JPWO2019188895A1 - Unsaturated group-containing alkali-soluble resin, photosensitive resin composition containing it as an essential component, and cured product thereof - Google Patents

Abstract

An alkali-soluble resin represented by the general formula (1) and having a carboxyl group and a polymerizable unsaturated group in one molecule, (i) an alkali-soluble resin of the general formula (1), and (ii) at least one polymerization. A photosensitive resin composition containing a photopolymerizable monomer having a sex unsaturated group, a (iii) photopolymerization initiator, and an optionally added (iv) epoxy compound. [Chemical 1]

Description

The present invention relates to an unsaturated group-containing alkali-soluble resin, a photosensitive resin composition containing the unsaturated group as an essential component, and a cured product obtained by curing the photosensitive resin composition. The photosensitive resin composition of the present invention and a cured product thereof are a solder resist, a plating resist, an etching resist for producing a circuit board, an insulating film for multi-layering a wiring board on which a semiconductor element is mounted, and a semiconductor gate insulating film. , Applicable to photosensitive adhesives and the like.

With the recent increase in performance and definition of electronic devices and display members, the electronic components used therein are required to be smaller and have higher densities. Further, in terms of workability of the insulating materials used for them, miniaturization and optimization of the cross-sectional shape of the processed pattern are required. A method of patterning by exposure and development is known as an effective means for microfabrication of an insulating material, and a photosensitive resin composition has been used there. Many properties such as heat resistance and chemical resistance are required. In addition, various studies have been conducted on the use of an organic insulating material in a gate insulating film for an organic TFT, but it is necessary to reduce the operating voltage of the organic TFT by thinning the gate insulating film. Here, in the case of an organic insulating material having an insulating withstand voltage of about 1 MV / cm, the application of a thin film having an insulating film thickness of about 0.2 μm is being studied.

In the conventional insulating material made of a photosensitive resin composition, a photocuring reaction by a reaction between a photoreactive alkali-soluble resin and a photopolymerization initiator is used, and a mercury lamp is mainly used as an exposure wavelength for photocuring. The i-line (365 nm), which is one of the line spectra of the above, is used. However, this i-ray is absorbed by the photosensitive resin itself or the colorant, and the degree of photocurability is lowered. Moreover, if it is a thick film, the amount of absorption increases. Therefore, the exposed portion has a difference in the cross-linking density with respect to the film thickness direction. As a result, even if the surface of the coating film is sufficiently photo-cured, it is difficult to photo-cure the bottom surface of the coating film, so that it is extremely difficult to make a difference in the crosslink density between the exposed portion and the unexposed portion. As a result, it is difficult to obtain a photosensitive insulating material that has desired pattern dimensional stability, development margin, pattern adhesion, pattern edge shape and cross-sectional shape and can be developed at high resolution.

Generally, a photosensitive resin composition in such an application contains a polyfunctional photocurable monomer having a polymerizable unsaturated bond, an alkali-soluble binder resin, a photopolymerization initiator and the like. , The photosensitive resin composition disclosed in the art as an application as a material for a color filter can be applied. For example, Patent Document 1 and Patent Document 2 disclose a copolymer of (meth) acrylic acid or (meth) acrylic acid ester having a carboxyl group as a binder resin, maleic anhydride, and another polymerizable monomer. Has been done. Further, Patent Document 3 discloses that an alkali-soluble unsaturated compound having a polymerizable unsaturated group and a carboxyl group in one molecule is effective for forming a negative pattern such as a color filter.

On the other hand, Patent Document 4, Patent Document 5, Patent Document 6 and Patent Document 7 disclose a liquid resin using a reaction product of an epoxy (meth) acrylate having a bisphenol fluorene structure and an acid anhydride.

Further, Patent Document 8 discloses polyfunctionalization of an alkali-soluble resin composition that increases the molecular weight of the carboxyl group-containing copolymer.

Japanese Unexamined Patent Publication No. 62-121313 Japanese Unexamined Patent Publication No. 1-152449 Japanese Unexamined Patent Publication No. 4-340965 Japanese Unexamined Patent Publication No. 4-345673 Japanese Unexamined Patent Publication No. 4-345608 Japanese Unexamined Patent Publication No. 4-355450 Japanese Unexamined Patent Publication No. 4-363311 Japanese Unexamined Patent Publication No. 9-325494

However, since the copolymers disclosed in Patent Documents 1 and 2 are random copolymers, the alkali dissolution rate is distributed in the light-irradiated portion and the light-non-irradiated portion, and the development operation is performed. Since the time margin becomes narrow, it is difficult to obtain a sharp pattern shape or a fine pattern.

Further, since the alkali-soluble unsaturated compound described in Patent Document 3 is insolubilized by light irradiation, it is expected that the sensitivity will be higher than that of the above-mentioned combination of the binder resin and the polyfunctional polymerizable monomer. .. Here, examples of the compounds described in Patent Document 3 include those in which acrylic acid having a polymerizable unsaturated group and an acid anhydride are arbitrarily added to the hydroxyl group of the phenol oligomer. Even in the compound of Patent Document 3, since the molecular weight and the amount of the carboxyl group of each molecule are widely distributed, the distribution of the alkali dissolution rate of the alkali-soluble resin is wide, and it is difficult to form a fine negative pattern. is there.

Further, examples of the resins described in Patent Document 4, Patent Document 5, Patent Document 6 and Patent Document 7 include reaction products of epoxy (meth) acrylate and acid monoanhydride. Since this reaction product has a small molecular weight, it is difficult to increase the difference in alkali solubility between the exposed portion and the unexposed portion, so that a fine pattern cannot be formed.

Further, since the copolymer described in Patent Document 8 has a small number of polymerizable unsaturated bonds, a sufficient cross-linking density cannot be obtained. Therefore, the copolymer such as increasing the ratio of polymerizable unsaturated bonds in one molecule is used. There is room for structural improvement.

An object of the present invention is to provide a photosensitive resin composition capable of patterning with excellent resolution by alkaline development. Further, the cured product has a characteristic of low thermal expansion rate even when heat is applied in the processing process after pattern formation in a semiconductor process or the like, and also has excellent chemical resistance when undergoing a processing process such as electrode formation. It is to provide a cured film having the characteristics shown.

As a result of diligent studies to solve the above problems, the present inventors have obtained (meth) acrylic acid by reacting an epoxy compound having two or more glycidyl ether groups derived from a polymer of naphthols with (meth) acrylic acid. A photosensitive resin composition using an alkali-soluble resin obtained by reacting a polyhydric alcohol having a polymerizable unsaturated group with a dicarboxylic acid, a tricarboxylic acid, or an acid monoanhydride thereof is an insulation that requires photopatterning. It has been found that it is suitable for forming a cured film pattern such as a film.

（Ｘは炭素数１〜２０の２価の炭化水素基を示す。上記２価の炭化水素基は直鎖または分岐を有してもよく、主鎖または分岐鎖に芳香環を有してもよい。Ｙは炭素数１〜５の炭化水素基Ｒまたは一般式（２）で表される分子内に重合性不飽和基とカルボキシル基を有する置換基Ｚであり、Ｒのモル数Ｃ_Ｒ、Ｚのモル数Ｃ_Ｚとしたとき、Ｃ_Ｒ／Ｃ_Ｚの値は０．０５〜２．０である。平均値としてのｎの値は１〜２０である。さらに、ナフタレン環の水素原子の一部はＲ_１で置換されていてもよく、Ｒ_１は炭素数１〜５の炭化水素基、ハロゲン原子またはフェニル基を示す。）

（Ｒ_３は水素原子またはメチル基を示す。Ｌは一般式（３）で表される置換基を示す。）

（Ｍは２または３価のカルボン酸残基を示し、ｐは１または２である。）That is, the embodiment of the present invention relates to (i) an alkali-soluble resin represented by the following general formula (1) and having a carboxyl group and a polymerizable unsaturated group in one molecule.

(X represents a divalent hydrocarbon group having 1 to 20 carbon atoms. The divalent hydrocarbon group may have a linear or branched structure, or may have an aromatic ring in the main chain or the branched chain. Good. Y is a hydrocarbon group R having 1 to 5 carbon atoms or a substituent Z having a polymerizable unsaturated group and a carboxyl group in the molecule represented by the general formula (2), and the number of moles CR of _R , when the Z moles _{C Z of,} C value of R / _{C Z} is the value of n as an 0.05 to 2.0. the average value is 1-20. in addition, the naphthalene ring of the hydrogen atom some may be substituted by R _1, R ₁ is a hydrocarbon group, a halogen atom or a phenyl group having 1 to 5 carbon atoms.)

(R ₃ represents a hydrogen atom or a methyl group. L represents a substituent represented by the general formula (3).)

(M indicates a divalent or trivalent carboxylic acid residue, p is 1 or 2.)

Moreover, the embodiment of the present invention is (i) an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in the above one molecule, and (ii) a photopolymerizable monomer having at least one polymerizable unsaturated group. The present invention relates to a photosensitive resin composition containing (iii) a photopolymerization initiator as an essential component.

Further, another embodiment of the present invention relates to a cured product obtained by curing the photosensitive resin composition.

According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a fine cured film pattern by photolithography by containing the alkali-soluble resin represented by the general formula (1). Further, according to the present invention, it is possible to provide a cured film pattern which has low thermal expansion property, is excellent in chemical resistance (alkali resistance, etc.), and exhibits excellent properties such as adhesion to a substrate, heat resistance, electrical reliability, and the like. it can.

Hereinafter, the photosensitive resin composition of the present invention will be described in detail. The present invention relates to a photosensitive resin composition containing an alkali-soluble resin represented by the general formula (1) as a main component, and a cured product obtained by curing the photosensitive resin composition.

The alkali-soluble resin represented by the general formula (1) is obtained by reacting an epoxy compound having two or more glycidyl ether groups derived from a polymer of naphthols with (meth) acrylic acid to obtain a non-polymerizable property. It is obtained by reacting a polyhydric alcohol having a saturated group with a dicarboxylic acid, a tricarboxylic acid or an acid monoanhydride thereof.

Since the alkali-soluble resin represented by the general formula (1) has both a polymerizable unsaturated group and a carboxyl group, it has excellent photocurability, good developability, and patterning properties in the alkali-developable photosensitive resin composition. Have. Further, when the photosensitive resin composition is made into a cured product, it can contribute to low thermal expansion property and alkali resistance.

The method for producing the alkali-soluble resin represented by the general formula (1) will be described in detail. First, the alkali-soluble resin of the general formula (1) has a naphthalene skeleton represented by the general formula (4) having two or more glycidyl ether groups obtained by converting the phenolic hydroxyl group of the naphthol compound into glycidyl ether. It is derived from a polyhydric alcohol containing a polymerizable unsaturated group obtained by reacting an epoxy compound with (meth) acrylic acid. As a method for producing an epoxy compound having a naphthol skeleton, for example, the production method described in JP-A-2006-160868 can be referred to.

In the general formula (4), X represents a divalent hydrocarbon group having 1 to 20 carbon atoms. The divalent hydrocarbon group may have a straight chain or a branched chain, and may have an aromatic ring in the main chain or the branched chain. Specifically, -CH _2- , -CH (CH ₃ )-, -CH (C ₂ H ₅ )-, -CH (C ₆ H ₅ )-, general formula (5), general formula (6) and It is a divalent binding group represented by the general formula (7). Here, the divalent linking group is preferably the general formula (5), the general formula (6), and the general formula (7). W represents a hydrocarbon group R or a glycidyl group G, of 1 to 5 carbon atoms, moles _C R of R, when the number of moles _{C G G,} then the value of C R / _{C G} 0.05 to 2 It is 0.0. R is preferably a methyl group or an ethyl group. When the resin of the general formula (4) is produced, it is usually obtained as a mixture of molecules having different numerical values n, but the value of n as an average value is preferably 1 to 20, and preferably 1 to 10. More preferably, 1 to 6 is particularly preferable. In addition, some of the substituent for the hydrogen atom of the benzene ring of a part of the hydrogen atoms of the naphthalene ring may be substituted with a substituent R _1, the general formula (5) to (7) of the general formula (4) It may be replaced with _{R 2.} R ₁ and R ₂ independently represent a hydrocarbon group having 1 to 5 carbon atoms, a halogen atom or a phenyl group.

As the polymerization method of naphthols, a general method for producing a phenol resin or a phenol aralkyl resin can be referred to, but in order to induce a compound of the general formula (4) characterized by having a hydrocarbon group R. As a method for producing the above, the method described in JP-A-2006-160868 can be referred to. Specifically, as a first step, naphthols and a cross-linking agent are condensed in the presence of an acidic catalyst, but 1-naphthol and / or 2-naphthol are used as the naphthols, and formaldehyde, acetaldehyde, etc. are used as the cross-linking agent. Aldehyde compounds such as benzaldehyde; 1,4-bis (chloromethyl) benzene, 1,4-bis (chloroethyl) benzene, 4,4'-bis (chloromethyl) biphenyl, 4,4'-bis (chloromethylbiphenyl) Alkyl halide compounds such as ether; p-xylylene glycol, p-di (hydroxyethyl) benzene, 4,4'-bis (hydroxymethyl) biphenyl, 2,6-bis (hydroxymethyl) naphthalene, 2,2' Alcohols such as −bis (hydroxymethyl) diphenyl ether; Dialkyl ethers of alcohols such as p-xylylene glycol dimethyl ether: Divinyl compounds such as divinylbenzene and divinylbiphenyl can be exemplified. Here, the cross-linking agent used is 1,4-bis (chloromethyl) benzene, 1,4-bis (chloroethyl) benzene, 4,4'-bis (chloromethyl) biphenyl, p-xylylene glycol, p-. It is preferably di (hydroxyethyl) benzene, p-xylylene glycol dimethyl ether, and 4,4'-bis (hydroxymethyl) biphenyl. The acidic catalyst can be appropriately selected from well-known inorganic acids and organic acids. For example, inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as formic acid, oxalic acid and p-toluenesulfonic acid, and Lewis such as aluminum chloride. Examples thereof include acids, active white clay, and solid acids such as zeolite. As a second step, a part of the hydroxyl groups of the resin obtained by reacting the naphthols with the cross-linking agent is made alkoxy. For example, a polymer of the naphthols of the present invention can be obtained by reacting the resin obtained in the first step with alcohols under an acidic catalyst. Examples of alcohols to be used include methanol, ethanol, propanol, butanol, pentanol and the like, and the catalyst exemplified in the first step can be used as the acidic catalyst. As another method for obtaining a polymer of the naphthols of the present invention, when the naphthols and the cross-linking agent are condensed in the presence of an acidic catalyst, in addition to 1-naphthol and / or 2-naphthol as the naphthols, alkoxy A production method in which naphthalene is used in combination may be used. Examples of alkoxynaphthalene include 1-methoxynaphthalene, 2-methoxynaphthalene, 1-ethoxynaphthalene, 2-ethoxynaphthalene, 1-propoxynaphthalene, 2-propoxynaphthalene.

By converting the phenolic hydroxyl group of the polymer of naphthols into glycidyl ether, an epoxy compound having a naphthalene skeleton represented by the general formula (4) having two or more glycidyl ether groups can be obtained. The production method can be carried out in the same manner as the usual epoxidation reaction of a hydroxyl group. For example, there is a method in which a polymer of naphthols is dissolved in excess epichlorohydrin and then reacted at 20 to 150 ° C. for 1 to 10 hours in the presence of an alkali metal hydroxide such as sodium hydroxide.

Next, a known method can be used for the reaction between such an epoxy compound and (meth) acrylic acid. For example, 2 mol of (meth) acrylic acid is used for 1 mol of the epoxy group. Since (meth) acrylic acid is reacted with all epoxy groups, (meth) acrylic acid may be used in a slightly larger amount than the equimolar amount of the epoxy group and the carboxyl group. The reactant obtained by this reaction is an epoxy (meth) acrylate as represented by the general formula (8).

（Ｘ、ｎの定義は一般式（７）の化合物と同様であり、Ｑは炭素数１〜５の炭化水素基または一般式（９）で表される分子内に重合性不飽和基を有する置換基を示す。）

(The definitions of X and n are the same as those of the compound of the general formula (7), and Q has a hydrocarbon group having 1 to 5 carbon atoms or a polymerizable unsaturated group in the molecule represented by the general formula (9). Indicates a substituent.)

（Ｒ_３は水素原子またはメチル基を示す。）

(R ₃ indicates a hydrogen atom or a methyl group.)

The solvent, catalyst and other reaction conditions used at this time are not particularly limited. For example, the solvent preferably does not have a hydroxyl group and has a boiling point higher than the reaction temperature. Examples of such solvents are cellosolvent solvents including ethyl cellosolve acetate and butyl cellosolve acetate; high boiling ether or ester systems including jiglime, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate. Solvent; A ketone solvent containing cyclohexanone, diisobutylketone and the like is included. Examples of catalysts include known catalysts such as ammonium salts containing tetraethylammonium bromide and triethylbenzylammonium chloride and the like; phosphines including triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine and the like.

By reacting the hydroxyl group of the compound represented by the general formula (8) with a dicarboxylic acid, a tricarboxylic acid or an acid monoanhydride thereof, an alkali-soluble resin represented by the general formula (1) can be obtained. Since the reaction is usually carried out using acid monoanhydride, it is exemplified as acid monoanhydride. Each hydrocarbon residue (structure excluding the carboxyl group) of these acid monoanhydrides may be further substituted with a substituent such as an alkyl group, a cycloalkyl group, or an aromatic group. Examples of acid monoanhydrides of saturated chain hydrocarbon dicarboxylic acids or tricarboxylic acids include succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citralinic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, Acid monoanhydrides such as pimeric acid, sebacic acid, suberic acid and diglycolic acid are included. Examples of acid monoanhydrides of saturated cyclic hydrocarbon dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornandicarboxylic acid and hexahydrotrimeric acid. Things are included. Examples of acid monoanhydrides of unsaturated dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as maleic acid, itaconic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid and chlorendic acid. Further, examples of acid monoanhydrides of aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids include acid anhydrides such as phthalic acid and trimellitic acid. Among these, the acid monoanhydride is preferably an acid monoanhydride of succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid, and succinic acid, itaconic acid, and so on. More preferably, it is an acid monoanhydride of tetrahydrophthalic acid. It should be noted that these acid monoanhydrides may be used alone or in combination of two or more.

The hydroxyl group of the compound represented by the general formula (8) is reacted with a dicarboxylic acid or a tricarboxylic acid or an acid monoanhydride thereof. The reaction temperature at the time of synthesizing the compound represented by the general formula (1) is preferably 20 to 120 ° C, more preferably 40 to 90 ° C. The molar ratio of the acid monoanhydride when synthesizing the compound represented by the general formula (1) can be arbitrarily changed for the purpose of adjusting the acid value of the alkali-soluble resin represented by the general formula (1).

The photosensitive resin composition of the present invention contains an alkali-soluble resin represented by the general formula (1) of (i) in the solid content (the solid content includes a monomer that becomes a solid content after curing) excluding the solvent. Is preferably contained in an amount of 30% by mass or more, and more preferably 50% by mass or more.

In order to make the best use of the characteristics of the photosensitive resin composition, it is preferable to contain the following components (i) to (iii) as essential components, and it is more preferable to contain the following components (iv) as essential components.
(I) An alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule represented by the general formula (1).
(Ii) A photopolymerizable monomer having at least one polymerizable unsaturated group,
(Iii) Photopolymerization Initiator,
(Iv) Epoxy compound

Among these, examples of the photopolymerizable monomer having at least one polymerizable unsaturated group as the component (ii) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-. Monomer having a hydroxyl group such as ethylhexyl (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di ( Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Trimethylol Ethantri (Meta) Acrylate, Pentaerythritol Di (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, Dipentaerythritol Tetra Includes (meth) acrylic acid esters such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and glycerol (meth) acrylate. When it is necessary to form a crosslinked structure between molecules of an alkali-soluble resin, it is preferable to use a photopolymerizable monomer having two or more polymerizable unsaturated groups, and three or more polymerizable unsaturated groups. It is more preferable to use a photopolymerizable monomer having the above. It should be noted that these compounds may be used alone or in combination of two or more.

The blending ratio [(i) / (ii)] of these (ii) components and the alkali-soluble resin [(i) component] represented by the general formula (1) may be 20/80 to 90/10. It is preferably 40/60 to 80/20, more preferably 40/60 to 80/20. Here, if the blending ratio of the alkali-soluble resin is small, the cured product after the photocuring reaction becomes brittle. Further, in the unexposed portion, since the acid value of the coating film is low, the solubility in the alkaline developer is lowered, so that there is a problem that the pattern edge is not sharpened. On the contrary, when the compounding ratio of the alkali-soluble resin is larger than the above range, the ratio of the photoreactive functional groups in the resin is reduced, so that the formation of the crosslinked structure by the photocuring reaction may be insufficient. Further, when the acid value of the resin component is too high, the exposed portion becomes highly soluble in the alkaline developer, so that the formed pattern tends to be thinner than the target line width, and the pattern is likely to be missing. Problems may occur.

Examples of the photopolymerization initiator of (iii) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone. Acetphenones such as benzophenones; benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2-( O-chlorophenyl) -4,5-phenylbiimidazole, 2- (O-chlorophenyl) 4,5-di (m-methoxyphenyl)) biimidazole, 2- (O-fluorophenyl) 4,5-diphenyl Biimidazole compounds such as biimidazole, 2- (O-methoxyphenyl) -4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole; 2-trichloromethyl-5-styryl-1,3 , 4-Oxaziazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4 -Halomethylthiazole compounds such as oxadiazole; 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3 5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5- Triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6 Halomethyl-s-triazine compounds such as -bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine Kind: 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1- (4-phenylsul) Fanylphenyl) butane-1,2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4-) O-acyloxime compounds such as methylsulfanylphenyl) butane-1-one oxime-O-acetate; benzyl dimethyl ketal, thioxanson, 2-chlorothioxone, 2,4-diethylthioxanson, 2-methylthioxanson , 2-Isopropylthioxanson and other sulfur compounds; 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone and other anthraquinones; azobisisobutylnitrile, benzoyl peroxide, cumemper Organic peroxides such as oxides; thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole; tertiary amines such as triethanolamine and triethylamine are included. These photopolymerization initiators may be used alone or in combination of two or more.

The amount of the photopolymerization initiator added is preferably 0.1 to 10 parts by mass, preferably 2 to 5 parts by mass, based on 100 parts by mass of the total amount of (i) alkali-soluble resin and (ii) photopolymerizable monomer. More preferably, it is a part. Here, if the amount of the photopolymerization initiator added is less than 0.1 parts by mass, sufficient sensitivity cannot be obtained, and if the amount of the photopolymerization initiator added exceeds 10 parts by mass, a tapered shape (film in the cross section of the developing pattern). Halation is likely to occur in which the hem is pulled without sharpening the shape in the thick direction. Further, decomposition gas may be generated when exposed to a high temperature in a subsequent process.

Examples of the epoxy compound (iv) include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, and oil ring. Epoxy resins such as formula epoxy resins, phenylglycidyl ethers, p-butylphenol glycidyl ethers, triglycidyl isocyanurates, diglycidyl isocyanurates, allylglycidyl ethers, glycidyl methacrylates and other compounds having at least one epoxy group are included. When it is necessary to increase the crosslink density of the alkali-soluble resin, a compound having at least two epoxy groups is preferable.

When the epoxy compound of (iv) is used, the amount added is preferably in the range of 10 to 40 parts by mass with respect to 100 parts by mass of the total of the components (i) and (ii). Here, one purpose of adding the epoxy compound is to reduce the amount of carboxyl groups remaining when the cured film is formed after patterning in order to improve the reliability of the cured film. In this case, If the amount of the epoxy compound used is less than 10 parts by mass, the moisture resistance reliability when used as an insulating film may not be ensured. Further, when the amount of the epoxy compound used is more than 40 parts by mass, the amount of photosensitive groups in the resin component in the photosensitive resin composition may decrease, and sufficient sensitivity for patterning may not be obtained. ..

Photosensitivity containing (i) an alkali-soluble resin represented by the general formula (1), (ii) a photopolymerizable monomer, (iii) a photopolymerization initiator, and (iv) an epoxy compound as essential components. The resin composition can be dissolved in a solvent or mixed with various additives, if necessary. That is, when the photosensitive resin composition of the present invention is used as an insulating material, it is preferable to use a solvent in addition to the essential components (i) to (iv). Examples of solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol; terpenes such as α- or β-terpineol; acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone. Ketones such as; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; cellosolve, methylcellosolve, ethylserosolve, carbitol, methylcarbitol, ethylcarbitol, butylcarbitol, propylene glycol monomethyl ether, propylene glycol. Glycol ethers such as monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate , Carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other acetic acid esters are included. By dissolving and mixing these alone or in combination of two or more, a uniform solution-like composition can be obtained.

Further, the photosensitive resin composition of the present invention contains, if necessary, a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, a defoaming agent, a coupling agent, and a surfactant. Additives such as and the like can be blended. Among these, as the curing accelerator, for example, known compounds known as curing accelerators, curing catalysts, latent curing agents and the like usually applied to epoxy compounds can be used, and tertiary amines, quaternary ammonium salts and tertiary compounds can be used. Phosphine, quaternary phosphonium salt, borate ester, Lewis acid, organic metal compounds, imidazoles, diazabicyclo compounds and the like are included. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenolic compounds, phosphorus thermal stabilizers and the like. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate and the like. Examples of fillers include glass fiber, silica, mica, alumina, precipitated barium sulfate, precipitated calcium carbonate and the like. Examples of defoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic-based compounds. Examples of coupling agents include vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (glycidyloxy) propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltriethoxysilane, Includes 3- (phenylamino) propyltrimethoxysilane and 3-ureidopropyltriethoxysilane. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants and the like.

The photosensitive resin composition of the present invention contains (i) an alkali-soluble resin represented by the general formula (1) in the solid content (the solid content includes a monomer that becomes a solid content after curing) from which the solvent has been removed. , (Ii) photopolymerizable monomer, (iii) photopolymerization initiator, and (iv) epoxy compound are preferably contained in a total amount of 70% by mass or more, preferably 80% by mass, more preferably 90% by mass or more. .. The amount of the solvent varies depending on the target viscosity, but is preferably 10 to 80% by mass with respect to the total amount.

Further, the coating film (cured product) of the present invention is, for example, applied to a substrate or the like with a solution of a photosensitive resin composition, dried by a solvent, and irradiated with light (including ultraviolet rays, radiation, etc.) to be cured. Obtained at. A coating film having a desired pattern can be obtained by providing a portion exposed to light and a portion not exposed to light using a photomask or the like, curing only the portion exposed to light, and dissolving the other portion with an alkaline solution. ..

To give a specific example of each step of the film forming method by applying and drying the photosensitive resin composition, when the photosensitive resin composition is applied to a substrate, a known solution dipping method, a spray method, and a roller coater machine are used. , A method using a land coater machine, a slit coat machine, a spinner machine, or the like can be adopted. By these methods, a film is formed by applying to a desired thickness and then removing the solvent (pre-baking). Pre-baking is performed by heating in an oven, hot plate, etc., vacuum drying, or a combination thereof. The heating temperature and heating time in the prebake can be appropriately selected depending on the solvent used, but are preferably carried out at 80 to 120 ° C. for 1 to 10 minutes, for example.

As the radiation used for exposure, for example, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like can be used, and the wavelength range of the radiation is preferably 250 to 450 nm. Further, as a developing solution suitable for this alkaline development, for example, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide or the like can be used. These developers can be appropriately selected according to the characteristics of the resin layer, but it is also effective to add a surfactant if necessary. The development temperature is preferably 20 to 35 ° C., and a fine image can be precisely formed by using a commercially available developing machine, an ultrasonic cleaner, or the like. After alkaline development, it is usually washed with water. As the developing method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid filling) developing method and the like can be applied.

After developing in this way, heat treatment (post-baking) is performed at 120 to 250 ° C. for 20 to 100 minutes. This post-baking is performed for the purpose of enhancing the adhesion between the patterned coating film and the substrate. This is done by heating in an oven, hot plate, etc., similar to pre-baking. The patterned coating film of the present invention is formed through each step by a photolithography method. Then, polymerization or curing (sometimes referred to as curing together) is completed by heat to obtain a cured film such as an insulating film having a desired pattern. The curing temperature at this time is preferably 140 to 250 ° C.

Since the photosensitive resin composition of the present invention has a larger number of polymerizable unsaturated groups in one molecule than the conventional one, the photocurability is improved, and the crosslink density after curing without increasing the amount of the photopolymerization initiator. Can be enhanced. That is, when the thick film is irradiated with ultraviolet rays or electron beams, the cured portion is cured to the bottom, and the difference in solubility in the alkaline developer between the exposed portion and the unexposed portion becomes large. The pattern adhesion is improved and the pattern can be formed with high resolution. Further, even in the case of a thin film, the increased sensitivity makes it possible to significantly improve the amount of residual film in the exposed portion and suppress peeling during development.

The photosensitive composition of the present invention includes a solder resist, a plating resist, and an etching resist for producing a circuit board, an insulating film for multi-layering a wiring board on which a semiconductor element is mounted, a semiconductor gate insulating film, and a photosensitive adhesive (). In particular, it is extremely useful for adhesives that require heat-adhesive performance even after pattern formation by photolithography).

Hereinafter, the present invention will be described in more detail based on examples of the alkali-soluble resin represented by the general formula (1). The scope of the present invention is not limited by these examples and the like. Moreover, the evaluation of the resin in these Examples was carried out as follows unless otherwise specified.

[Solid content concentration]
The solid content concentration was measured by impregnating a glass filter [mass: W0 (g)] with the resin solution, photosensitive resin composition, etc. (1 g) obtained in Example 1 (and Comparative Example 1) and weighing [W1]. (G)], calculated from the following formula using the value of mass [W2 (g)] after heating at 160 ° C. for 2 hours.
Solid content concentration (mass%) = 100 × (W2-W0) / (W1-W0)

[Acid value]
The acid value was determined by dissolving the resin solution in dioxane and titrating with a 1/10 N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.), and the required KOH per 1 g of solid content. Was used as the acid value.

[Molecular weight]
The molecular weight is gel permeation chromatography (GPC) ("HLC-8220 GPC" manufactured by Tosoh Corporation, column: TSKgelSuperH2000 (2) + TSKgelSuperH3000 (1) + TSKgelSuperH4000 (1) + TSKgelSuperH5000 (1), both of which are stocks (1). (Manufactured by the company), solvent: tetrahydrofuran, temperature: 40 ° C., rate: 0.6 ml / min), and the value obtained as a standard polystyrene (“PS-oligoene kit” manufactured by Tosoh Corporation) conversion value is the weight average molecular weight. It was set to (Mw).

The abbreviations used in Example 1 and Comparative Example 1 are as follows.
NAMMEA: A compound in which a reaction product of 1-naphthol and p-xylylene glycol dimethyl ether (naphthol aralkyl resin) is reacted with methanol to methoxylate a part of the hydroxyl groups (the ratio of methoxy groups to the total amount of hydroxyl groups and methoxy groups is 28). %) Is reacted with chloromethyloxylane to obtain an epoxy compound (epoxide equivalent: 406, in the general formula (4), X is the general formula (5), W is the methyl group (R) and the glycidyl group (G). the C R _/ C value of _G is 0.39), the compound was further obtained by reacting acrylic acid (equal equivalent reaction product of the epoxy group and a carboxyl group)
THPA: 1,2,3,6-tetrahydrophthalic anhydride TEAB: Tetraethylammonium bromide PEGMEA: Propylene glycol monomethyl ether acetate

The following Example 1 is a synthesis example of an alkali-soluble resin represented by the general formula (1) and having a carboxyl group and a polymerizable unsaturated group in one molecule. Further, Comparative Example 1 is an alkali-soluble resin having a structure different from that of the alkali-soluble resin of the general formula (1).

[Example 1]
(Synthesis of alkali-soluble resin)
A 50% PEGMEA solution of NAMMEA (337.2 g), THPA (49.1 g), TEAB (0.90 g), and PEGMEA (5.4 g) were placed in a 1000 ml four-necked flask equipped with a return condenser. , 120-125 ° C. for 6 hours to obtain an alkali-soluble resin (i) -1. The solid content concentration of the obtained resin was 56.0% by mass, the acid value (in terms of solid content) was 88.0 mgKOH / g, and the molecular weight (Mw) was 1000.

[Comparative Example 1]
(Synthesis of alkali-soluble resin)
A 50% PGMEA solution (291.0 g) of an equivalent reaction product of bisphenol A type epoxy compound (epoxy equivalent = 182) and acrylic acid (epoxy group and carboxyl group equivalent) in a 1000 ml four-necked flask with a return cooler. , Dimethylolpropionic acid (4.0 g), 1,6-hexanediol (11.8 g), and PGMEA (84 g) were charged, and the temperature was raised to 45 ° C. Next, isophorone diisocyanate (61.8 g) was added dropwise while paying attention to the temperature inside the flask. After completion of the dropping, the mixture was stirred at 75 to 80 ° C. for 6 hours. Further, THPA (21.0 g) was charged and stirred at 90 to 95 ° C. for 6 hours to obtain an alkali-soluble resin solution (i) -2. The solid content concentration of the obtained resin was 66.5% by mass, the acid value (in terms of solid content) was 38.4 mgKOH / g, and the molecular weight (Mw) was 12220.

Next, the present invention will be specifically described with respect to the production and evaluation of the photosensitive resin composition and the cured product thereof based on Example 2 and Comparative Example 2, but the present invention is not limited thereto. .. Here, the raw materials and abbreviations used in the following Example 2 and Comparative Example 2 are as follows.

(i) -1: Alkali-soluble resin obtained in Example 1
(i) -2: Alkali-soluble resin obtained in Comparative Example 1.
(ii): Dipentaerythritol hexaacrylate
(iii) -1: Irgacure 184 (BASF, "Irgacure" is a registered trademark of BASF)
(iii) -2: 4,4'-bis (dimethylamino) benzophenone (Michler ketone)
(iv): Cresol novolac type epoxy resin Solvent: Propylene glycol monomethyl ether acetate

The photosensitive resin compositions of Example 2 and Comparative Example 2 were prepared by blending each component in the ratio shown in Table 1. All the numerical values in Table 1 represent mass%.

[Evaluation of Photosensitive Resin Compositions of Example 2 and Comparative Example 2]
The photosensitive resin composition shown in Table 1 is applied to a glass substrate of 125 mm × 125 mm using a spin coater so that the film thickness after post-baking is 30 μm, and prebaked at 110 ° C. for 5 minutes to coat the coating plate. Was produced. Then, ultraviolet rays having a wavelength of 365 nm were irradiated with a high-pressure mercury lamp of ^{500 W / cm 2} through a photomask for pattern formation, and a photocuring reaction of the exposed portion was carried out. Next, this exposed coating film was developed with a 0.8 mass% tetramethylammonium hydroxide (TMAH) aqueous solution and shower development at 23 ° C. for another 30 seconds from the time when the pattern began to appear, and then spray-washed. , The unexposed part of the coating film was removed. Then, it was heat-cured at 230 ° C. for 30 minutes using a hot air dryer to obtain a cured film according to Example 2 and Comparative Example 2.

The following evaluation was performed on the cured film obtained under the above conditions. When preparing the cured film for the film thickness test, the alkali resistance test, and the acid resistance test, after full exposure without passing through a photomask, development, washing with water, and heat curing treatment were performed.

[Film thickness]
The film thickness was measured by scraping a part of the applied film and using a stylus type step shape measuring device "P-10" (manufactured by KLA Tencor Co., Ltd.).

[Alkali resistance test]
In the alkali resistance test, a glass substrate with a cured film is immersed in a solution of a mixture of 30 parts by mass of 2-aminoethanol and 70 parts by mass of glycol ether held at 80 ° C., pulled up after 10 minutes, washed with pure water, and dried. Then, a sample immersed in chemicals was prepared and the adhesion was evaluated. At least 100 cross-cuts were made on the film of the sample immersed in the chemical so as to form a grid pattern, and then a peeling test was performed using cellophane tape to visually evaluate the state of the grid pattern.
⊚: No peeling is observed ○: Slight peeling can be confirmed on the coating film △: Peeling can be confirmed on some coating films ×: Most of the film is peeled off

[Acid resistance test]
In the acid resistance test, a glass substrate with a cured film is immersed in a solution of aqua regia (hydrochloric acid: nitric acid = 7: 3) maintained at 50 ° C., pulled up after 10 minutes, washed with pure water, dried, and immersed in chemicals. The sample was prepared and the adhesion was evaluated. At least 100 cross-cuts were made on the film of the sample immersed in the chemical so as to form a grid pattern, and then a peeling test was performed using cellophane tape to visually evaluate the state of the grid pattern.
⊚: No peeling is observed ○: Slight peeling can be confirmed on the coating film △: Peeling can be confirmed on some coating films ×: Most of the film is peeled off

[Heat resistance test]
In the heat resistance test, the photosensitive resin composition shown in Table 1 was applied to a glass substrate to which a 125 mm × 125 mm release film was attached using a spin coater so that the film thickness after post-baking was 30 μm. A coated plate was prepared by prebaking at 110 ° C. for 5 minutes. Then, ultraviolet rays having a wavelength of 365 nm were irradiated with a high-pressure mercury lamp of ^{500 W / cm 2} through a photomask for pattern formation, and a photocuring reaction of the exposed portion was carried out. Next, this exposed coating film was developed with a 0.8 mass% tetramethylammonium hydroxide (TMAH) aqueous solution and shower development at 23 ° C. for another 30 seconds from the time when the pattern began to appear, and then spray-washed. , The unexposed part of the coating film was removed. Then, it was heat-cured at 230 ° C. for 30 minutes using a hot air dryer, and the obtained pattern was peeled off from the release film to obtain a cured film according to Example 2 and Comparative Example 2.

The heat resistance of the insulating film obtained under the above conditions was evaluated by measuring the coefficient of linear expansion (α1) using a thermomechanical analyzer (TMA).

As shown in Table 2, the photosensitive resin composition containing the alkali-soluble resin and the cured product thereof prepared in Example 2 show good results in the alkali resistance test, the acid resistance test and the heat resistance test. I understood. Therefore, it is considered that the photosensitive resin composition containing the alkali-soluble resin of the present invention and the cured product thereof can form a fine cured film pattern by photolithography.

From the above, the photosensitive resin composition of the present invention and its cured product are a solder resist, a plating resist, an etching resist for producing a circuit board, an insulating film for multi-layering a wiring board on which a semiconductor element is mounted, and a semiconductor. It can be applied to gate insulating films, photosensitive adhesives, etc.

This application claims priority under Japanese Patent Application No. 2018-060780 filed on March 27, 2018. All the contents described in the application specification are incorporated in the application specification.

Claims (6)

An alkali-soluble resin represented by the following general formula (1) and having a carboxyl group and a polymerizable unsaturated group in one molecule.

(X represents a divalent hydrocarbon group having 1 to 20 carbon atoms. The divalent hydrocarbon group may have a linear or branched structure, or may have an aromatic ring in the main chain or the branched chain. Good. Y is a hydrocarbon group R having 1 to 5 carbon atoms or a substituent Z having a polymerizable unsaturated group and a carboxyl group in the molecule represented by the general formula (2), and the number of moles CR of _R , when the Z moles _{C Z of,} C value of R / _{C Z} is the value of n as an 0.05 to 2.0. the average value is 1-20. in addition, the naphthalene ring of the hydrogen atom some may be substituted by R _1, R ₁ is a hydrocarbon group, a halogen atom or a phenyl group having 1 to 5 carbon atoms.)

(R ₃ represents a hydrogen atom or a methyl group. L represents a substituent represented by the general formula (3).)

(M indicates a divalent or trivalent carboxylic acid residue, p is 1 or 2.) (I) An alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule according to claim 1.
(Ii) With a photopolymerizable monomer having at least one polymerizable unsaturated group,
(Iii) Photopolymerization initiator and
A photosensitive resin composition comprising the above as an essential component. A photosensitive resin composition according to claim 2, further comprising (iv) an epoxy compound as an essential component in the photosensitive resin composition. The photosensitivity according to claim 2 or 3, wherein the component (iii) is contained in an amount of 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the component (i) and the component (ii). Resin composition. Claimed to contain 0.1 to 10 parts by mass of the component (iii) and 10 to 40 parts by mass of the component (iv) with respect to a total of 100 parts by mass of the component (i) and the component (ii). Item 3. The photosensitive resin composition according to Item 3. A cured product obtained by curing the photosensitive resin composition according to any one of claims 2 to 5.