JPWO2019188897A1 - 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 the same as an essential component, and a cured film thereof. - Google Patents

Abstract

For a reaction product of an epoxy compound having a structure represented by the following general formula (1) and an acrylic acid or a methacrylic acid, (a) a dicarboxylic acid or a tricarboxylic acid or an acid dianhydride thereof, and (b) a tetracarboxylic dianoxide are used. A method for producing a polymerizable unsaturated group-containing alkali-soluble resin by reacting an acid or an acid dianhydride thereof. [Chemical formula 1] (In the general formula (1), R1 to R8 represent hydrocarbon groups having 4 to 12 carbon atoms, and two or more of R1 to R8 may be the same, and n has an average value of 0. Represents a number of ~ 3, where G represents a glycidyl group.)

Description

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 the same as an essential component, and a cured film obtained by curing the same. The photosensitive resin composition containing the specific polymerizable unsaturated group-containing alkali-soluble resin of the present invention and its cured product are a solder resist layer, a plated resist layer, a resist layer such as an etching resist layer, and layers such as a multilayer printed wiring board. It can be applied as an insulating layer, a film for a gas barrier, a sealing material for semiconductor light emitting elements such as lenses and light emitting diodes (LEDs), a top coat for paints and inks, a hard coat for plastics, a rust preventive film for metals, etc. is there.

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

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

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

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

However, since the copolymers disclosed in Patent Document 1 and Patent Document 2 are random copolymers, the alkali dissolution rate is distributed in the light-irradiated portion and the light-non-irradiated portion, and the development operation is performed. The time margin is narrow, and it is difficult to obtain sharp-angled pattern shapes and fine patterns. In particular, when a high-concentration pigment is contained, the exposure sensitivity is significantly lowered, and a fine negative pattern cannot be obtained.

Further, since the alkali-soluble unsaturated compound described in Patent Document 3 is insolubilized by light irradiation, it is expected that the sensitivity will be higher than that of the above-mentioned combination of the binder resin and the polyfunctional polymerizable monomer. However, the compound exemplified here is obtained by arbitrarily adding a polymerizable unsaturated group, acrylic acid and an acid anhydride, to the hydroxyl group of the phenol oligomer, and even in the case of such a proposal, each molecule is used. Since a wide distribution is formed in the molecular weight and the amount of carboxyl groups of the alkali-soluble resin, the distribution of the alkali dissolution rate of the alkali-soluble resin becomes wide, and it is difficult to form a fine negative pattern.

Further, the resins exemplified in Patent Document 4, Patent Document 5, Patent Document 6 and Patent Document 7 have a small molecular weight because they are reaction products of epoxy (meth) acrylate and acid monoanhydride. Therefore, it is difficult to increase the difference in alkali solubility between the exposed portion and the unexposed portion, and it is not possible to form a fine pattern.

As described above, a photolithography method using various photosensitive resin compositions is used as a microfabrication method for an insulating material, but the insulating film formed after the pattern can be miniaturized and the shape can be optimized. On the other hand, many properties such as adhesion to a substrate, reliability, heat resistance, and chemical resistance are required. For example, when used in a flexible display or a touch panel, it may be necessary to have resistance to breakage, and to provide a material having excellent chemical resistance required in an electrode processing process after forming an insulating film. Is becoming necessary.

INDUSTRIAL APPLICABILITY The present invention provides a photosensitive resin composition which is a photosensitive resin composition capable of patterning with excellent resolution by alkaline development and which can be applied to an insulating film or the like having excellent reliability such as fold resistance. is there. It is also an object of the present invention 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.

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 in order to solve the above problems. The invention was completed.

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

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

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

In the 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, and X Indicates a tetravalent carboxylic acid residue, Y indicates 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 to 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.

In addition, other embodiments of the present invention
(I) The above-mentioned 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.

Further, another embodiment of the present invention relates to a cured product obtained by curing the 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 alkaline development, and the cured product has a low elastic modulus and excellent foldability. It can be used as a flexible display or a touch panel insulating film. Further, when it is necessary to go through a processing process such as electrode formation after forming the insulating film in the touch panel manufacturing process or the like, a cured product pattern having excellent chemical resistance can be obtained.

Hereinafter, the present invention will be described in detail.

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

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

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

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

The dimer diol compound can be synthesized from a polymerized fatty acid (dimer acid) in which the carboxyl group is reduced 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 several unsaturated double bonds in the 6-membered ring and the hydrocarbon groups corresponding to R1 to R4, but most of them are hydrogenated when the carboxyl group is reduced to form an unsaturated double bond. Becomes a saturated carbon-carbon single bond. At this time, even if a small amount of unsaturated double bonds remain, that is, even when epoxidized using a dimerdiol compound containing unsaturated double bonds, the main skeleton is the epoxy compound of the general formula (1). , Can be used as a raw material for the unsaturated group-containing alkali-soluble resin of the present invention.

Examples of commercially available products containing the dimer diol compound include Croda's Pripol 2030, 2033 and the like.

The dimerdiol compound and epihalohydrin can be reacted by a method known as epoxidation. For example, the dimerdiol compound is dissolved in excess epihalohydrin and then reacted at 40 to 120 ° C. for 1 to 10 hours in the presence of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide to cause the epoxy. Can be converted. From the viewpoint of reducing hydrolyzable halogen, the above reaction is preferably carried out at 50 to 70 ° C.

Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, and mixtures thereof. These alkali metal hydroxides are preferably used in an aqueous solution or 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 dimerdiol compound. More preferably. By setting the amount of the alkali metal hydroxide used to 0.8 mol or more with respect to 1 mol of the hydroxyl group in the dimerdiol compound, the amount of residual hydrolyzable halogen can be reduced. Further, by setting the amount of the alkali metal hydroxide used to 15.0 mol or less with respect to 1 mol of the hydroxyl group in the dimerdiol compound, the amount of gel produced during the synthesis of the epoxy compound is reduced, and the amount of gel produced during washing with water is reduced. It makes it difficult to form an emulsion and can increase the yield.

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 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 1.0 part by weight or more with respect to 100 parts by weight of the dimerdiol compound. It is more preferably 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, based on 1 mol of the total amount of hydroxyl groups in the dimerdiol compound. More preferably, it is 5.5 mol or more and 10 mol or less. By setting the amount of epihalohydrin used to 1.5 mol or more with respect to 1 mol of the hydroxyl group in the dimer diol compound, the molecular weight of the epoxy compound can be adjusted to the extent that the viscosity does not become excessively high. Productivity can be further enhanced by setting the amount of the epihalohydrin used to 30 mol or less with respect to 1 mol of the hydroxyl group in the dimerdiol compound.

The reaction (epoxidation) between the dimerdiol compound and epihalohydrin is preferably carried out in a solvent that does not react with the epoxy group. Examples of the above solvents 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 and 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 dimethylsulfoxide and the like. Is done. 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, and 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of epihalohydrin. Is even more preferable.

After completion of the reaction, excess epihalohydrin can be distilled off, and the above epoxy compound can be obtained by dissolving in a solvent, filtering, removing an inorganic salt by washing with water, and distilling off the solvent.

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, a purification reaction is carried out at a temperature of 60 to 90 ° C. for 10 minutes to 2 hours in addition to the epoxy compound obtained by obtaining an alkali metal hydroxide in an amount of 1 to 30 times the amount of the remaining hydrolyzable halogen. After that, it can be carried out by neutralizing, washing with water or the like to remove excess alkali metal hydroxide or by-product salt, and further distilling off the solvent under reduced pressure.

The epoxy compound is reacted with (meth) acrylic acid 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 mol of (meth) acrylic acid is used for 1 mol of the above epoxy compound group, but since (meth) acrylic acid is reacted with all the epoxy groups, it is slightly larger than the equimolar of the epoxy group and the carboxyl group. Excessive (meth) acrylic acid may be used. By this reaction, an epoxy (meth) acrylate compound in which the G portion in the general formula (1) is replaced with the group represented by the general formula (5) is obtained.

In the 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, as the solvent, it is preferable to use a solvent having no hydroxyl group and having a boiling point higher than the reaction temperature. Examples of such solvents include cellosolvent solvents including ethyl cellosolve acetate and butyl cellosolve acetate, high boiling ether or ester systems including jiglime, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate. , And a ketone solvent containing cyclohexanone, diisobutylketone and the like. Examples of the catalysts include known catalysts such as ammonium salts containing tetraethylammonium bromide and triethylbenzylammonium chloride and the like, and phosphines including triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine and the like. ..

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

Examples of (a) dicarboxylic acid or tricarboxylic acid or acid monoanhydride thereof include saturated chain hydrocarbon dicarboxylic acid or tricarboxylic acid or their acid monoanhydride, saturated ring hydrocarbon dicarboxylic acid or tricarboxylic acid or these. Acid monoanhydrides, unsaturated hydrocarbon dicarboxylic acids or tricarboxylic acids or their acid monoanhydrides, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids or their acid monoanhydrides and the like are included. The hydrocarbon residues (structure excluding the carboxyl group) of these dicarboxylic acids or tricarboxylic acids or their acid monoanhydrides are further substituted with substituents such as alkyl groups, cycloalkyl groups and aromatic groups. May be.

Examples of saturated chain hydrocarbon dicarboxylic acids or tricarboxylic acids include succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citric acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimeric acid, sebacic acid. , Succinic acid, and diglycolic acid. Examples of saturated cyclic hydrocarbon dicarboxylic acids or tricarboxylic acids include hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornandicarboxylic 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 aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids include phthalic acids and trimellitic acids. Acid monoanhydrides of these dicarboxylic acids 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 anhydrides are preferred, and succinic acid, itaconic acid and tetrahydrophthalic acid or their acids. Monoanhydrides are more preferred.

Examples of (b) tetracarboxylic acid or acid dianhydride thereof include chain hydrocarbon tetracarboxylic acid or acid dianhydride thereof, alicyclic tetracarboxylic acid or acid dianhydride thereof, and aromatic polyvalent. A carboxylic acid or an acid dianhydride thereof and the like are included. Even if each hydrocarbon residue (structure excluding the carboxyl group) of these tetracarboxylic acids or their acid dianhydrides is 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, hexanetetracarboxylic acid and the like as examples of the chain hydrocarbon tetracarboxylic acid. Examples of alicyclic tetracarboxylic dians include cyclobutanetetracarboxylic dians, cyclopentanetetracarboxylic dians, cyclohexanetetracarboxylic dians, cycloheptantetracarboxylic dians, norbornanetetracarboxylic dians and the like. Examples of aromatic polyvalent carboxylic acids include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenyl ether tetracarboxylic acid and the like. 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 used in the above reaction to (b) tetracarboxylic acid or its acid dianhydride is 0.01 to. It is 0.5, preferably 0.02 or more and less than 0.1. If the molar ratio (a) / (b) deviates from the above range, the optimum molecular weight for obtaining a photosensitive resin composition having good photopatterning properties cannot be obtained, which is not preferable. The smaller the molar ratio (a) / (b), the greater the alkali solubility and the larger the molecular weight.

Regarding the ratio of reacting the epoxy (meth) acrylate compound (c) containing the polymerizable unsaturated group with the carboxylic acid components (a) and (b), it is preferable that the end of the compound becomes a carboxyl group. In addition, it is desirable to carry out 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 of the total amount of the acid component to the epoxy (meth) acrylate compound is (c) / [(a) / 2+ (b)] = 0.5 to 1.0. desirable. When this molar ratio is less than 0.5, the terminal of the alkali-soluble resin becomes an acid anhydride, and the content of the unreacted acid dianhydride increases, and there is a concern that the stability of the alkali-soluble resin composition with time may decrease. Will be 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 increases, and there is a concern that the stability of the alkali-soluble resin composition with time may decrease. The molar ratio of each component (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 (a) dicarboxylic acid or tricarboxylic acid or its acid monoanhydride, and (b) tetracarboxylic acid or its acid dianhydride is carried out by, for example, a catalyst such as triethylamine, tetraethylammonium bromide and triphenylphosphine. In the presence, it can be heated at 90-130 ° C. and stirred to react.

The polymerizable unsaturated group-containing alkali-soluble resin produced by the above-mentioned production method preferably has an acid value of 30 to 200 mgKOH / g, and more preferably 50 to 150 mgKOH / g. If the oxidation is less than 30 mgKOH / g, a residue tends to remain during alkaline development, and if it exceeds 200 mgKOH / g, the penetration of the alkaline developer becomes too fast, and peeling development may occur.

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

The polymerizable unsaturated group-containing alkali-soluble resin produced by the above-mentioned production method preferably has a hydrolyzable halogen content of 0.2% by mass or less. When the hydrolyzable halogen content is 0.2% by mass or less, the curing reaction is less likely to be hindered by the hydrolyzable halogen, and the physical properties of the cured product, particularly the insulation reliability, are less likely to deteriorate. 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 above-mentioned production method, for example, when n = 0 in the general formula (1), a polymerizable unsaturated group-containing alkaline availability resin having a structure represented by the following general formula (2) is produced.

In the general formula (2), R5 to R8 represent hydrocarbon groups 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 or a hydrogen atom represented by the following general formula (3). However, of the plurality of Ys in the polymerizable unsaturated group-containing alkaline availability resin containing a plurality of molecules, one or more is of 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-mentioned 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 a photosensitive resin composition containing (iii) a photopolymerization initiator and (iv) a 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, and tetraethylene glycol. Di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropantri (meth) acrylate, trimethylol ethanetri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Elythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate, sorbitol hexa. (Meta) Acrylates including (meth) acrylates, alkylene oxide-modified hexa (meth) acrylates of phosphazenes, and caprolactone-modified dipentaerythritol hexa (meth) acrylates, and polyhydric alcohols including pentaerythritol and dipentaerythritol. Includes vinyl benzyl ether compounds of polyvalent phenols such as phenol novolac, and addition polymers of divinyl compounds such as divinylbenzene. When it is necessary to form a crosslinked structure between molecules of a 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) a 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, preferably 10 to 150 parts by mass with respect to 100 parts by mass of the component (i). If the compounding 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 part. There is a problem that the solubility in an alkaline developer is lowered and the pattern edge is not sharpened. On the other hand, when the compounding 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 groups in the resin is small and the formation of the crosslinked structure is not sufficient, and further. Since the acid value of the resin component is high, the solubility in the alkaline developer in the exposed area is high, so that the formed pattern becomes thinner than the target line width, and the pattern is likely to be missing. Problems can occur.

Examples of the photopolymerization initiator (iii) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone. Acetphenones containing, benzophenone, 2-chlorobenzophenone, and benzophenones including p, p'-bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin ethers including benzoin isobutyl ether, etc. 2- (o-chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5 Biimidazole compounds, including −diphenylbiimidazole, 2- (o-methoxyphenyl) -4,5-diphenylbiimidazole, and 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, and 2-trichloromethyl-5- (p-methoxystyryl)- Halomethyldiazole compounds including 1,3,4-oxadiazole, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloro) Methyl) -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-tri) Methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, etc. Halomethyl-s-triazine compounds, including 1,2-octanedione, 1- [4- (phenylthio) pheni -, 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) butane-1-one-oxime-O-acetate, etanone, 1- [9-ethyl-6- (2-methylbenzoyl)) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), methanone, (9-ethyl-6-nitro-9H-carbazole-3-yl) [4- (2-methoxy-1-methyl) Ethoxy) -2-methylphenyl]-, O-acetyloxime, methanone, (2-methylphenyl) (7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-, acetyloxime, etanone, 1 -[7- (2-Methylbenzoyl) -9,9-dipropyl-9H-fluoren-2-yl]-, 1- (O-acetyloxime), and etanone, 1- (-9,9-dibutyl-7) -Nitro-9H-fluoren-2-yl)-, O-acyloxime compounds including 1-O-acetyloxime, benzyl dimethyl ketal, thioxanson, 2-chlorothioxenson, 2,4-diethyl thioxime Sulfur compounds containing son, 2-methylthioxanthone, 2-isopropylthioxanthone and the like, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benz anthraquinone and 2,3-diphenylanthraquinone, azobis Included are organic peroxides such as isobutylnitrile, benzoyl peroxide, and oxime peroxide, thiol compounds including 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole and the like. These photopolymerization initiators may be used alone or in combination of two or more. The photopolymerization initiator referred to in the present invention is used in the sense of including a sensitizer.

Further, as (iii) a photopolymerization initiator, a compound that does not act as a photopolymerization initiator or a sensitizer by itself, 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 benzophenones.

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 a total of 100 parts by mass of the component (i) and the component (ii). Good. When the compounding ratio of the component (iii) is less than 0.1 parts by mass, the photopolymerization rate becomes slow and the sensitivity decreases, while 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 risk that the line width faithful to the mask cannot be reproduced, or the pattern edge is not sharpened.

Examples of solvents (iv) 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, etc., terpenes including α- or β-terpineol, etc., ketones including acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, etc., toluene, xylene, and tetramethylbenzene and the like. Aromatic hydrocarbons, 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 mono Glycol ethers including ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, etc., ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, cellosolve acetate, Includes esters including ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like. These solvents may be used alone or in combination of two or more in order to satisfy characteristics such as coatability.

In addition, the above-mentioned photosensitive resin composition may contain, if necessary, a curing accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a filler, a leveling agent, a defoaming agent, a coupling agent, a surfactant and the like. Additives can be added. As the curing accelerator, for example, known compounds known as curing accelerators, curing catalysts, latent curing agents and the like usually applied to epoxy compounds can be used, and tertiary amines, quaternary ammonium salts, tertiary phosphines, and quaternary compounds can be used. Class phosphonium salts, borate esters, Lewis acids, organic metal compounds, imidazoles, diazabicyclo compounds and the like are included. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenolic compounds, phosphorus thermal stabilizers and the like. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate and the like. Examples of fillers include glass fiber, silica, mica, alumina, precipitated barium sulphate, 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, 3-isocyanatopropyltriethoxysilane. , 3-Aminopropyltriethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-ureidopropyltriethoxysilane and other silane coupling agents are included. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and the like.

In the photosensitive resin composition, (v) an epoxy resin or an epoxy compound having two or more epoxy groups can be used in addition 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, and cresol novolac. Type epoxy compound, glycidyl ether of polyhydric alcohol, glycidyl ester of polyvalent carboxylic acid, polymer containing glycidyl (meth) acrylate as a unit, 3,4-epoxycyclohexanecarboxylic acid [(3,4-epoxycyclohexyl) methyl ], An alicyclic epoxy compound, 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (for example, "EHPE3150", Daicel Co., Ltd.) ), Phenylglycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, epoxidized polybutadiene (for example, "NISSO-PB / JP-100", manufactured by Nippon Soda Co., Ltd.), epoxy with a silicone skeleton Contains compounds. 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 kind of compound may be used, or two or more kinds may be used in combination. When it is necessary to increase the crosslink density of the alkali-soluble resin, a compound having at least two epoxy groups is preferable.

When the epoxy compound (v) is used, the amount added is preferably 10 to 40 parts by mass with respect to 100 parts by mass in total of the component (i) and the component (ii). Here, one purpose of adding the epoxy compound is to reduce the amount of carboxyl groups remaining when the cured film is formed after patterning in order to improve the reliability of the cured film. If the amount of the epoxy compound added is less than 10 parts by mass, the moisture resistance reliability when used as an insulating film, for example, may not be ensured. Further, when the compounding amount of the epoxy compound is more than 40 parts by mass, the amount of the photosensitive groups in the resin component in the photosensitive resin composition may decrease, and the sensitivity for patterning may not be sufficiently 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 solid content contains 70% by mass, preferably 80% by mass or more of the components (i) to (iii) and (v) in total. (Iv) The amount of the solvent varies depending on the target viscosity, but it is preferable that the amount of the solvent is contained in the photosensitive resin composition in the range of 60 to 90% by mass.

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

Specifically, when the photosensitive resin composition is applied to the substrate, any method such as a known solution dipping method, a spray method, a roller coater machine, a land coater machine, a slit coat machine or a 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 (pre-baked) to form a film. Pre-baking is performed by heating in an oven, hot plate, etc., vacuum drying, and a combination thereof. The heating temperature and heating time in the prebake are appropriately selected depending on the solvent used, and are carried out at a temperature of, for example, 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.

Alkaline development can be carried out using, for example, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide or the like as a developing solution. These developers are selected according to the characteristics of the resin layer, but a surfactant may be added if necessary. Development is preferably carried out 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 precisely formed. After alkaline development, it is usually washed with water. Examples of the developing method include a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (filling) developing method, and the like.

After developing in this way, heat treatment (post-baking) is performed at a temperature of 120 to 250 ° C. and conditions of 20 to 100 minutes. This post-baking is performed for the purpose of enhancing the adhesion between the patterned coating film and the substrate. Post-baking is performed by heating in an oven, a hot plate, or the like, similar to pre-baking.

After that, polymerization or curing (sometimes referred to as curing together) is completed by heat, 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 to 250 ° C.

The cured product is used for 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 element such as a light emitting diode (LED). It can also be used as a sealing material, a top coat for paints and inks, a hard coat for plastics, a rust preventive film for metals, and the like.

Hereinafter, embodiments of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto.

First, a synthetic example of a polymerizable unsaturated group-containing alkali-soluble resin containing a structure represented by the general formula (2) will be described. Unless otherwise specified, the evaluation of the resin in these synthetic examples is carried out as follows. It was.

[Solid content concentration]
A glass filter [mass: W0 (g)] was impregnated with 1 g of the resin solution, the photosensitive resin composition, etc. obtained in the synthesis example (and comparative synthesis example) and weighed [W1 (g)] at 160 ° C. It was calculated from the following formula from the mass [W2 (g)] after heating for 2 hr.
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 1 g of solid content is acid. It was a 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), and weight average molecular weight (Mw) as a standard polystyrene (PS-oligoform kit manufactured by Tosoh Corporation) ) Is the calculated value.
The abbreviations used in the synthesis example and the comparative synthesis example are as follows.
DDOEA: A reaction product of a dimerdiol compound (Pripol 2033 manufactured by Crowder Co., Ltd., hydroxyl group equivalent 270 g / eq) and chloromethyloxylane (having a skeleton of the general formula (1)) and a reaction product of acrylic acid (epoxy group and 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]
351.0 g of DDOEA 50% PGMEA solution, 30.2 g of BPDA, 15.6 g of THPA, 0.43 g of TEAB, 8.5 g of PGMEA were charged in a 1000 ml four-necked flask equipped with a return condenser, 120 to The mixture was stirred under heating at 125 ° C. for 6 hours to obtain an alkali-soluble resin (i) -1. The solid content concentration of the obtained resin was 54.6% by mass, the acid value (in terms of solid content) was 84.1 mgKOH / g, and the molecular weight (Mw) was 3400.

[Comparative Example 1]
A 50% PGMEA solution of an equivalent reaction product of a bisphenol A type epoxy compound (epoxy equivalent = 182) and acrylic acid (equal equivalent reaction product of an epoxy group and a carboxyl group) was placed in a 1000 ml four-necked flask equipped with a return cooler. 0.0 g, 4.0 g of dimethylol propionic 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 inside the flask. After completion of the dropping, the mixture was stirred for 6 hours under heating at 75 to 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 solid content concentration of the obtained resin was 66.5% by mass, the acid value (in terms of solid content) was 38.4 mgKOH / g, and the molecular weight (Mw) was 12220.

Next, the present invention will be specifically described 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 above (i) -2: Alkali-soluble resin obtained in Comparative Example 1 above (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 ketone)
(Iv) Propylene Glycol Monomethyl Ether Acetate (v): Cresol Novolac Epoxy Resin

The above-mentioned compounding components were blended in the ratio shown in Table 1 to prepare the photosensitive resin compositions of Example 2 and Comparative Examples 2 and 3. All the numerical values in Table 1 represent parts by mass.

[Evaluation of Photosensitive Resin Compositions of Example 2 and Comparative Examples 2 and 3]
The photosensitive resin composition shown in Table 1 is applied to a glass substrate of 125 mm × 125 mm using a spin coater so that the film thickness after post-baking is 30 μm, and prebaked at 110 ° C. for 5 minutes to coat the coating plate. It was created. Then, ultraviolet rays having a wavelength of 365 nm were irradiated with a high-pressure mercury lamp of ^{500 W / cm 2} through a photomask for pattern formation, and a photocuring reaction of the exposed portion was carried out. Next, this exposed coating film was developed with a 0.8 mass% tetramethylammonium hydroxide (TMAH) aqueous solution and shower development at 23 ° C. for another 30 seconds from the time when the pattern began to appear, and then spray-washed. , The unexposed part of the coating film was removed. Then, it was heat-cured at 230 ° C. for 30 minutes using a hot air dryer to obtain a cured film according to Example 2 and Comparative Examples 2 and 3.

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

(Film thickness)
A part of the applied film was scraped off, and the measurement was performed using a stylus type step shape measuring device (trade name P-10 manufactured by KLA Tencor Co., Ltd.).

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

(Acid resistance test)
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 after 10 minutes, washed with pure water, dried, and a sample immersed in chemicals is prepared. The adhesion was evaluated. At least 100 cross-cuts were made on the film of the sample immersed in the chemical so as to form a grid pattern, and then a peeling test was performed using cellophane tape to visually evaluate the state of the grid pattern.
◎: No peeling is seen at all ○: Slight peeling can be confirmed on the coating film △: Peeling can be confirmed on some coating films ×: Most of the film is peeled off

(Bending test)
The photosensitive resin composition shown in Table 1 was applied to a glass substrate to which a 125 mm × 125 mm release film was attached using a spin coater so that the film thickness after post-baking was 30 μm, and the film thickness was 110 ° C. for 5 minutes. A coating plate was prepared by prebaking. Then, ultraviolet rays having a wavelength of 365 nm were irradiated with a high-pressure mercury lamp of ^{500 W / cm 2} through a photomask for pattern formation, and a photocuring reaction of the exposed portion was carried out. Next, this exposed coating film was developed with a 0.8 mass% tetramethylammonium hydroxide (TMAH) aqueous solution and shower development at 23 ° C. for another 30 seconds from the time when the pattern began to appear, and then spray-washed. , The unexposed part of the coating film was removed. Then, it was heat-cured at 230 ° C. for 30 minutes using a hot air dryer, and the obtained pattern was peeled off from the release film to obtain films according to Example 2 and Comparative Examples 2 and 3.

After folding the film obtained under the above conditions in half, the film was spread with the crown of the crease facing up. This test was repeated and evaluated by the number of times cracks and breaks were observed.

From the results of Example 2 and Comparative Examples 2 and 3, (a) a dicarboxylic acid or a tricarboxylic acid or a reaction product of an epoxy compound having a structure represented by the general formula (1) and an acrylic acid or a methacrylic acid was obtained. When a polymerizable unsaturated group-containing alkali-soluble resin containing a polymerizable unsaturated group-containing alkali-soluble resin that reacts the acid monoanhydride and (b) tetracarboxylic acid or its acid dianhydride is used, it is subjected to alkaline development. It can be seen that patterning with excellent resolution is possible, and a cured film having excellent reliability such as resistance to alkalinity can be produced.

This application claims priority under Japanese Patent Application No. 2018-063232 filed on March 28, 2018. All the contents described in the application specification are incorporated in the application specification.

Claims (6)

With respect to the reaction product of the epoxy compound having the structure represented by the following general formula (1) and acrylic acid or methacrylic acid, (a) dicarboxylic acid or tricarboxylic acid or its acid dianhydride, and (b) tetracarboxylic A method for producing a polymerizable unsaturated group-containing alkali-soluble resin by reacting an acid or an acid dianhydride thereof.

(In the general formula (1), R1 to R8 represent hydrocarbon groups having 4 to 12 carbon atoms, and 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 according to claim 1, which 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, and two or more of R5 to R8 may be the same, and 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 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 containing (iii) a photopolymerization initiator and (iv) a solvent as essential components. (V) The photosensitive resin composition according to claim 3, further containing an epoxy resin or an epoxy compound having two or more epoxy groups. Claimed to contain 0.1 to 30 parts by mass of the component (iii) and 10 to 40 parts by mass of the component (v) with respect to a total of 100 parts by mass of the component (i) and the component (ii). Item 4. 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.