WO2019188897A1

WO2019188897A1 - Production method for polymerizable-unsaturated-group-containing alkali-soluble resin, polymerizable-unsaturated-group-containing alkali-soluble resin, photosensitive resin composition including polymerizable-unsaturated-group-containing alkali-soluble resin as essential ingredient, and cured film of photosensitive resin composition including polymerizable-unsaturated-group-containing alkali-soluble resin as essential ingredient

Info

Publication number: WO2019188897A1
Application number: PCT/JP2019/012351
Authority: WO
Inventors: 滑川　崇平; 正臣高野
Original assignee: 日鉄ケミカル＆マテリアル株式会社
Priority date: 2018-03-28
Filing date: 2019-03-25
Publication date: 2019-10-03
Also published as: TW201942185A; TWI793289B; JPWO2019188897A1; JP7260524B2

Abstract

A production method for a polymerizable-unsaturated-group-containing alkali-soluble resin, the production method involving reacting an epoxy compound that has the structure indicated by general formula (1) and an acrylic acid or a methacrylic acid with (a) a dicarboxylic or tricarboxylic acid or an acid monoanhydride thereof and (b) a tetracarboxylic acid or an acid dianhydride thereof. (In general formula (1), R1–R8 represent a C4–12 hydrocarbon group, two or more of R1–R8 may be the same, n represents a number that has an average value of 0–3, and G represents a glycidyl group.)

Description

Method for producing polymerizable unsaturated group-containing alkali-soluble resin, polymerizable unsaturated group-containing alkali-soluble resin, photosensitive resin composition containing the same as an essential component, and cured film thereof

The present invention relates to a method for producing a polymerizable unsaturated group-containing alkali-soluble resin, a polymerizable unsaturated group-containing alkali-soluble resin, a photosensitive resin composition containing it as an essential component, and a cured film formed by curing the same. The photosensitive resin composition containing the specific polymerizable unsaturated group-containing alkali-soluble resin of the present invention and the cured product thereof are a resist layer such as a solder resist layer, a plating resist layer and an etching resist layer, and an interlayer such as a multilayer printed wiring board. Applicable as insulating layers, gas barrier films, sealing materials for semiconductor light emitting devices such as lenses and light emitting diodes (LEDs), top coats of paints and inks, hard coats of plastics, rust preventive films of metals, etc. is there.

With recent high performance and high definition of electronic devices and display members, electronic components used there are required to be downsized and high density. And in the workability of the insulating material used for them, refinement | miniaturization and optimization of the cross-sectional shape of the processed pattern have come to be requested | required. A method of patterning by exposure and development is known as an effective means for fine processing of an insulating material, and a photosensitive resin composition has been used there, but high sensitivity, adhesion to a substrate, reliability, Many characteristics such as heat resistance and chemical resistance have been demanded. In addition, various studies have been made to use an organic insulating material in a gate insulating film for an organic TFT. However, it is necessary to reduce the operating voltage of the organic TFT by thinning the gate insulating film, and the withstand voltage is generally high. In particular, in the case of an organic insulating material of about 1 MV / cm, application of a thin film of about 0.2 μm is being studied.

A conventional insulating material made of a photosensitive resin composition uses a photocuring reaction by a reaction between a photoreactive alkali-soluble resin and a photopolymerization initiator, and mainly uses a mercury lamp as an exposure wavelength for photocuring. I line (365 nm), which is one of the line spectra, is used. However, the i-line is absorbed by the photosensitive resin itself or the colorant, and the photocuring degree is lowered. Moreover, the amount of absorption increases if the film is thick. Therefore, a difference in crosslink density in the film thickness direction occurs in the exposed part, and even if photocured sufficiently on the surface of the coating, it is difficult to photocure on the bottom of the film, so the difference in crosslink density between the exposed and unexposed areas. Since the pattern dimension stability, development margin, pattern adhesion, pattern edge shape and cross-sectional shape deteriorated, it was difficult to obtain a photosensitive insulating material that can be developed with high resolution.

In general, a photosensitive resin composition for such an application includes a polyfunctional photocurable monomer having a polymerizable unsaturated bond, an alkali-soluble binder resin, a photopolymerization initiator, and the like. A photosensitive resin composition that is technically disclosed as an application as a color filter material can be applied. For example, Patent Document 1 and Patent Document 2 disclose copolymers of (meth) acrylic acid or (meth) acrylic acid ester having a carboxyl group as a binder resin, maleic anhydride, and other polymerizable monomers. Has been. 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 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 liquid resins using a reaction product of an epoxy (meth) acrylate having a bisphenolfluorene structure and an acid anhydride.

Japanese Patent Laid-Open No. 61-213213 Japanese Unexamined Patent Publication No. 1-152449 JP-A-4-340965 JP-A-4-345673 JP-A-4-345608 JP-A-4-355450 JP-A-4-3631111

However, since the copolymers disclosed in Patent Document 1 and Patent Document 2 are random copolymers, an alkali dissolution rate distribution is generated in the light-irradiated part and in the light-unirradiated part. The time margin is narrow and it is difficult to obtain an acute-angle pattern shape or a fine pattern. In particular, when a high concentration of pigment is included, the exposure sensitivity is remarkably lowered, and a fine negative pattern cannot be obtained.

Moreover, since the alkali-soluble unsaturated compound described in Patent Document 3 is insolubilized by light irradiation, it is expected to have higher sensitivity than the combination of the binder resin and the polyfunctional polymerizable monomer described above. However, the compounds exemplified here are those obtained by arbitrarily adding acrylic acid and acid anhydride, which are polymerizable unsaturated bonds, to the hydroxyl group of the phenol oligomer. Therefore, it is difficult to form a fine negative pattern because the alkali dissolution rate distribution of the alkali-soluble resin is broadened.

In addition, the resins exemplified in Patent Document 4, Patent Document 5, Patent Document 6, and Patent Document 7 have a low molecular weight because they are reaction products of epoxy (meth) acrylate and acid monoanhydride. Therefore, it is difficult to increase the alkali solubility difference between the exposed part and the unexposed part, and a fine pattern cannot be formed.

As described above, a photolithography method using various photosensitive resin compositions is used as a microfabrication method of an insulating material. However, the pattern can be miniaturized and the shape can be optimized, and the formed insulating film can be formed. On the other hand, many characteristics such as adhesion to a substrate, reliability, heat resistance, and chemical resistance have been demanded. For example, providing a material with excellent chemical resistance required in electrode processing processes after forming an insulating film may be required, as in the case of use in flexible displays and touch panels. Is becoming necessary.

The present invention provides a photosensitive resin composition that can be patterned with excellent resolution by alkali development, and can be applied to an insulating film having excellent reliability such as goby folding resistance. is there. 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. Another object of the present invention is to provide a cured film obtained by curing the photosensitive resin composition.

In order to solve the above problems, the present inventors have found that it is effective to use a photosensitive resin composition using a polymerizable unsaturated group-containing alkali-soluble resin having a specific alicyclic structure. Completed the invention.

One embodiment of the present invention for solving the above-described problems is obtained by reacting an epoxy compound having a structure represented by the following general formula (1) with a reaction product of acrylic acid or methacrylic acid with (a) dicarboxylic acid or The present invention relates to a method for producing a polymerizable unsaturated group-containing alkali-soluble resin, in which tricarboxylic acid or its acid monoanhydride and (b) tetracarboxylic acid or its acid dianhydride are reacted.

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

Another embodiment of the present invention is a polymerizable unsaturated group-containing alkali-soluble resin obtained by the above-described production method, and has a structure represented by the general formula (2), and contains a polymerizable unsaturated group-containing alkali-soluble resin. It relates to resin.

In the general formula (2), R5 to R8 each represent a hydrocarbon group having 4 to 12 carbon atoms, two or more of R5 to R8 may be the same, R9 represents a hydrogen atom or a methyl group, and X Represents a tetravalent carboxylic acid residue, Y represents a substituent represented by the following general formula (3) or a hydrogen atom, but one or more is the general formula (3), and m is an average value of 1 to It is a number of 20.

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

In addition, other embodiments of the present invention
(I) the polymerizable unsaturated group-containing alkali-soluble resin,
(Ii) a photopolymerizable monomer having at least two polymerizable unsaturated groups,
The present invention relates to a photosensitive resin composition comprising (iii) a photopolymerization initiator, and (iv) a solvent as essential components.

Moreover, other embodiment of this invention is related with the hardened | cured material 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 elastic modulus and excellent goat folding characteristics. It can be used as a flexible display or a touch panel insulating film. Moreover, the cured | curing material pattern which has the outstanding chemical resistance can be obtained when it is necessary to pass through processing processes, such as electrode formation, after forming an insulating film by a touchscreen manufacturing process.

Hereinafter, the present invention will be described in detail.

In one embodiment of the present invention, a reaction product of an epoxy compound having a structure represented by the general formula (1) and acrylic acid or methacrylic acid, (a) dicarboxylic acid or tricarboxylic acid or acid monoanhydride thereof And (b) a method for producing a polymerizable unsaturated group-containing alkali-soluble resin in which tetracarboxylic acid or its acid dianhydride is reacted, and a polymerizable unsaturated group-containing alkali-soluble resin produced by the method.

The epoxy compound having the structure represented by the general formula (1) can be synthesized by reacting (epoxidizing) the dimer diol compound represented by the general formula (4) with epihalohydrin.

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

The above dimer diol compound can be synthesized from a product obtained by reducing a carboxyl group of a polymerized fatty acid (dimer acid) to a hydroxyl group. The polymerized fatty acid is a compound obtained by an intermolecular reaction of two or more unsaturated fatty acids (linoleic acid, oleic acid, etc.), and the main component is a dibasic acid having 36 carbon atoms. is there. The dimer acid skeleton contains some unsaturated double bonds in the hydrocarbon group corresponding to the 6-membered ring and R1 to R4, but most of them are hydrogenated when the carboxyl group is reduced. To saturated carbon-carbon single bond. At this time, even when a small amount of unsaturated double bonds remain, that is, when epoxidized using a dimer diol compound containing an unsaturated double bond, the main skeleton becomes an epoxy compound of the general formula (1). The unsaturated group-containing alkali-soluble resin of the present invention can be used as a raw material.

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

The dimer diol compound and epihalohydrin can be reacted by a known method as epoxidation. For example, the above dimer diol compound is dissolved in an excess of epihalohydrin and then reacted in the presence of an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide at 40 to 120 ° C. for 1 to 10 hours, whereby the epoxy Is possible. From the viewpoint of reducing hydrolyzable halogen, the above reaction is preferably performed at 50 to 70 ° C.

Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide and a mixture thereof. These alkali metal hydroxides are preferably used in an aqueous solution or in a solid state.

The amount of the alkali metal hydroxide used is preferably 0.8 mol or more and 15.0 mol or less, and 0.9 mol or more and 2.0 mol or less with respect to 1 mol of the hydroxyl group in the dimer diol compound. More preferably. The amount of residual hydrolyzable halogen can be reduced by making the usage-amount of the said alkali metal hydroxide into 0.8 mol or more with respect to 1 mol of hydroxyl groups in a dimer diol compound. In addition, the amount of the alkali metal hydroxide used is 15.0 mol or less with respect to 1 mol of the hydroxyl group in the dimer diol compound, thereby reducing the amount of gel produced during epoxy compound synthesis and It is difficult to produce an emulsion and the yield can be increased.

At this time, a phase transfer catalyst may be used in combination from the viewpoint of promoting the reaction. Examples of phase transfer catalysts include quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride and methyltrioctylammonium chloride. These ammonium salts may be used independently and may use 2 or more types together. 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, with respect to 100 parts by weight of the dimer diol compound, and 1.0 part by weight or more. More preferably, it is 5.0 parts by weight or less.

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

The amount of the epihalohydrin used is preferably 1.5 mol or more and 30 mol or less, more preferably 2 mol or more and 15 mol or less, with respect to 1 mol of the total amount of hydroxyl groups in the dimer diol compound. More preferably, it is 5 mol or more and 10 mol or less. The molecular weight of an epoxy compound can be adjusted to such an extent that a viscosity does not become excessively high by making the usage-amount of the said epihalohydrin into 1.5 mol or more with respect to 1 mol of hydroxyl groups in a dimer diol compound. Productivity can be improved more by making the usage-amount of the said epihalohydrin 30 mol or less with respect to 1 mol of hydroxyl groups in a dimer diol compound.

The reaction (epoxidation) of the dimer diol compound and epihalohydrin is preferably performed in a solvent that does not react with the epoxy group. Examples of the solvent include aromatic hydrocarbons including toluene, xylene and benzene, ketones including methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone and acetone, alcohols including propanol and butanol, diethylene glycol methyl ether, propylene glycol Includes glycol ethers including methyl ether and dipropylene glycol methyl ether, aliphatic ethers including diethyl ether, dibutyl ether and ethylpropyl ether, alicyclic ethers including dioxane and tetrahydrofuran, and dimethyl sulfoxide It is. These solvents may be used alone or in combination of two or more.

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

After completion of the reaction, excess epihalohydrin is distilled off, dissolution in a solvent, filtration, removal of inorganic salts by washing with water, and distillation of the solvent to obtain the above epoxy compound.

At this time, if the amount of hydrolyzable halogen is too large, purification may be performed to reduce the amount of hydrolyzable halogen. In the above purification, 1 to 30 times the amount of the remaining hydrolyzable halogen is added to the obtained epoxy compound, and a purification reaction is performed at a temperature of 60 to 90 ° C. for 10 minutes to 2 hours. Thereafter, neutralization, washing with water and the like are performed to remove excess alkali metal hydroxide and by-product salts, and the solvent is distilled off under reduced pressure.

The epoxy compound is reacted with (meth) acrylic acid to form an epoxy (meth) acrylate compound having a polymerizable unsaturated group.

The above epoxy compound and (meth) acrylic acid can be reacted by a known method. For example, 2 moles of (meth) acrylic acid is used for 1 mole of the above epoxy compound group, but (meth) acrylic acid is reacted with all the epoxy groups, so that it is slightly more than an equimolar amount of the epoxy group and the carboxyl group. An excess of (meth) acrylic acid may be used. By this reaction, an epoxy (meth) acrylate compound in which the G part in the general formula (1) is replaced with a group represented by the general formula (5) is obtained.

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

The solvent and catalyst used at this time and other reaction conditions are not particularly limited. For example, it is preferable to use a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature. Examples of such solvents include cellosolv solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high boiling ethers or esters such as diglyme, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate. As well as ketone solvents including cyclohexanone and diisobutyl ketone. Examples of the catalyst include known catalysts such as ammonium salts including tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines including triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine. .

Further, the epoxy (meth) acrylate compound is reacted with (a) dicarboxylic acid or tricarboxylic acid or acid monoanhydride thereof, and (b) tetracarboxylic acid or acid dianhydride thereof, to contain a polymerizable unsaturated group. An alkali-soluble resin can be obtained.

Examples of the above (a) dicarboxylic acid or tricarboxylic acid or acid monoanhydride include saturated chain hydrocarbon dicarboxylic acid or tricarboxylic acid or acid monoanhydride, saturated cyclic hydrocarbon dicarboxylic acid or tricarboxylic acid or these Acid monoanhydrides, unsaturated hydrocarbon dicarboxylic acids or tricarboxylic acids, or acid monoanhydrides thereof, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, or acid monoanhydrides thereof. In addition, each hydrocarbon residue (structure excluding the carboxyl group) of these dicarboxylic acid or tricarboxylic acid or these acid monoanhydrides is further substituted with a substituent such as an alkyl group, a cycloalkyl group, or an aromatic group. It may be.

Examples of saturated chain hydrocarbon dicarboxylic acids or tricarboxylic acids include succinic acid, acetyl succinic acid, adipic acid, azelaic acid, citralmalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid , Suberic acid, diglycolic acid and the like. Examples of the saturated cyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, hexahydrotrimellitic acid, and the like. Examples of unsaturated dicarboxylic acids or tricarboxylic acids include maleic acid, itaconic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, and chlorendic acid. Examples of the aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include phthalic acid and trimellitic acid. Acid monoanhydrides of these dicarboxylic acid or tricarboxylic acid compounds can also be used. Of these, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid and trimellitic acid or their monohydrates are preferred, and succinic acid, itaconic acid and tetrahydrophthalic acid or these acids are preferred. Monoanhydride is more preferred.

Examples of the above (b) tetracarboxylic acid or acid dianhydride include chain hydrocarbon tetracarboxylic acid or acid dianhydride, alicyclic tetracarboxylic acid or acid dianhydride, and aromatic polyvalent Carboxylic acid or its acid dianhydride is included. In addition, each hydrocarbon residue (structure excluding the carboxyl group) of these tetracarboxylic acids or acid dianhydrides may be further substituted with a substituent such as an alkyl group, a cycloalkyl group, or an aromatic group. Good.

Specific examples of the tetracarboxylic acid include butanetetracarboxylic acid, pentanetetracarboxylic acid, and hexanetetracarboxylic acid. Examples of the alicyclic tetracarboxylic acid include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, and norbornanetetracarboxylic acid. Examples of the aromatic polyvalent carboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and biphenyl ether tetracarboxylic acid. 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 monoanhydride and (b) tetracarboxylic acid or its acid dianhydride used in the above reaction is 0.01 to 0.5, preferably 0.02 or more and less than 0.1. When the molar ratio (a) / (b) is out of the above range, the optimum molecular weight for obtaining a photosensitive resin composition having good photopatterning properties cannot be obtained, which is not preferable. In addition, there exists a tendency for alkali solubility to become large and molecular weight to become large, so that molar ratio (a) / (b) is small.

About the ratio with which the epoxy (meth) acrylate compound (c) containing the polymerizable unsaturated group is reacted with the carboxylic acid components (a) and (b), preferably, the end of the compound becomes a carboxyl group. In addition, it is desirable to make the reaction quantitatively so that the molar ratio of each component is (c) :( a) :( b) = 1: 0.2 to 1.0: 0.01 to 1.0. In this case, the reaction may be carried out quantitatively so that the molar ratio (c) / [(a) / 2 + (b)] = 0.5 to 1.0 of the total amount of the acid component relative to the epoxy (meth) acrylate compound. desirable. When this molar ratio is less than 0.5, the end of the alkali-soluble resin becomes an acid anhydride, and the content of unreacted acid dianhydride increases, and there is a concern that the stability over time of the alkali-soluble resin composition may decrease. Is done. 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 is increased, and there is a concern that the temporal stability of the alkali-soluble resin composition may be lowered. The molar ratio of each component of (a), (b) and (c) can be arbitrarily changed within the above range for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin.

The reaction with the above (a) dicarboxylic acid or tricarboxylic acid or its acid monoanhydride, and (b) tetracarboxylic acid or its acid dianhydride is, for example, a catalyst such as triethylamine, tetraethylammonium bromide and triphenylphosphine. The reaction can be carried out by stirring at 90 to 130 ° C. in the presence.

The polymerizable unsaturated group-containing alkali-soluble resin produced by the production method described above preferably has an acid value of 30 to 200 mgKOH / g, more preferably 50 to 150 mgKOH / g. If the oxidation is less than 30 mg KOH / g, a residue is likely to remain during alkali development, and if it exceeds 200 mg KOH / g, the alkaline developer may permeate too quickly and release development may occur.

In the production method described above, from the viewpoint of lowering the viscosity of the polymerizable unsaturated group-containing alkali-soluble resin to be produced, the content of n = 0 (n = 0 isomer) in the general formula (1) is 50. % Or more is preferable, and 70% or more is more preferable.

Moreover, the polymerizable unsaturated group-containing alkali-soluble resin produced by the production method described above preferably 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 hydrolysis reaction to be inhibited by the hydrolyzable halogen, and the physical properties of the cured product, in particular, the insulation reliability is not easily lowered. Preferred for use. The hydrolyzable halogen content is preferably 0.1% by mass or less, and more preferably 0.05% by mass or less.

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

In general formula (2), R5 to R8 represent a hydrocarbon group having 4 to 12 carbon atoms, and two or more of R5 to 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. However, one or more of Y in the polymerizable unsaturated group-containing alkali availability resin containing a plurality of molecules is represented by the general formula (3). m is a number having an average value of 1 to 20. )

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

[Photosensitive resin composition]
The polymerizable unsaturated group-containing alkali-soluble resin having the structure represented by the above general formula (2) is:
(I) a polymerizable unsaturated group-containing alkali-soluble resin having a structure represented by the general formula (2) (ii) a photopolymerizable monomer having at least two polymerizable unsaturated groups;
It can be set as the photosensitive resin composition containing (iii) photoinitiator and (iv) solvent.

(Ii) Examples of 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, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol (meth) acrylate, sorbitol penta (meth) acrylate, dipenta Includes lithitol penta (meth) acrylate or dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide modified hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Includes (meth) acrylic acid esters, polyhydric alcohols including pentaerythritol and dipentaerythritol, vinylbenzyl ether compounds of polyhydric phenols such as phenol novolac, addition polymers of divinyl compounds such as divinylbenzene, etc. It is. When it is necessary to form a crosslinked structure between molecules of the polymerizable unsaturated group-containing alkali-soluble resin, 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. Note that (ii) the photopolymerizable monomer having at least two polymerizable unsaturated groups does not have a free carboxy group.

The blending ratio of the component (ii) is preferably 5 to 400 parts by mass, and preferably 10 to 150 parts by mass with respect to 100 parts by mass of the component (i). When the blending ratio of the component (ii) is more than 400 parts by mass with respect to 100 parts by mass of the component (i), the cured product after photocuring becomes brittle, and the acid value of the coating film is low in the unexposed area. There arises a problem that the solubility in an alkaline developer is lowered and the pattern edge is not jagged and sharp. On the other hand, when the blending ratio of the component (ii) is less than 5 parts by mass with respect to 100 parts by mass of the component (i), the ratio of the photoreactive functional group in the resin is small and the formation of the crosslinked structure is not sufficient. Since the acid value in the resin component is high, the solubility in an alkaline developer in the exposed area is high, and thus the formed pattern becomes thinner than the target line width or the pattern is easily lost. Problems may arise.

(Iii) Examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone. Benzophenones including acetophenones, benzophenone, 2-chlorobenzophenone, and benzophenones including p, p'-bisdimethylaminobenzophenone, benzoin ethers including benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether, 2- (o-chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole Biimidazoles including 2- (o-fluorophenyl) -4,5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole and the like Compounds, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, and 2- Halomethyldiazole compounds including trichloromethyl-5- (p-methoxystyryl) -1,3,4-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-bis (trichloromethyl) -1,3,5-triazine, and 2- (4 -Methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like halomethyl-s-triazine compounds, 1,2-octanedione, 1- [4- (phenylthio) phen Nyl]-, 2- (O-benzoyloxime), 1- (4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanylphenyl) butane- 1,2-dione-2-oxime-O-acetate, 1- (4-methylsulfanylphenyl) butan-1-one oxime-O-acetate, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), methanone, (9-ethyl-6-nitro-9H-carbazol-3-yl) [4- (2-methoxy-1-methyl) Ethoxy) -2-methylphenyl]-, O-acetyloxime, methanone, (2-methylphenyl) (7-nitro-9,9-dipropyl-9H-fluoro N-2-yl)-, acetyloxime, ethanone, 1- [7- (2-methylbenzoyl) -9,9-dipropyl-9H-fluoren-2-yl]-, 1- (O-acetyloxime), And O-acyloxime compounds such as 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-, 1-O-acetyloxime, benzyldimethyl ketal, thioxanthone, Sulfur compounds including 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone Anthraquinones such as 2,3-diphenylanthraquinone, azobisisobutylnitrile Organic peroxides including benzoyl peroxide and cumene peroxide, 2-mercaptobenzimidazole, and the like 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole thiol compounds and the like. These photopolymerization initiators may be used alone or in combination of two or more. In addition, the photoinitiator as used in the field of this invention is used by the meaning containing a sensitizer.

In addition, (iii) a compound that does not act as a photopolymerization initiator or a sensitizer by itself as a photopolymerization initiator, but can increase the ability of the photopolymerization initiator or sensitizer when used in combination. Can also be added. Examples of such compounds include tertiary amines such as triethanolamine and triethylamine which are effective when used in combination with benzophenone.

The blending ratio of the component (iii) is preferably 0.1 to 30 parts by mass, preferably 1 to 25 parts by mass based on 100 parts by mass of the total of the components (i) and (ii). Good. (Iii) When the blending ratio of the component is less than 0.1 parts by mass, the rate of photopolymerization is reduced and the sensitivity is decreased, whereas when it exceeds 30 parts by mass, the sensitivity is too strong, The pattern line width becomes thicker than the pattern mask, and there is a possibility that a line width that is faithful to the mask cannot be reproduced, or the pattern edge does not become jagged and sharp.

(Iv) Examples of solvents include methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol Alcohols including, terpenes including α- or β-terpineol, etc., ketones including acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, etc., including toluene, xylene, tetramethylbenzene, etc. Aromatic hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene Glycol ethers including lenglycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether, 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, and propylene glycol monoethyl ether acetate Esters containing and the like are included. These solvents may be used alone or in combination of two or more in order to satisfy properties such as coating properties.

In addition, the photosensitive resin composition includes a curing accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a coupling agent, and a surfactant as necessary. Additives can be blended. As the curing accelerator, for example, a known compound commonly known as a curing accelerator, a curing catalyst, a latent curing agent and the like which are usually applied to an epoxy compound can be used, and tertiary amine, quaternary ammonium salt, tertiary phosphine, Secondary phosphonium salts, boric acid esters, Lewis acids, organometallic 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 phenol compounds, phosphorus heat stabilizers and the like. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. 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 compounds. Examples of coupling agents include vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (glycidyloxy) propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane Silane coupling agents such as 3-aminopropyltriethoxysilane, 3- (phenylamino) propyltrimethoxysilane, and 3-ureidopropyltriethoxysilane. Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant.

The photosensitive resin composition can also be used by adding (v) an epoxy resin or 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 compounds, phenol novolac type epoxy compounds, cresol novolacs. Type epoxy compound, glycidyl ether of polyhydric alcohol, glycidyl ester of polycarboxylic acid, polymer containing glycidyl (meth) acrylate as a unit, 3,4-epoxycyclohexanecarboxylic acid [(3,4-epoxycyclohexyl) methyl ], 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (for example, “E PE3150 "(manufactured by Daicel Corporation), phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, epoxidized polybutadiene (for example," NISSO-PB / JP-100 ", manufactured by Nippon Soda Co., Ltd.) And epoxy compounds having a silicone skeleton. These components are preferably compounds having an epoxy equivalent of 100 to 300 g / eq and a number average molecular weight of 100 to 5000. As the component (v), only one type of compound may be used, or two or more types may be used in combination. When there is a need to increase the crosslinking density of the alkali-soluble resin, a compound having at least two epoxy groups is preferred.

When the epoxy compound (v) is used, the addition amount is preferably 10 to 40 parts by mass with respect to 100 parts by mass in 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 forming a cured film after patterning in order to increase the reliability of the cured film. If the addition amount of the epoxy compound is less than 10 parts by mass, for example, the moisture resistance reliability when used as an insulating film may not be ensured. Moreover, when there are more compounding quantities of an epoxy compound than 40 mass parts, there exists a possibility that the quantity for the photosensitive group in the resin component in the photosensitive resin composition may reduce, and the sensitivity for patterning may not fully be obtained. .

The photosensitive resin composition contains the components (i) to (iv) or the components (i) to (v) as main components. It is desirable that the components (i) to (iii) and (v) are contained in a total of 70% by mass, preferably 80% by mass or more in the solid content. (Iv) The amount of the solvent varies depending on the target viscosity, but is preferably included in the photosensitive resin composition in the range of 60 to 90% by mass.

[Cured product]
The photosensitive resin composition is applied to, for example, a substrate, dried, irradiated (exposed) with light (including ultraviolet rays and radiation), and cured to obtain a cured product (coating film). be able to. At this time, using a photomask or the like to provide a portion that is exposed to light and a portion that is not exposed to light, only the portion that is exposed to light is cured, and the other portion is dissolved with an alkaline solution. (Coating film) is obtained.

Specifically, when the photosensitive resin composition is applied to the substrate, any method such as a known solution dipping method, spray method, roller coater machine, land coater machine, slit coater or spinner machine is used. Can also be adopted.

By these methods, the photosensitive resin composition is applied to a desired thickness, and then the solvent is removed (prebaked) to form a film. Pre-baking is performed by heating with an oven and a hot plate, vacuum drying, and a combination thereof. The heating temperature and heating time in the pre-baking are appropriately selected according to the solvent to be used, for example, at a temperature of 80 to 120 ° C. for 1 to 10 minutes.

Examples of radiation used for exposure include visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray, but radiation having a wavelength in the range of 250 to 450 nm is preferable.

Alkali development can be performed using, for example, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, and the like as a developer. These developing solutions are selected according to the characteristics of the resin layer, but a surfactant may be added as necessary. The development is preferably performed at a temperature of 20 to 35 ° C. By using a commercially available developing machine, ultrasonic cleaner, or the like, a fine image can be accurately formed. In addition, it is usually washed with water after alkali development. Examples of the development processing method include a shower development method, a spray development method, a dip (immersion) development method, and a paddle (liquid buildup) development method.

After the development, heat treatment (post-bake) is performed at a temperature of 120 to 250 ° C. and a condition of 20 to 100 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned coating film and the substrate. Post-baking is performed by heating with an oven, a hot plate, or the like, as in pre-baking.

Thereafter, polymerization or curing (sometimes referred to as curing together) is completed by heat to obtain a cured film such as an insulating film. The curing temperature at this time is preferably in the range of 160 to 250 ° C.

The cured product is a resist layer such as a solder resist layer, a plating resist layer, an etching resist layer, an interlayer insulating layer such as a multilayer printed wiring board, a film for a gas barrier, a lens, and a semiconductor light emitting device such as a light emitting diode (LED). It can also be used for sealing materials, top coats of paints and inks, hard coats of plastics, rust preventive films of metals, and the like.

Hereinafter, although embodiments of the present invention will be specifically described based on examples and comparative examples, the present invention is not limited to these.

First, synthesis examples of the polymerizable unsaturated group-containing alkali-soluble resin containing the structure represented by the general formula (2) will be described. Evaluation of the resin in these synthesis examples is performed as follows unless otherwise noted. It was.

[Solid content]
1 g of the resin solution, photosensitive resin composition, etc. obtained in the synthesis examples (and comparative synthesis examples) was impregnated into a glass filter [mass: W0 (g)] and weighed [W1 (g)], 160 ° C. From the mass [W2 (g)] after heating for 2 hours, the following formula was used.
Solid content concentration (mass%) = 100 × (W2-W0) / (W1-W0)

[Acid value]
The resin solution is dissolved in dioxane, and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titrator (COM-1600 manufactured by Hiranuma Sangyo Co., Ltd.), and the amount of KOH required per gram of solid content is determined by acid. It was set as the value.

[Molecular weight]
Gel permeation chromatography (GPC) (HLC-8220GPC manufactured by Tosoh Corporation), solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper-H5000 (1) 1) (manufactured by Tosoh Corporation), temperature: 40 ° C., speed: 0.6 ml / min), weight average molecular weight (Mw) as standard polystyrene (PS-oligomer kit made by Tosoh Corporation) equivalent ).
Abbreviations used in the synthesis examples and comparative synthesis examples are as follows.
DDOEA: Dimer diol compound (Cropa Pripol 2033, hydroxyl group equivalent 270 g / eq) and a reaction product of chloromethyloxirane (having the skeleton of the general formula (1)) and acrylic acid (an epoxy group and a carboxyl group) Equivalent reactant)
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 1000 ml four-necked flask equipped with a reflux condenser, 351.0 g of a 50% PGMEA solution of DDOEA, 30.2 g of BPDA, 15.6 g of THPA, 0.43 g of TEAB, and 8.5 g of PGMEA are charged. The mixture was stirred at 125 ° C. for 6 hours with heating to obtain an alkali-soluble resin (i) -1. The obtained resin had a solid content concentration of 54.6% by mass, an acid value (in terms of solid content) of 84.1 mgKOH / g, and a molecular weight (Mw) of 3400.

[Comparative Example 1]
A 291% 50% PGMEA solution of an equivalent reaction product of bisphenol A type epoxy compound (epoxy equivalent = 182) and acrylic acid (equivalent reaction product of epoxy group and carboxyl group) is put into a 1000 ml four-necked flask equipped with a reflux condenser. 0.0 g, 4.0 g of dimethylolpropionic acid, 11.8 g of 1,6-hexanediol and 84 g of PGMEA were charged, and the temperature was raised to 45 ° C. Next, 61.8 g of isophorone diisocyanate was added dropwise while paying attention to the temperature in the flask. After completion of the dropwise addition, the mixture was stirred for 6 hours under heating at 75-80 ° C. Further, 21.0 g of THPA was charged and stirred for 6 hours under heating at 90 to 95 ° C. to obtain an alkali-soluble resin solution (i) -2. The obtained resin had a solid content concentration of 66.5% by mass, an acid value (in terms of solid content) of 38.4 mgKOH / g, and a molecular weight (Mw) of 12,220.

Next, the present invention will be specifically described based on Examples and Comparative Examples relating to the photosensitive resin composition and the cured product, 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: Alkali-soluble resin obtained in Example 1 (i) -2: Alkali-soluble resin obtained in Comparative Example 1 (i) -3: 68 of cresol novolac type acid-modified epoxy acrylate resin .9% PGMEA solution (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 (Michler's ketone)
(Iv) Propylene glycol monomethyl ether acetate (v): Cresol novolac type epoxy resin

The above-described blending components were blended in the proportions shown in Table 1 to prepare 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 Examples 2 to 3]
The photosensitive resin composition shown in Table 1 was coated on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post-baking was 30 μm, and pre-baked at 110 ° C. for 5 minutes to be coated. It was created. Thereafter, ultraviolet light having a wavelength of 365 nm was irradiated through a photomask for pattern formation with a high-pressure mercury lamp of 500 W / cm ² to carry out photocuring reaction of the exposed portion. Next, this exposed coated plate is further developed for 30 seconds from the time when the pattern started to appear in a 0.8 mass% tetramethylammonium hydroxide (TMAH) aqueous solution and 23 ° C. shower development, and further washed with spray water. The unexposed part of the coating film was removed. Thereafter, heat curing treatment was performed at 230 ° C. for 30 minutes using a hot air dryer, and cured films according to Example 2 and Comparative Examples 2 to 3 were obtained.

The following evaluation was performed on the cured film obtained under the above conditions. In addition, at the time of creation of a cured film for a film thickness test, an alkali resistance test, and an acid resistance test, development, washing with water, and heat curing treatment were performed after the entire exposure without passing through a photomask.

(Film thickness)
A portion of the applied film was shaved and measured using a stylus type step shape measuring device (trade name P-10, manufactured by KLA-Tencor Corp.).

(Alkali resistance test)
A glass substrate with a cured film is immersed in a solution of 30 parts by mass of 2-aminoethanol and 70 parts by mass of glycol ether maintained at 80 ° C., pulled up after 10 minutes, washed with pure water, dried, and immersed in a chemical. Samples prepared were evaluated for adhesion. A crosscut was put on the film of the sample immersed in the chemical so as to form at least 100 grids, and then a peeling test was performed using a cellophane tape, and the grids were visually evaluated.
◎: No peeling at all ○: Some peeling can be confirmed on the coating film △: Some peeling can be confirmed on the coating film ×: The film almost peeled off

(Acid resistance test)
A glass substrate with a cured film is immersed in a solution of aqua regia (hydrochloric acid: nitric acid = 7: 3) held at 50 ° C., pulled up 10 minutes later, washed with pure water and dried to prepare a sample immersed in chemicals. The adhesion was evaluated. A crosscut was put on the film of the sample immersed in the chemical so as to form at least 100 grids, and then a peeling test was performed using a cellophane tape, and the grids were visually evaluated.
◎: No peeling at all ○: Some peeling can be confirmed on the coating film △: Some peeling can be confirmed on the coating film ×: The film almost peeled off

(Bending test)
The photosensitive resin composition shown in Table 1 was applied on a glass substrate on which a 125 mm × 125 mm release film was pasted using a spin coater so that the film thickness after post-baking was 30 μm, and at 110 ° C. for 5 minutes. Pre-baked to prepare a coated plate. Thereafter, ultraviolet light having a wavelength of 365 nm was irradiated through a photomask for pattern formation with a high-pressure mercury lamp of 500 W / cm ² to carry out photocuring reaction of the exposed portion. Next, this exposed coated plate is further developed for 30 seconds from the time when the pattern started to appear in a 0.8 mass% tetramethylammonium hydroxide (TMAH) aqueous solution and 23 ° C. shower development, and further washed with spray water. The unexposed part of the coating film was removed. Thereafter, heat curing treatment 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 films according to Example 2 and Comparative Examples 2 to 3.

The film obtained under the above conditions was folded in half, and then spread with the top of the fold line facing up. This test was repeated and evaluated by the number of times cracks and fractures were observed.

From the results of Example 2 and Comparative Examples 2 to 3, with respect to the reaction product of the epoxy compound having the structure represented by the general formula (1) and acrylic acid or methacrylic acid, (a) dicarboxylic acid or tricarboxylic acid or By using a polymerizable unsaturated group-containing alkali-soluble resin, including a polymerizable unsaturated group-containing alkali-soluble resin, which reacts with the acid monoanhydride and (b) tetracarboxylic acid or acid dianhydride. It can be seen that patterning with excellent resolution is possible, and a cured film with excellent reliability such as goby folding resistance can be manufactured.

This application claims priority based on Japanese Patent Application No. 2018-066322 filed on Mar. 28, 2018. All the contents described in the application specification are incorporated herein by reference.

Claims

For a reaction product of an epoxy compound having a structure represented by the following general formula (1) and acrylic acid or methacrylic acid, (a) dicarboxylic acid or tricarboxylic acid or acid monoanhydride thereof, and (b) tetracarboxylic acid A method for producing a polymerizable unsaturated group-containing alkali-soluble resin in which an acid or an acid dianhydride is reacted.

(In the general formula (1), R1 to R8 represent a hydrocarbon group having 4 to 12 carbon atoms, two or more of R1 to R8 may be the same, and n is a number having an average value of 0 to 3 And G represents a glycidyl group.)
A polymerizable unsaturated group-containing alkali-soluble resin obtained by the production method of claim 1, wherein the polymerizable unsaturated group-containing alkali-soluble resin has a structure represented by the general formula (2).

(In the general formula (2), R5 to R8 represent a hydrocarbon group having 4 to 12 carbon atoms, two or more of R5 to 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 or a hydrogen atom represented by the following general formula (3), but one or more is the general formula (3), and m has an average value of 1 It is a number of ~ 20.)

(In the general formula (3), M represents a divalent or trivalent carboxylic acid residue, and p is 1 or 2.)
(I) The polymerizable unsaturated group-containing alkali-soluble resin according to claim 2,
(Ii) a photopolymerizable monomer having at least two polymerizable unsaturated groups,
A photosensitive resin composition comprising (iii) a photopolymerization initiator, and (iv) a solvent as essential components.
(V) The photosensitive resin composition according to claim 3, further comprising an epoxy resin or an epoxy compound having two or more epoxy groups.
(Iii) 0.1 to 30 parts by mass of component (iii) and 10 to 40 parts by mass of component (v) with respect to 100 parts by mass in total of component (ii) and component (ii), Item 5. The photosensitive resin composition according to Item 4.
A cured film obtained by curing the photosensitive resin composition according to any one of claims 3 to 5.