TWI793289B - Process for producing alkali-soluble resin containing polymerizable unsaturated group, alkali-soluble resin containing polymerizable unsaturated group, photosensitive resin composition containing it as an essential component, and cured film thereof - Google Patents

Abstract

A method for producing an alkali-soluble resin containing a polymerizable unsaturated group, comprising (a) dicarboxylic acid or tricarboxylic acid or its monoanhydride, and (b) tetracarboxylic acid or its acid dianhydride with the following: The epoxy compound of the structure shown in general formula (1) reacts with the reaction product of acrylic acid or methacrylic acid:

(In the general formula (1), R1~R8 represent a hydrocarbon group with 4~12 carbon atoms, two or more of R1~R8 can be the same, n represents a number with an average value of 0~3, and G represents a glycidyl group).

Description

Production method of alkali-soluble resin containing polymerizable unsaturated group method, an alkali-soluble resin containing a polymerizable unsaturated group, a photosensitive resin composition containing it as an essential component, and a cured film thereof

The present invention relates to a method for producing an alkali-soluble resin containing a polymerizable unsaturated group, an alkali-soluble resin containing a polymerizable unsaturated group, a photosensitive resin composition containing it as an essential component, and a cured product obtained by curing it membrane. The photosensitive resin composition containing the specific polymerizable unsaturated group-containing alkali-soluble resin of the present invention and its cured product can be suitably used as resist layers such as solder resists, plating resists, and resist layers, and multilayer printed wiring. Interlayer insulating layers such as boards, films for gas barriers, sealing materials for semiconductor light-emitting elements such as lenses and Light Emitting Diodes (Light Emitting Diodes, LEDs), topcoats for paints or inks, hard plastics Coatings, antirust films for metals, etc.

Along with recent improvements in performance and definition of electronic devices and display members, electronic components used therein have been required to be miniaturized and denser. Furthermore, miniaturization and rationalization of the cross-sectional shape of the processed pattern are also required for the processability of the insulating material used in these. As an effective means of microfabrication of insulating materials, a patterning method by exposure and development is known. In this method, a photosensitive resin composition is used, and high sensitivity, adhesion to the substrate, reliability, and heat resistance are required. , chemical resistance Sex and many other characteristics. In addition, various studies have been conducted on using organic insulating materials in gate insulating films for organic thin film transistors (TFTs), and it is necessary to reduce the operating voltage of organic TFTs by reducing the thickness of the gate insulating films. , in the case of an organic insulating material whose dielectric withstand voltage is generally about 1MV/cm, the application of a thin film of about 0.2μm has been studied.

The previous insulating material comprising a photosensitive resin composition utilizes a photohardening reaction caused by the reaction of a photoreactive alkali-soluble resin and a photopolymerization initiator, and mainly uses one of the line spectra of a mercury lamp, that is, i-ray (365nm ) as the exposure wavelength for photohardening. However, this i-ray is absorbed by the photosensitive resin itself or a colorant, and the degree of photocuring decreases. Moreover, if it is a thick film, the absorption amount will increase. Therefore, there will be a difference in crosslink density with respect to the film thickness direction at the exposed part. Even if the photocuring is sufficiently carried out on the surface of the coating film, it is difficult to photocure on the bottom surface of the coating film, so it is obviously difficult to make the exposed part There is a difference in crosslink density between the unexposed part and the dimensional stability of the pattern, the development margin (margin), the adhesion of the pattern, the shape of the edge (edge) of the pattern, and the cross-sectional shape. It is difficult to obtain a high-resolution image. Photosensitive insulating material.

Generally speaking, in the photosensitive resin composition of this kind of application, those containing polyfunctional photocurable monomers having polymerizable unsaturated bonds, alkali-soluble binder resins, photopolymerization initiators, etc. are used. A photosensitive resin composition technically disclosed as an application in the form of a color filter material. For example, Patent Document 1 and Patent Document 2 disclose copolymers of (meth)acrylic acid or (meth)acrylate, maleic anhydride, and other polymerizable monomers having a carboxyl group as binder resins. and Furthermore, Patent Document 3 discloses that an alkali-soluble unsaturated compound having a polymerizable unsaturated double bond and a carboxyl group in one molecule is effective for forming negative patterns such as color filters.

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 epoxy (meth)acrylate having a bisphenolfluorene structure and an acid anhydride.

[Prior art literature]

[Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 61-213213

[Patent Document 2] Japanese Patent Laid-Open No. 1-152449

[Patent Document 3] Japanese Patent Laid-Open No. 4-340965

[Patent Document 4] Japanese Patent Laid-Open No. 4-345673

[Patent Document 5] Japanese Patent Laid-Open No. 4-345608

[Patent Document 6] Japanese Patent Laid-Open No. 4-355450

[Patent Document 7] Japanese Patent Laid-Open No. 4-363311

However, the copolymer disclosed in Patent Document 1 or Patent Document 2 is a random copolymer, so the distribution of the alkali dissolution rate occurs in the light-irradiated part and the light-unirradiated part, and the margin at the time of the developing operation is narrow. It is difficult to obtain an acute-angled pattern shape or a fine pattern. In particular, when the pigment is contained at a high concentration, the exposure sensitivity is remarkably lowered, and a fine negative pattern cannot be obtained.

Furthermore, since the alkali-soluble unsaturated compound described in Patent Document 3 is insolubilized by light irradiation, it is expected to be more sensitive than the combination of the binder resin and a polyfunctional polymerizable monomer. The compound is obtained by arbitrarily adding acrylic acid and acid anhydride as a polymerizable unsaturated bond group to the hydroxyl group of a phenol oligomer. A wide distribution appears in the amount of carboxyl groups, and the distribution of the alkali dissolution rate of the alkali-soluble resin becomes wide, making it difficult to form a fine negative pattern.

Furthermore, the resins shown in Patent Document 4, Patent Document 5, Patent Document 6, and Patent Document 7 are reaction products of epoxy (meth)acrylates and acid monoanhydrides, and therefore have small molecular weights. Therefore, it is difficult to increase the alkali solubility difference between the exposed part and the unexposed part, and it is impossible to form a fine pattern.

In this way, photolithography using various photosensitive resin compositions is used as a microfabrication method for insulating materials. In order to achieve miniaturization of the pattern and rationalization of the shape, the formed insulating film requires adhesion to the substrate, Reliability, heat resistance, chemical resistance and many other characteristics. For example, folding resistance is also required when used in flexible displays or touch panels, so it is necessary to provide a material that is also excellent in chemical resistance required for the electrode processing process after the insulating film is formed.

The present invention provides a photosensitive resin composition capable of patterning with excellent resolution by alkali development and applicable to insulating films and the like that are as reliable as folding resistance. It is also an object to provide a method for producing a specific polymerizable unsaturated group-containing alkali-soluble resin used in the photosensitive resin composition, and a polymerizable unsaturated group-containing alkali-soluble resin produced by the method. and Moreover, it also aims at providing the cured film which hardened this photosensitive resin composition.

The present inventors found that in order to solve the above-mentioned problems, it is effective to use a photosensitive resin composition using a specific alicyclic structure-containing polymerizable unsaturated group-containing alkali-soluble resin, and completed the present invention.

One embodiment of the present invention to solve the above-mentioned problems relates to a method for producing an alkali-soluble resin containing a polymerizable unsaturated group, which comprises (a) dicarboxylic acid or tricarboxylic acid or its monoanhydride, And (b) tetracarboxylic acid or its acid dianhydride reacts with the epoxy compound which has the structure represented by following general formula (1), and the reaction product of acrylic acid or methacrylic acid.

In the general formula (1), R1~R8 represent hydrocarbon groups with 4~12 carbon atoms, two or more of R1~R8 may be the same, n represents a number with an average value of 0~3, and G represents glycidyl.

Moreover, another embodiment of the present invention relates to an alkali-soluble resin containing a polymerizable unsaturated group, which is an alkali-soluble resin containing a polymerizable unsaturated group obtained by the production method, and has a general formula (2 ) structure shown.

In the general formula (2), R5~R8 represents a hydrocarbon group with 4~12 carbons, more than two of R5~R8 can be the same, R9 represents a hydrogen atom or a methyl group, X represents a 4-valent carboxylic acid residue, and Y represents the following The substituents or hydrogen atoms represented by the general formula (3) above, but more than one is the general formula (3), and m is a number with an average value of 1 to 20.

In the general formula (3), M represents a divalent or trivalent carboxylic acid residue, and p is 1 or 2.

And another embodiment of the present invention relates to a photosensitive resin A composition characterized by containing the following components as essential components: (i) the alkali-soluble resin containing a polymerizable unsaturated group; (ii) a photopolymerizable monomer having at least two polymerizable unsaturated groups; ( iii) a photopolymerization initiator; and (iv) a solvent.

Moreover, another aspect of this invention is related with the cured film obtained by hardening the said photosensitive resin composition.

The photosensitive resin composition using the polymerizable unsaturated group-containing alkali-soluble resin having a specific alicyclic structure of the present invention can be patterned by alkali development, and the cured product has a low modulus of elasticity and is excellent in folding properties. Used as an insulating film for flexible displays or touch panels. Furthermore, in the touch panel manufacturing process etc., when it is necessary to pass through the process process, such as electrode formation, after forming an insulating film, the hardened|cured material pattern which has excellent chemical resistance can be obtained.

Hereinafter, the present invention will be described in detail.

One embodiment of the present invention is related to a kind of (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) tetracarboxylic acid or its acid dianhydride with the following general formula (1) Production method of alkali-soluble resin containing polymerizable unsaturated group reacting epoxy compound with structure and reaction product of acrylic acid or methacrylic acid method, and the alkali-soluble resin containing polymerizable unsaturated groups produced by this method.

In the general formula (1), R1~R8 represent a hydrocarbon group with 4~12 carbon atoms, two or more of R1~R8 may be the same, n represents a number with an average value of 0~3, and G represents a glycidyl group.

The epoxy compound having a structure represented by general formula (1) can be prepared by reacting (epoxidation) a dimer diol compound represented by general formula (4) with epihalohydrin. synthesis.

In the general formula (4), R1~R4 represent a hydrocarbon group having 4~12 carbon atoms, and two or more of R1~R8 may be the same.

The dimer alcohol compound can be synthesized by reducing the carboxyl group of a polymerized fatty acid (dimer acid) to a hydroxyl group. In addition, the polymerized fatty acid is a compound obtained by the intermolecular reaction of two or more unsaturated fatty acids (linolenic acid, oleic acid), and the main component is a diprotic acid with 36 carbon atoms. The dimer acid skeleton contains several unsaturated double bonds in the six-membered ring and the hydrocarbon groups corresponding to R1~R4, but when the carboxyl group is reduced, most of them are hydrogenated and the unsaturated double bonds become saturated carbon-carbon single bonds. At this time, even if a small amount of unsaturated double bonds remain, that is, in the case of epoxidation using a dimer alcohol compound containing unsaturated double bonds, the main skeleton is also an epoxy compound of the general formula (1), so it can be used It is used as a raw material of the unsaturated group-containing alkali-soluble resin of the invention of this application.

Examples of commercially available products containing the dimer alcohol compound include Pripol 2030 and 2033 manufactured by Croda Corporation.

The dimer alcohol compound and epihalohydrin can be reacted by a method known as epoxidation. For example, after dissolving the dimer alcohol compound in excess epihalohydrin, it is reacted at 40° C. to 120° C. for 1 hour to 10 minutes in the presence of alkali metal oxides such as sodium hydroxide and potassium hydroxide. hours, whereby the epoxidation can be carried out. Moreover, it is preferable to perform the said reaction at 50-70 degreeC from a viewpoint of reducing a hydrolyzable halogen.

Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and lithium hydroxide, mixtures thereof, and the like. These alkali metal hydroxides are preferably Use in aqueous solution or solid state.

The usage amount of the alkali metal hydroxide is preferably from 0.8 mol to 15.0 mol, more preferably from 0.9 mol to 2.0 mol, relative to 1 mol of hydroxyl groups in the dimer alcohol compound. By setting the usage-amount of the said alkali metal hydroxide to 0.8 mol or more with respect to 1 mol of hydroxyl groups in a dimer alcohol compound, the amount of a residual hydrolyzable halogen can be reduced. Furthermore, by setting the usage amount of the alkali metal hydroxide to 15.0 mol or less with respect to 1 mol of the hydroxyl group in the dimer alcohol compound, the yield of gel at the time of epoxy compound synthesis can be reduced, and It is not easy to form latex when washing with water, which can improve the yield.

In this case, from the viewpoint of promoting the reaction, an interphase transfer catalyst may also be used in combination. Examples of the interphase transfer catalyst include quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, and methyltrioctylammonium chloride. These ammonium salts may be used alone or in combination of two or more. The amount of the phase transfer catalyst used is preferably 20 parts by weight or less, more preferably 0.5 parts by weight or more and 10 parts by weight or less, and still more preferably 1.0 parts by weight or more and 5.0 parts by weight relative to 100 parts by weight of the dimer alcohol compound. the following.

Examples of the epihalohydrin include epichlorohydrin, epiiodohydrin, epibromohydrin, and the like. Among these, epichlorohydrin is preferred.

The amount of the epihalohydrin used is preferably 1.5 mol to 30 mol, more preferably 2 mol to 15 mol, relative to 1 mol of the total amount of hydroxyl groups in the dimer alcohol compound. , and more preferably not less than 2.5 moles and not more than 10 moles. By setting the usage amount of the epihalohydrin relative to the hydroxyl group in the dimer alcohol compound 1 When the mole is 1.5 mole or more, the molecular weight of the epoxy compound can be adjusted so that the viscosity does not become too high. Productivity can be further improved by setting the usage-amount of the said epihalohydrin to 30 mol or less with respect to 1 mol of hydroxyl groups in a dimer alcohol compound.

The reaction (epoxidation) between the dimer alcohol compound and epihalohydrin is preferably performed in a solvent that does not react with epoxy groups. Examples of the solvent include aromatic hydrocarbons including toluene, xylene, and benzene, ketones including methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, and acetone, and propanol and butanol Alcohols such as diethylene glycol methyl ether, propylene glycol methyl ether and dipropylene glycol methyl ether, glycol ethers such as diethylene glycol methyl ether, propylene glycol methyl ether, and dipropylene glycol methyl ether, and fatty acids such as diethyl ether, dibutyl ether, and ethyl propyl ether Ethers, including alicyclic ethers such as dioxane and tetrahydrofuran, and dimethylsulfoxide. These solvents may be used alone or in combination of two or more.

The usage-amount of the said solvent is preferably 200 mass parts or less with respect to 100 mass parts of epihalohydrin, More preferably, it is 5 mass parts or more and 150 mass parts or less, More preferably, it is 10 mass parts or more and 100 mass parts or less.

After completion of the reaction, excess epihalohydrin was distilled off, inorganic salts were removed by dissolving in a solvent, filtration, and water washing, and the solvent was distilled off to obtain the epoxy compound.

In addition, at this time, when the amount of hydrolyzable halogen is too large, purification for reducing the amount of hydrolyzable halogen may be performed. The purification can be performed at a temperature of 60° C. to 90° C. by adding an alkali metal hydroxide in an amount of 1 to 30 times the amount of the remaining hydrolyzable halogen to the obtained epoxy compound. After 10 minutes to 2 hours of refining reaction, neutralize, wash with water, etc. to remove excess alkali metal hydroxide or by-products Salt was produced, and then the solvent was distilled off under reduced pressure.

The epoxy compound and (meth)acrylic acid are reacted to obtain an epoxy (meth)acrylate compound having a polymerizable unsaturated group.

The epoxy compound and (meth)acrylic acid can be reacted by a known method. For example, 2 moles of (meth)acrylic acid are used with respect to 1 mole of the epoxy compound group, but in order to make the (meth)acrylic acid react with all the epoxy groups, the ratio of the epoxy group to the carboxyl group is Equimolar, a slight excess of (meth)acrylic acid can be used. By this reaction, the epoxy (meth)acrylate compound which the part of G in general formula (1) substituted with the group represented by general formula (5) is obtained.

In the general formula (5), R9 represents a hydrogen atom or a methyl group.

The solvent and catalyst or other reaction conditions used at this time are not particularly limited. For example, as a solvent, it is preferable to use a solvent that does not have a hydroxyl group but has a boiling point higher than the reaction temperature. Examples of such solvents include cellosolve-based solvents containing ethyl cellosolve acetate, butyl cellosolve acetate, and the like; (Diglyme), ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate and other high-boiling ether or ester solvents; and cyclohexanone and diisobutyl Ketone-based solvents such as ketones, etc. Examples of the catalyst include ammonium salts including tetraethylammonium bromide and triethylbenzylammonium chloride; and triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine Known catalysts such as phosphines and the like.

Furthermore, (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride, and (b) tetracarboxylic acid or its acid dianhydride are reacted with the epoxy (meth)acrylate compound to obtain a Alkali soluble resin with unsaturated groups.

Examples of (a) dicarboxylic acid or tricarboxylic acid or its anhydride include saturated chain hydrocarbon dicarboxylic acid or tricarboxylic acid or their anhydride, saturated cyclic hydrocarbon dicarboxylic acid or tricarboxylic acid Acids or their anhydrides, unsaturated hydrocarbon dicarboxylic acids or tricarboxylic acids or their anhydrides, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids or their anhydrides, etc. In addition, each hydrocarbon residue (structure except the carboxyl group) of these dicarboxylic acids or tricarboxylic acids or their monoanhydrides may be further substituted with substituents such as alkyl groups, cycloalkyl groups, and aromatic groups.

Examples of saturated chain hydrocarbon dicarboxylic or tricarboxylic acids include succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, Tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, etc. Examples of saturated cyclic hydrocarbon dicarboxylic or tricarboxylic acids include hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, and hexahydrotrimellitic acid. Acid etc. Examples of unsaturated dicarboxylic or tricarboxylic acids include maleic acid, itaconic acid, tetrahydrophthalic acid, methyl Endomethylene tetrahydrophthalic acid, chlorendic acid, etc. Examples of the aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include phthalic acid, trimellitic acid, and the like. Monoanhydrides of these dicarboxylic or tricarboxylic acid compounds can also be used. Among these, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid or their monoanhydrides are preferred, and butyric acid is more preferred. diacid, itaconic acid, tetrahydrophthalic acid or their anhydrides.

Examples of the (b) tetracarboxylic acid or its acid dianhydride include chain hydrocarbon tetracarboxylic acid or its acid dianhydride, alicyclic tetracarboxylic acid or its acid dianhydride, and aromatic polycarboxylic acid or its acid Dianhydride, etc. In addition, each hydrocarbon residue (structure except the carboxyl group) of these tetracarboxylic acids or their acid dianhydrides may be further substituted with substituents such as an alkyl group, a cycloalkyl group, and an aromatic group.

As a specific tetracarboxylic acid, butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, etc. are mentioned in the example of a chain hydrocarbon tetracarboxylic acid. Examples of the alicyclic tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and the like. Examples of the aromatic polycarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and the like. The acid dianhydrides of these tetracarboxylic acid compounds can also be used.

The molar ratio (a)/(b) of (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride and (b) tetracarboxylic acid or its acid dianhydride used in the reaction is 0.01～0.5, Preferably, it is more than 0.02 and less than 0.1. When molar ratio (a)/(b) deviates from the said range, since the optimum molecular weight for making the photosensitive resin composition which has favorable photopatternability cannot be obtained, it is unpreferable. In addition, there is a molar ratio (a)/(b) The smaller the alkali solubility, the greater the tendency of the molecular weight.

The reaction ratio of the polymerizable unsaturated group-containing epoxy (meth)acrylate compound (c) and the carboxylic acid components (a) and (b) is preferably expressed in moles of each component. The ratio is (c): (a): (b) = 1: 0.2 to 1.0: 0.01 to 1.0 so that the compound is reacted quantitatively so that the terminal of the compound becomes a carboxyl group. At this time, it is desirable to quantify the total amount of the acid component to the molar ratio (c)/[(a)/2+(b)]=0.5 to 1.0 of the epoxy (meth)acrylate compound. react. If this molar ratio is less than 0.5, the terminal of the alkali-soluble resin becomes an acid anhydride, and the content of unreacted acid dianhydride increases, and there is a concern that the temporal stability of the alkali-soluble resin composition may decrease. On the other hand, when the molar ratio exceeds 1.0, the content of the hydroxyl group-containing compound containing an unreacted polymerizable unsaturated group increases, and there is a concern that the temporal stability of the alkali-soluble resin composition may decrease. For the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin, the molar ratio of each component (a), (b) and (c) can be changed arbitrarily within the above range.

The reaction of (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride with (b) tetracarboxylic acid or its acid dianhydride can be, for example, in triethylamine, tetraethylammonium bromide and triphenylphosphine, etc. In the presence of a catalyst, it reacts by heating and stirring at 90-130 degreeC.

The alkali-soluble resin containing polymerizable unsaturated groups produced by the production method preferably has an acid value of 30 mgKOH/g-200 mgKOH/g, more preferably 50 mgKOH/g-150 mgKOH/g. If the acid value is less than 30 mgKOH/g, residues tend to remain during alkali development, and if it exceeds 200 mgKOH/g, the permeation of alkali developing solution may be too fast and peeling may occur.

In the production method, the produced polymeric unsaturated From the viewpoint of the viscosity of the base-based alkali-soluble resin, in the general formula (1), the content of n=0 (n=0 body) is preferably 50% or more, more preferably 70% or more.

Furthermore, it is preferable that the polymerizable unsaturated group-containing alkali-soluble resin produced by the above production method has a hydrolyzable halogen content of 0.2% by mass or less. If the hydrolyzable halogen content is 0.2% by mass or less, it is difficult for the hydrolyzable halogen to hinder the hardening reaction, and the physical properties of the hardened product, especially the insulation reliability, are not easy to decrease, so it is not easy for electrical. It is preferable for use in the electronic field. The hydrolyzable halogen content is preferably at most 0.1% by mass, more preferably at most 0.05% by mass.

In the production method, for example, when n=0 in the general formula (1), a polymerizable unsaturated group-containing alkali-soluble resin having a structure represented by the following general formula (2) is produced.

In the general formula (2), R5~R8 represent a hydrocarbon group having 4~12 carbon atoms, and two or more of R5~R8 may be the same. R9 represents a hydrogen atom or a methyl group. X represents a tetravalent carboxylic acid residue. Y represents a substituent represented by the following general formula (3) or a hydrogen atom. Among them, there are many molecules in the polymerizable unsaturated group-containing alkali-soluble resin Of the Y's, one or more is the general formula (3). m is a number from 1 to 20 on average.

In the general formula (3), M represents a divalent or trivalent carboxylic acid residue. p is 1 or 2.

[Photosensitive resin composition]

The alkali-soluble resin containing a polymerizable unsaturated group having a structure represented by general formula (2) can be made into (i) an alkali-soluble resin containing a polymerizable unsaturated group having a structure represented by general formula (2). A resin; (ii) a photopolymerizable monomer having at least two polymerizable unsaturated groups; (iii) a photopolymerization initiator; and (iv) a photosensitive resin composition of a solvent.

Examples of (ii) photopolymerizable monomers having at least two polymerizable unsaturated groups include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene Glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, Methylolethane Tri(meth)acrylate, Pentaerythritol Di(meth)acrylate ester, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerin (meth)acrylate, sorbitol penta(meth)acrylate, di Pentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, or alkylene oxide modified hexa(meth)acrylate of phosphazene , and (meth)acrylates such as caprolactone-modified dipentaerythritol hexa(meth)acrylate, polyhydric alcohols such as pentaerythritol and dipentaerythritol, and vinyl benzyl ethers of polyphenols such as phenol novolac Compounds, addition polymers of divinyl compounds such as divinylbenzene, etc. When it is necessary to form a crosslinked structure between molecules of the alkali-soluble resin containing a polymerizable unsaturated group, it is more preferable to use a photopolymerizable monomer having three or more polymerizable unsaturated groups. These photopolymerizable monomers may be used alone or in combination of two or more. In addition, (ii) the photopolymerizable monomer having at least two polymerizable unsaturated groups does not have a free carboxyl group.

The compounding ratio of (ii) component is suitable for 5 mass parts - 400 mass parts with respect to 100 mass parts of (i) component, More preferably, it is 10 mass parts - 150 mass parts. If the blending ratio of (ii) component is more than 400 parts by mass relative to 100 parts by mass of component (i), the cured product after photocuring will become brittle, and the acid value of the coating film in the unexposed part will be low. The solubility of the alkali developing solution decreases, and problems such as blurring and inconspicuous edges of patterns occur. On the other hand, when the compounding ratio of (ii) component is less than 5 mass parts with respect to 100 mass parts of (i) components, the ratio of a photoreactive functional group in a resin will be small, and the formation of a crosslinked structure will be insufficient. Furthermore, since the acid value of the resin component is high, the solubility to the alkali developing solution in the exposed part becomes high, so that some damage occurs. The formed pattern may be thinner than the target line width, and problems such as pattern loss may easily occur.

Examples of (iii) photopolymerization initiators include: acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloro Acetophenones such as acetophenone, trichloroacetophenone, and p-tert-butylacetophenone, including benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethyl Benzophenones such as aminobenzophenone, including benzoin ethers such as Benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether, including 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl )-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, and 2,4,5-triarylbiimidazole and other biimidazole compounds class, including 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyano-styryl)-1,3,4- Halomethyldiazole compounds such as oxadiazole and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole, including 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-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methylthiostyryl )-4,6-bis(trichloromethyl)-1,3,5-triazine and other halomethyl-s-triazine compounds, including 1,2-octanedione, 1-[4-( phenylthio)phenyl]-,2-(O-benzoyloxime), 1-(4-phenylthiophenyl)butane-1,2-dione-2-oxime-O-benzene Formate, 1-(4-Methylthiophenyl)butane-1,2-dione-2-oxime-O-acetic acid Ester, 1-(4-methylthiophenyl)butane-1-one oxime-O-acetate, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl) )-9H-carbazol-3-yl]-, 1-(0-acetyl oxime), ketone, (9-ethyl-6-nitro-9H-carbazol-3-yl)[4- (2-Methoxy-1-methylethoxy)-2-methylphenyl]-,O-acetyl oxime, ketone, (2-methylphenyl)(7-nitro-9 ,9-dipropyl-9H-fluoren-2-yl)-,acetyl oxime, ethyl ketone,1-[7-(2-methylbenzoyl)-9,9-dipropyl-9H -Fluoren-2-yl]-, 1-(O-acetyl oxime), and ethyl ketone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)- , O-acyl oxime compounds such as 1-O-acetyl oxime, including benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone , 2-methylthioxanthone, and 2-isopropylthioxanthone and other sulfur compounds, including 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3- Anthraquinones such as diphenylanthraquinone, organic peroxides including azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide, including 2-mercaptobenzimidazole, 2-mercaptobenzene Thiol compounds such as oxazole and 2-mercaptobenzothiazole, etc. These photopolymerization initiators may be used alone or in combination of two or more. In addition, the photoinitiator mentioned in this invention is used in the meaning containing a sensitizer.

Furthermore, as (iii) a photopolymerization initiator, it is also possible to add a photopolymerization initiator or a sensitizer which does not function as a photopolymerization initiator or a sensitizer by itself, but can increase the photopolymerization initiator or sensitizer by using it in combination. sensitizer-like compounds. Examples of the compound include tertiary amines such as triethanolamine and triethylamine, which are effective when used in combination with benzophenone.

Based on the total of 100 parts by mass of component (i) and component (ii), the blending ratio of component (iii) is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass. Where the compounding ratio of (iii) component is less than 0.1 parts by mass In this case, the speed of photopolymerization becomes slow and the sensitivity decreases. On the other hand, if it exceeds 30 parts by mass, the sensitivity is too strong, and the pattern line width becomes thicker than that of the pattern mask, and reproduction may not be possible. There is a risk of faithfulness to the lineweight of the mask or blurred edges of the pattern.

Examples of (iv) solvents include: methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3- Alcohols such as hydroxy-2-butanone and diacetone alcohol, terpenes such as α- or β-terpineol, etc., including acetone, methyl ethyl ketone, cyclohexanone, and N-methyl - Ketones such as 2-pyrrolidone, aromatic hydrocarbons including toluene, xylene, and tetramethylbenzene, including cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, Methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, and triethylene glycol Glycol ethers such as alcohol monoethyl ether, including ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, cellosolve Acetate, Ethyl Cellosolve Acetate, Butyl Cellosolve Acetate, Carbitol Acetate, Ethyl Carbitol Acetate, Butyl Carbitol Acetate, Propylene Glycol Monomethyl Ether Acetate, esters such as propylene glycol monoethyl ether acetate, etc. These solvents may be used alone or in combination of two or more to improve properties such as coatability.

Furthermore, in the photosensitive resin composition, additives such as hardening accelerators, thermal polymerization inhibitors, antioxidants, plasticizers, fillers, leveling agents, defoamers, coupling agents, and surfactants may be formulated as needed. . As the hardening accelerator, for example, hardening accelerators, hardening catalysts, latent Known compounds known as hardeners, including tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, diazabicyclic compounds wait. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, gallicol, tert-butylcatechol, phenothiazine, hindered phenolic compounds, phosphorus-based heat stabilizers, etc. wait. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of the filler include glass fiber, silica, mica, alumina, precipitated barium sulfate, precipitated calcium carbonate, and the like. Examples of leveling agents and antifoaming agents include silicone-based, fluorine-based, and acrylic-based compounds. Examples of coupling agents include vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-urea Silane coupling agents such as propyltriethoxysilane, etc. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and the like.

The photosensitive resin composition may be used by adding (v) an epoxy resin or an epoxy compound having two or more epoxy groups to (i) to (iv). Examples of such epoxy resins or epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy resins, biphenyl type epoxy resins, bisphenol fluorene type epoxy Oxygen compounds, phenol novolak-type epoxy compounds, cresol novolak-type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, polymers containing glycidyl (meth)acrylate as units , 3,4-epoxycyclohexane Alicyclic epoxy compound represented by carboxylic acid [(3,4-epoxycyclohexyl)methyl], 1,2-epoxy-4 of 2,2-bis(hydroxymethyl)-1-butanol -(2-Oxiranyl)cyclohexane adduct (such as "EHPE3150", manufactured by Daicel Co., Ltd.), phenyl glycidyl ether, p-butylphenol glycidyl ether, tris Glycidyl isocyanurate, diglycidyl isocyanurate, epoxidized polybutadiene (such as "NISSO-PB. JP-100", manufactured by Nippon Soda Co., Ltd.), silicone skeleton epoxy compound. These components are preferably compounds having an epoxy equivalent of 100 g/eq to 300 g/eq and a number average molecular weight of 100 to 5000. (v) A component may use only 1 type of compound, and may use 2 or more types together. When there is a need to increase the crosslink density of the alkali-soluble resin, a compound having at least two or more epoxy groups is preferable.

The addition amount when using the epoxy compound of (v) is preferably 10 mass parts - 40 mass parts with respect to a total of 100 mass parts of (i) component and (ii) component. Here, one of the purposes 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 the case of this purpose, if the epoxy compound When the amount added is less than 10 parts by mass, for example, moisture resistance reliability when used as an insulating film may not be ensured. Moreover, when the compounding quantity of an epoxy compound is more than 40 mass parts, the quantity of the photosensitive group in the resin component in the photosensitive resin composition will decrease, and the sensitivity for patterning cannot fully be obtained. .

The said photosensitive resin composition contains the said (i)-(iv) component or (i)-(v) component as a main component. Among the solid components, it is desirable to contain (i) to (iii) and (v) components in a total of 70% by mass, preferably 80% by mass or more. (iv) Although the amount of the solvent changes according to the target viscosity, it is preferable to include it in the range of 60% by mass to 90% by mass in the photosensitive resin composition.

[hardened object]

The photosensitive resin composition can be formed into a cured product (coating film) by, for example, applying it to a substrate, drying it, and irradiating it with light (including ultraviolet rays, radiation, etc.) (exposure) to cure it. At this time, a light-irradiated part and a non-irradiated part are provided using a photomask, etc., and only the light-irradiated part is cured, and the other parts are dissolved with an alkali solution to obtain a cured product (coating film) with a desired pattern.

Specifically, when applying the photosensitive resin composition to the substrate, a known solution dipping method, a spray method, a roll coater, a land coater, a slit coater or a known solution may be used. Any method such as the spin coater method.

A film is formed by applying the photosensitive resin composition to a desired thickness by these methods, and then removing the solvent (prebaking). Prebaking is performed by heating with an oven, a hot plate, etc., vacuum drying, and combining them. The heating temperature and heating time of the pre-baking can be appropriately selected depending on the solvent to be used, for example, at a temperature of 80° C. to 120° C. for 1 minute to 10 minutes.

Examples of radiation used for exposure include visible rays, ultraviolet rays, extreme ultraviolet rays, electron beams, and X-rays, and are preferably radiation having a wavelength in the range of 250 nm to 450 nm.

Alkali image development can be performed using aqueous solutions, such as sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, and tetramethylammonium hydroxide, as a developing solution, for example. These developing solutions can be properly selected according to the characteristics of the resin layer, and a surfactant can also be added if necessary. show Shadowing is preferably carried out at a temperature of 20°C to 35°C. A fine image can be precisely formed by using a commercially available developing machine, an ultrasonic cleaner, or the like. In addition, washing with water is usually performed after alkali image development. Examples of the developing treatment method include a shower developing method, a spray developing method, a dip developing method, a puddle developing method, and the like.

After developing in this way, heat treatment (post-baking) is performed at a temperature of 120° C. to 250° C. and on conditions of 20 minutes to 100 minutes. Post-baking is performed for the purpose of improving the adhesiveness of the patterned coating film and a board|substrate, etc. Post-baking is performed by heating with an oven, a hot plate, etc. similarly to pre-baking.

After that, polymerization or hardening is completed by heat (sometimes both are collectively referred to as hardening), and a cured film such as an insulating film can be obtained. The curing temperature at this time is preferably in the range of 160°C to 250°C.

The cured product can also be used for resist layers such as solder resists, plating resists, and corrosion resists, interlayer insulating layers such as multilayer printed wiring boards, films for gas barriers, lenses, and light-emitting diodes (LEDs). Sealing materials for semiconductor light-emitting elements, outer coatings of paints or inks, hard coatings of plastics, antirust films of metals, etc.

[Example]

Hereinafter, although the embodiment of this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited to these.

First, synthesis examples of polymerizable unsaturated group-containing alkali-soluble resins having a structure represented by general formula (2) will be described, and evaluation of the resins in these synthesis examples will be performed as follows unless otherwise specified.

[Solid content concentration]

Impregnate 1 g of the resin solution and photosensitive resin composition obtained in Synthesis Example (and Comparative Synthesis Example) into glass fiber [mass: W0 (g)], weigh [W1 (g)], and heat at 160°C The mass [W2(g)] after 2 hrs was calculated|required by the following formula.

Solid content concentration (mass%)=100×(W2-W0)/(W1-W0)

[acid value]

The resin solution was dissolved in dioxane, and titrated with a 1/10N-KOH aqueous solution using a potentiometric titration device (COM-1600 manufactured by Hiranuma Sangyo Co., Ltd.), and the amount of KOH required per 1 g of the solid content was defined as the acid value.

[molecular weight]

By gel permeation chromatography (Gel Permeation Chromatography, GPC) (HLC-8220GPC manufactured by Tosoh Co., Ltd., solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2 pieces) + TSKgelSuperH-3000 (1 piece) + TSKgelSuperH -4000 (1 piece) + TSKgelSuper-H5000 (1 piece) (manufactured by Tosoh Co., Ltd.), temperature: 40°C, speed: 0.6ml/min), measured with standard polystyrene (manufactured by Tosoh Co., Ltd. The PS-Oligomer Kit (PS-Oligomer Kit) conversion value obtained by calculating the weight average molecular weight (Mw).

In addition, the abbreviations used in the synthesis examples and comparative synthesis examples are as follows.

DDOEA: Reaction of dimer alcohol compound (Pripol (Pripol) 2033, hydroxyl equivalent weight 270g/eq manufactured by Croda Company) with chloromethyl oxirane Product (having the skeleton of general formula (1)) and the reaction product of acrylic acid (equivalent reaction product of epoxy group and carboxyl group)

BPDA: 3,3'4,4'-Biphenyltetracarboxylic dianhydride

THPA: 1,2,3,6-tetrahydrophthalic anhydride

TEAB: Tetraethylammonium bromide

PGMEA: Propylene Glycol Monomethyl Ether Acetate

[Example 1]

In a 1000ml four-necked flask with a reflux cooler, put 351.0g of DDOEA 50% PGMEA solution, 30.2g of BPDA, 15.6g of THPA, 0.43g of TEAB and 8.5g of PGMEA, and stir for 6hr under heating at 120°C~125°C. Alkali-soluble resin (i)-1 was obtained. The solid content concentration of the obtained resin was 54.6 mass %, the acid value (solid content conversion) was 84.1 mgKOH/g, and the molecular weight (Mw) was 3400.

[Comparative example 1]

50% PGMEA solution of bisphenol A type epoxy compound (epoxy equivalent = 182) and acrylic acid equivalent reaction product (epoxy group and carboxyl equivalent reaction product) in the 1000ml four-necked flask with reflux cooler 291.0 g, 4.0 g of dimethylolpropionic acid, 11.8 g of 1,6-hexanediol, and 84 g of PGMEA were heated up to 45°C. Next, 61.8 g of isophorone diisocyanate was dripped, paying attention to the temperature in the flask. After the dropwise addition was completed, the mixture was stirred under heating at 75° C. to 80° C. for 6 hr. Furthermore, 21.0 g of THPA was charged and stirred for 6 hr under heating at 90°C to 95°C to obtain an alkali-soluble resin solution (i)-2. The solid content concentration of the obtained resin was 66.5 mass %, the acid value (solid content conversion) was 38.4 mgKOH/g, and the molecular weight (Mw) was 12220.

Next, the present invention will be specifically described based on Examples and Comparative Examples of photosensitive resin compositions and cured products, but the present invention is not limited thereto. Here, the raw materials and abbreviations used in the following examples and comparative examples are as follows.

(i)-1: the alkali-soluble resin obtained in the embodiment 1

(i)-2: Alkali-soluble resin obtained in Comparative Example 1

(i)-3: 68.9% PGMEA solution of cresol novolak type acid-modified epoxy acrylate resin (CCR-1172, manufactured by Nippon Kayaku Co., Ltd.)

(ii): dipentaerythritol hexaacrylate

(iii)-1: Irgacure 184 (manufactured by BASF)

(iii)-2: 4,4'-bis(dimethylamino)benzophenone (Michelerone)

(iv): Propylene glycol monomethyl ether acetate

(v): Cresol novolak type epoxy resin

The blended components were blended in the ratios shown in Table 1 to prepare the photosensitive resin compositions of Example 2 and Comparative Examples 2 to 3. In addition, all the numerical values in Table 1 represent parts by mass.

[Evaluation of Photosensitive Resin Compositions of Example 2 and Comparative Example 2 to Comparative Example 3]

The photosensitive resin composition shown in Table 1 was coated on a glass substrate of 125 mm x 125 mm using a spin coater so that the film thickness after post-baking was 30 μm, and prebaked at 110° C. for 5 minutes to prepare a coated sheet. . Thereafter, ultraviolet light with a wavelength of 365 nm was 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 proceeded. Next, the coated plate after this exposure was sprayed and developed with 0.8% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at 23°C for 30 seconds from the time when the pattern began to appear, and then sprayed with water to remove The unexposed portion of the coating film. Thereafter, using a hot air dryer, heat curing was performed at 230° C. for 30 minutes to obtain the cured films of Example 2 and Comparative Examples 2 to 3.

The cured film obtained under the above conditions was evaluated as follows. In addition, when forming a cured film for a film thickness test, an alkali resistance test, and an acid resistance test, development, water washing, and heat curing are performed after exposure of the entire surface without passing through a photomask.

(film thickness)

A part of the coated film was cut and measured using a stylus type step shape measuring device (trade name P-10 manufactured by Kla-Tencor Co., Ltd.).

(alkali resistance test)

The glass substrate with the cured film was immersed in a solution maintained at 80° C. of a mixed solution of 30 parts by mass of 2-aminoethanol and 70 parts by mass of glycol ether, and lifted up after 10 minutes. Cleaning was performed with pure water, and drying was performed to prepare a chemical-impregnated sample, and the adhesiveness was evaluated. At least 100 cross-cuts were performed on the film of the chemical-impregnated sample, and then a peeling test was performed using cellophane tape, and the state of the grid was evaluated visually.

◎: The stripper is not observed at all

○: Slight peeling can be confirmed in the coating film

△: Peeling can be confirmed in a part of the coating film

×Those who peel off most of the film

(acid resistance test)

Immerse the glass substrate with a hardened film in a solution of aqua regia (hydrochloric acid: nitric acid = 7:3) maintained at 50°C, lift it up after 10 minutes, wash it with pure water, and dry it to obtain a chemical-impregnated product. samples to evaluate the adhesion. At least 100 cross-cuts were performed on the film of the sample impregnated with chemicals, and then a peeling test was performed using cellophane tape, and the state of the grid was evaluated visually.

◎: The stripper is not observed at all

○: Slight peeling can be confirmed in the coating film

△: Peeling can be confirmed in a part of the coating film

×: Most of the film peeled off

(Bending test)

The photosensitive resin composition shown in Table 1 was coated onto a 125 mm x 125 mm glass substrate with a peel-off film using a spin coater so that the film thickness after post-baking would be 30 μm, and a pre-treatment was performed at 110° C. for 5 minutes. Bake to make a coated board. Thereafter, ultraviolet light with a wavelength of 365 nm was 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 proceeded. Next, the coated plate after this exposure was sprayed and developed with 0.8% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at 23°C for 30 seconds from the time when the pattern began to appear, and then sprayed with water to remove The unexposed portion of the coating film. Thereafter, heat curing was performed at 230° C. for 30 minutes using a hot air dryer, and the obtained pattern was peeled off from the release film to obtain the films of Example 2 and Comparative Examples 2 to 3.

After folding the film obtained under the above conditions in half, it unfolded with the top of the crease facing upward. This test was repeated and evaluated by the number of times when cracks or fractures were observed.

According to the results of Example 2 and Comparative Example 2~Comparative Example 3, it can be seen that if the use includes (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride and (b) tetracarboxylic acid or its acid dianhydride with general The epoxy compound of the structure represented by formula (1) reacts with the reaction product of acrylic acid or methacrylic acid, the alkali-soluble resin containing the polymerizable unsaturated group of the alkali-soluble resin containing the polymerizable unsaturated group, then can manufacture can It is a cured film that can be patterned with excellent resolution by alkali development and has excellent reliability like folding resistance.

This application claims priority based on Japanese Patent Application No. 2018-063232 filed on March 28, 2018. All the content described in this application specification is used for this application specification.

Claims (6)

A method for producing an alkali-soluble resin containing a polymerizable unsaturated group, comprising: combining (a) dicarboxylic acid or tricarboxylic acid or its monoanhydride, and (b) tetracarboxylic acid or its acid dianhydride with the following: The epoxy compound of the structure shown in general formula (1) is reacted with the reaction product of acrylic acid or methacrylic acid:

(In general formula (1), R1 to R8 represent hydrocarbon groups with 4 to 12 carbon atoms, two or more of R1 to R8 may be the same, n represents a number with an average value of 0 to 3, and G represents a glycidyl group). An alkali-soluble resin containing polymerizable unsaturated groups, which is obtained by the production method of item 1 of the scope of the patent application, and has the structure shown in general formula (2):

(In general formula (2), R5~R8 represents a hydrocarbon group with 4 to 12 carbons, two or more of R5~R8 can be the same, R9 represents a hydrogen atom or a methyl group, X represents a tetravalent carboxylic acid residue, Y represents Substituents or hydrogen atoms represented by the following general formula (3) but one or more are general formula (3), m is a number with an average value of 1 to 20),

(In the general formula (3), M represents a divalent or trivalent carboxylic acid residue, and p is 1 or 2). A photosensitive resin composition characterized in that it contains the following components as essential components: (i) Alkali-soluble resins containing polymerizable unsaturated groups as described in item 2 of the patent application; (ii) photopolymerizable monomers having at least 2 polymerizable unsaturated groups; (iii) photopolymerization initiators; and (iv) Solvents. The photosensitive resin composition according to claim 3, further comprising (v) an epoxy resin or epoxy compound having two or more epoxy groups. The photosensitive resin composition according to Claim 4, which contains 0.1 to 30 parts by mass of the component (iii) with respect to 100 parts by mass of the component (i) and (ii) in total, and (v) 10 mass parts - 40 mass parts of components. A cured film obtained by curing the photosensitive resin composition described in any one of claims 3 to 5.