resin (a1) represented by the following formula (1); In the formula, m1, m2 and m3 are integers each independently representing 1 or 2, and n is an integer representing 0 to 10. The alkali-developing type resin according to claim 5, wherein the phenol resin (a1) is a phenol resin containing a resorcin structure. The alkali-developable resin according to claim 6, wherein the phenol resin having a resorcinol structure has a hydroxyl equivalent of 70 to 170 g/eq. The alkaline developing type resin according to any one of the preceding claims, wherein the compound (b) is glycidol. The alkali-developable resin according to any one of the preceding claims, wherein the polybasic acid anhydride (c) is a polybasic acid anhydride having two or three carboxyl groups. A photosensitive resin composition comprising: (A) an alkali-developable resin according to any one of items 1 to 9 of the invention, (B) an epoxy resin, (C) photopolymerization Starting agent, and (D) diluent. The photosensitive resin composition according to claim 10, wherein the diluent is a polymerizable unsaturated compound and/or a solvent. The photosensitive resin composition according to claim 10, wherein (A) is from 10 to 80% by weight based on the total amount of the composition; (B) relative to The total amount of the composition, the epoxy resin is 1 to 50% by weight; (C) the photopolymerization initiator is 0.5 to 20% by weight based on the total amount of the composition; and (D) relative to the alkali developing resin 100 parts by weight of the diluent is 10 to 200 parts by weight. The photosensitive resin composition according to the item 10 or claim 11, wherein the photosensitive resin composition contains 5 to 200 parts by weight based on 100 parts by weight of the alkali developing type resin. A range of polymeric unsaturated compounds is used as a diluent. The photosensitive resin composition as described in claim 13, wherein the polymerizable unsaturated compound is a (meth) acrylate compound. A cured product of the photosensitive resin composition according to any one of claims 10 to 14. The cured product of the photosensitive resin composition according to the fifteenth aspect of the invention is a cured product which is patterned by a photolithography method capable of ultra-fine processing by light. A substrate having a layer of a cured product as described in claim 15 or 16. An article having the substrate of claim 17 of the patent application. A method for forming a cured coating film, which comprises applying a photosensitive resin composition according to any one of claims 10 to 14 on a printed circuit board to form a coating film, and performing exposure and development. It is hardened by irradiation and/or heating of ultraviolet rays. A use of a reaction product X having both a phenolic hydroxyl group and an alcoholic hydroxyl group, which is used for producing the alkali-developable resin described in claim 1, wherein the reaction product X is a phenol resin ( The hydroxyl group of a) is obtained by reacting a compound (b) having an alcoholic hydroxyl group and one epoxy group in the molecule.