JP2019174670A - Photosensitive resin composition containing polymerizable unsaturated group-containing alkali-soluble resin as essential component, and cured film thereof - Google Patents

Abstract

To provide a photosensitive resin composition which contains various dispersoids including a colorant and realizes a smooth surface pattern upon pattern formation by photolithography, without wrinkles on the surface of the pattern.SOLUTION: A photosensitive resin composition contains, as essential components, (i) a polymerizable unsaturated group-containing alkali-soluble resin, including a polymer having a structure represented by general formula (1), (ii) a photopolymerizable monomer having at least two polymerizable unsaturated groups, (iii) a photoinitiator, and (iv) dispersoids.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition containing a polymerizable unsaturated group-containing alkali-soluble resin having a specific structure and containing a dispersoid including a colorant as an essential component, and a cured film obtained by curing the photosensitive resin composition. . The photosensitive resin composition of the present invention and its cured product include solder resists, plating resists, etching resists for circuit board production, color filters such as liquid crystal display devices, organic EL display devices, μLED display devices, and image sensors. It can be applied as various cured films formed by photolithography methods such as light shielding films.

  With recent high performance and high definition of electronic devices and display members, electronic components used therein 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. The pattern dimensional stability, development margin, pattern adhesion, pattern edge shape and cross-sectional shape deteriorated, making it difficult to obtain a photosensitive material that can be developed at 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.

  Patent Document 8, Patent Document 9 and Patent Document 10 include an alkali-developable unsaturated resin composition obtained by copolymerization of a dihydroxypropyl acrylate compound and an acid dianhydride, or an acid monoanhydride and an acid dianhydride. An alkali developable unsaturated resin composition by copolymerization with a dihydroxypropyl acrylate compound is disclosed. In this case, the copolymerization of the acid dianhydride and the dihydroxypropyl acrylate compound proceeds to obtain an oligomer.

Japanese Laid-Open Patent Publication No. 61-213213 Japanese Patent Laid-Open No. 1-152449 JP-A-4-340965 JP-A-4-345673 JP-A-4-345608 JP-A-4-355450 JP-A-4-363111 JP-A-5-339356 JP-A-5-146132 International Publication No. 94/00801

  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.

  Moreover, since resin illustrated by patent document 4, patent document 5, patent document 6, and patent document 7 is a reaction product of an epoxy (meth) acrylate and acid monoanhydride, its molecular weight is small. 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.

  In addition, the copolymers described in Patent Document 8, Patent Document 9 and Patent Document 10 may not have a sufficient crosslinking density due to a small number of polymerizable unsaturated bonds. It may be difficult to form. Therefore, there is room for improvement of the copolymer structure such as increasing the ratio of polymerizable unsaturated bonds in one molecule.

  Furthermore, with colored resists for various color filters, etc., the surface of the pattern formed by photolithography has wrinkles that are thought to be due to curing shrinkage, which makes it impossible to obtain a smooth surface. Sometimes it becomes. In particular, in a film with a large degree of light shielding represented by a black resist, when the degree of curing on the substrate side on which the film is applied is lower than the degree of curing of the film surface during exposure, the surface is more easily wrinkled during heat curing. However, there is a concern that a smooth cured film pattern cannot be obtained, or a manufacturing condition margin for obtaining an appropriate pattern is small, resulting in a decrease in manufacturing yield.

  The present invention provides a photosensitive resin composition containing various dispersoids including a colorant, in which when a pattern is formed by photolithography, the surface of the pattern is not wrinkled and becomes a smooth surface pattern. The purpose is to do. In particular, when a thick film is formed, or when a photosensitive resin composition containing a dispersoid having a large light shielding degree, that is, there is a difference between the degree of curing near the surface of the film applied to the substrate and the degree of curing of the film part in contact with the substrate. Although it is characterized in that the smoothness of the surface can be maintained when it becomes large, it is also effective when a low elastic modulus due to the skeleton characteristics of the unsaturated group-containing alkali-soluble resin to be used is required. is there.

  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.

An embodiment of the present invention for solving the above problems is as follows.
(I) a polymerizable unsaturated group-containing alkali-soluble resin comprising a polymer having a structure represented by the general formula (1);
(Ii) a photopolymerizable monomer having at least two polymerizable unsaturated groups,
(Iii) a photopolymerization initiator, and (iv) a dispersoid,
Is contained as an essential component.

  In the general formula (1), 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, and X Represents a tetravalent carboxylic acid residue, Y represents a substituent represented by the following general formula (2) or a hydrogen atom, and m represents an average value of 1 to 20.

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

  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 formed pattern has no wrinkles on the surface and is smooth. It becomes a surface pattern. In particular, it is possible to form a smooth surface pattern when a thick film is formed or when a cured product pattern having a high light shielding degree is formed. In addition, since the cured product has low elasticity, it includes solder resists, plating resists, etching resists for circuit board creation, color filters such as liquid crystal display devices, organic EL display devices, μLED display devices, and image sensors. In a light-shielding film or the like, various dispersoids can be added to form a cured film pattern having various functions.

  Hereinafter, the present invention will be described in detail.

One embodiment of the present invention
(I) a polymerizable unsaturated group-containing alkali-soluble resin comprising a polymer having a structure represented by the general formula (1);
(Ii) a photopolymerizable monomer having at least two polymerizable unsaturated groups,
(Iii) a photopolymerization initiator, and (iv) a dispersoid,
Is contained as an essential component.

  In General Formula (1), 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 (2) or a hydrogen atom. m is a number having an average value of 1 to 20.

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

  A polymerizable unsaturated group-containing alkali-soluble resin containing a polymer having a structure represented by the general formula (1) is a reaction between an epoxy compound having a structure represented by the general formula (3) and acrylic acid or methacrylic acid. The product can be produced by reacting (a) a dicarboxylic acid or tricarboxylic acid or its acid monoanhydride and (b) tetracarboxylic acid or its acid dianhydride.

  In General Formula (3), 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. G represents a glycidyl group.

  The epoxy compound having the structure represented by the general formula (3) can be synthesized by reacting (epoxidizing) the dimer diol compound represented by the general formula (4) with an 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 said dimer diol compound is compoundable from what reduced the carboxyl group of the polymeric fatty acid (dimer acid) to the 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 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 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, after the dimer diol compound is dissolved in excess epihalohydrin, the epoxy is reacted in the presence of alkali metal hydroxide such as sodium hydroxide and potassium hydroxide at 40 to 120 ° C. for 1 to 10 hours. Is possible. In addition, it is preferable to perform the said reaction at 50-70 degreeC from a viewpoint of reducing a hydrolyzable halogen.

  Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide and lithium hydroxide, and mixtures 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, from the viewpoint of promoting the reaction, a phase transfer catalyst may be used in combination. 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 mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, with respect to 100 parts by mass of the dimer diol compound, and 1.0 part by mass or more. More preferably, it is 5.0 parts by mass 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.

  Excess epihalohydrin is distilled off after completion of the reaction, and the above epoxy compound can be obtained by dissolving in a solvent, filtering, removing inorganic salts by washing with water, and distilling off the solvent.

  At this time, when the amount of hydrolyzable halogen is too large, purification for reducing the amount of hydrolyzable halogen may be performed. In the above purification, 1 to 30 times the amount of the alkali metal hydroxide with respect to the remaining hydrolyzable halogen amount 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 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 is replaced by the general formula (5) in the general formula (3) 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 molar ratio (c) / [(a) / 2 + (b)] = 0.5 to 1.0 of the total amount of the acid component to the epoxy (meth) acrylate compound may be quantitatively reacted. 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, and 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, in general formula (3), the content of n = 0 (n = 0 isomer) is 50. % Or more is preferable, and 70% or more is more preferable.

  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.

  The polymerizable unsaturated group-containing alkali-soluble resin produced by the production method described above has a structure represented by the general formula (1), which is a reaction product of an epoxy compound with n = 0 in the general formula (3). The above-mentioned polymers having are included.

  From the viewpoint of reducing the viscosity of the polymerizable unsaturated group-containing alkali-soluble resin, the polymerizable unsaturated group-containing alkali-soluble resin has a polymer content of 50% or more having a structure represented by the general formula (1). It is preferable that it is 70% or more.

  (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, dipentaeth Including thritol 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 photopolymerization initiators 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, Biimidazole systems including-(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-trichloro Halomethyldiazole compounds including methyl-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, , 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- Halomethyl-s-triazine compounds including methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 1,2-octanedione, 1- [4- (phenylthio) pheny L]-, 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-fluore -2-yl)-, acetyloxime, ethanone, 1- [7- (2-methylbenzoyl) -9,9-dipropyl-9H-fluoren-2-yl]-, 1- (O-acetyloxime), and O-acyloxime compounds including etanone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-, 1-O-acetyloxime, benzyldimethyl ketal, thioxanthone, 2 -Sulfur compounds including chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, Anthraquinones such as 2,3-diphenylanthraquinone, azobisisobutylnitrile, Emissions benzoyl peroxide, and organic peroxides, including cumene peroxide, 2-mercaptobenzimidazole, and the like 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole thiol compounds and the like. Among these, from the viewpoint of obtaining a highly sensitive photosensitive resin composition when forming a cured film pattern having a high light shielding degree as in the case of containing a dispersoid at a high concentration, an O-acyloxime compound is used. Are preferably used. 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 the total of 100 parts by mass of the component (i) and the component (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) The dispersoid that can be used in the present invention is dispersed with an average particle diameter of 1 to 1000 nm (average particle diameter measured by a laser diffraction / scattering particle size distribution meter or a dynamic light scattering particle size distribution meter). If it is a thing, the well-known dispersoid conventionally used for the photosensitive resin composition can be especially used without a restriction | limiting. (Iv) Examples of dispersoids include azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, selenium pigments, perylene pigments, perinone pigments, quinophthalone pigments, Organic pigments including diketopyrrolopyrrole pigments and thioindigo pigments, inorganic pigments including titanium oxide pigments and composite oxide pigments, and pigments including carbon black pigments (colorants that do not substantially dissolve in the medium) included. Examples of (iv) dispersoids include organic fillers including acrylic polymer particles and urethane polymer particles, and silica, talc, mica, glass fiber, carbon fiber, calcium silicate, magnesium carbonate, calcium carbonate. Further, compounds other than pigments such as inorganic fillers including calcium sulfate and barium sulfate are also included. Furthermore, (iv) other examples of the dispersoid include metal or metal oxide nanoparticles.

  These (iv) dispersoids are used singly or in combination depending on the function of the desired photosensitive resin composition. For example, as a light-shielding resist used in the production of a black matrix of a color filter, carbon black, titanium Black and black organic pigments can be used, and red, orange, yellow, green, blue, and purple organic pigments can be used as color resists used in the manufacture of color filter pixels. As the solder resist used for the production of the insulating film of the wiring board, organic pigments, inorganic pigments, inorganic fillers, etc. can be used, and as the decorative resist used for the design of the front glass of the touch panel, carbon black, titanium Using black, black organic pigments, white pigments, etc. Come, high hardness, high refractive index, the transparent resist high durability can be used a transparent fillers such as silica and titania, can be used by appropriately selected, respectively.

  In addition, (iv) when the dispersoid is a light-shielding material, it can be a black organic pigment, a mixed color organic pigment, a black inorganic pigment, etc., and depends on the application, but has insulation, heat resistance, light resistance and solvent resistance. It is preferable that it is excellent in property. Examples of black organic pigments used here include perylene black, aniline black, cyanine black, and lactam black. Examples of mixed color organic pigments used here include mixed pigments that are pseudo-black by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, and the like. Examples of the black inorganic pigment used here include carbon black, chromium oxide, iron oxide, and titanium black. As these (iv) dispersoids, only one type of compound may be used, or a plurality may be used in combination.

In addition, as an organic pigment which can be used as (iv) component, the thing of the following numbers can be illustrated by a color index name, However, It is not limited to this.
Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272 279, etc.Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.Pigment Yellow 1, 3, 12, 13 , 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 27, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc. Pigment Green 7, 36, 58, etc. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, 80, etc. Pigment Violet 19, 23, 37, etc.

  As other dispersoids, a known rubber component may be added for improving impact resistance, adhesion to a plated metal during processing, and the like. Among the rubber components, a crosslinked elastic polymer having a carboxyl group is preferable in order to ensure developability. Specifically, a crosslinked acrylic rubber having a carboxyl group, a crosslinked NBR having a carboxyl group, and a crosslinked MBS having a carboxyl group. Etc. can be mentioned. When a rubber component is used, it is preferable to add a material having an average particle size of 0.1 μm or less in a range of 3 to 10 parts by mass with respect to 100 parts by mass of the resin component.

  Examples of the solvent for dispersing the (iv) dispersoid include methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2 Alcohols including butanone and diacetone alcohol, terpenes including α- or β-terpineol, etc., ketones including acetone, methyl ethyl ketone, cyclohexanone and N-methyl-2-pyrrolidone, toluene, xylene, And aromatic hydrocarbons including tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol mono Glycol ethers including methyl ether, propylene glycol 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 mono Esters including ethyl ether acetate 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.

  (Iv) Preferably, the dispersoid is preferably dispersed in a solvent together with a dispersant to obtain a dispersoid dispersion, and then blended as a photosensitive resin composition. About the compounding ratio of the dispersoid which forms a dispersoid dispersion liquid, 1-95 mass% can be added and used with respect to the total solid of the photosensitive resin composition of this invention. In addition, the said solid content means the component except the solvent among compositions. The solid content includes a component (ii) that becomes a solid content after photocuring. The wide range of addition amount of 1 to 95% by mass of the dispersoid is, for example, from the case of using a dispersoid having a low specific gravity of organic matter such as acrylic resin particles and rubber particles, to a dispersoid having a high specific gravity such as metal particles and metal oxide particles. This is because it may be used. For example, when adding a dispersoid for the purpose of coloring, it is preferable that it is 5-80 mass%. When the content is less than 5% by mass in the solid content, it becomes impossible to impart a function to which the dispersoid should be imparted, such as the desired coloring cannot be achieved or the desired coloring property (color) cannot be imparted. When it exceeds 80% by mass in the solid content, the content of the photosensitive resin which is originally a binder is reduced, so that development characteristics are impaired and film forming ability is impaired. Therefore, the component (iv) in the solid content is more preferably 10 to 70% by mass and further preferably 20 to 60% by mass in the case of a colorant (including a light shielding material).

  In the dispersion, a dispersant is used for stably dispersing the dispersoid. For this purpose, known dispersants such as various polymer dispersants can be used. As examples of the dispersant, known compounds conventionally used for pigment dispersion (compounds marketed under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) can be used without particular limitation. Examples thereof include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, pigment derivative dispersants (dispersion aids), and the like. In particular, it has a cationic functional group such as an imidazolyl group, pyrrolyl group, pyridyl group, primary, secondary or tertiary amino group as an adsorption point to the pigment, an amine value of 1 to 100 mgKOH / g, and a number average molecular weight Is preferably a cationic polymer dispersant having a molecular weight of 1,000 to 100,000. The amount of the dispersing agent is 1 to 35% by mass, preferably 2 to 25% by mass, based on the dispersoid. High viscosity substances such as resins generally have an action of stabilizing the dispersion, but those not having the ability to promote dispersion are not treated as dispersants. However, it is not limited to use for the purpose of stabilizing dispersion.

  (I) a polymerizable unsaturated group-containing alkali-soluble resin including a polymer having a structure represented by the general formula (1), (ii) a photopolymerizable monomer, (iii) a photopolymerization initiator, and (iv) ) A photosensitive resin composition containing a dispersoid as an essential component can be used usually by dissolving it in a solvent and further blending various additives. As a solvent used at this time, (iv) what was illustrated as a solvent used in order to disperse | distribute a dispersoid can be used 1 type or in combination of 2 or more types.

  The photosensitive resin composition may contain additives such as a curing accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a leveling agent, an antifoaming agent, a coupling agent, and a surfactant as necessary. 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, quaternary 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 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 may further include (v) an epoxy resin or an epoxy compound having two or more epoxy groups. (V) Examples of epoxy resins or epoxy compounds having two or more epoxy groups 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 compound, 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], a 1,2-epoxy-4- (2-oxiranyl) cyclohexane of 2,2-bis (hydroxymethyl) -1-butanol Sun adduct (eg, “EHPE3150”, manufactured by Daicel Corporation), phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, epoxidized polybutadiene (eg, “NISSO-PB • JP-100”, 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 as a 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) as main components and (v) as an optional component. It is desirable that the components (i) to (v) are contained in a total of 70% by mass, preferably 80% by mass or more in the solid content. Although the quantity of a solvent changes with target viscosity, it is good to make it contain in the range of 60-90 mass% in the photosensitive resin composition.

[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 applying the photosensitive resin composition to a desired thickness by these methods, the solvent is removed (pre-baking) to form a coating 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, and are performed, 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, and radiation having a wavelength in the range of 250 to 450 nm is preferable.

  The alkali development can be performed using, for example, an aqueous solution such as sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, and tetramethylammonium hydroxide as a developer. These developing solutions are selected according to the characteristics of the resin layer, but a surfactant may be added as necessary. 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 as described above, a heat treatment (post-bake) is performed at a temperature of 180 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 by combining both) 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 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, etc. Further, it is extremely useful because it can be applied not only as a coating agent but also to production of a film, a substrate, a plastic part, an optical lens, etc. by molding the thermosetting composition itself.

  Hereinafter, although an embodiment of the present invention is described concretely based on an example and a comparative example, 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 (1) will be described. Evaluation of resins 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 (% by 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 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 Corp.), temperature: 40 ° C., speed: 0.6 ml / min), and weight average molecular weight (Mw) as standard polystyrene (PS-oligomer kit manufactured by Tosoh Corp.) ).
Abbreviations used in the synthesis examples and comparative synthesis examples are as follows.
DDOEA: Dimerdiol compound (Pripol 2033 by Croda, hydroxyl equivalent 270 g / eq) and a reaction product of chloromethyloxirane (having the skeleton of 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

[Synthesis 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, 120 to 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 wt%, an acid value (in terms of solid content) of 84.1 mgKOH / g, and a molecular weight (Mw) of 3400.

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

(I) -1: Alkali-soluble resin obtained in Synthesis Example 1 (i) -2: 68.9% PGMEA solution of cresol novolac acid-modified epoxy acrylate resin (CCR-1172, manufactured by Nippon Kayaku Co., Ltd.)
(Ii): Dipentaerythritol hexaacrylate (iii): Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) ( OXE02 manufactured by BASF)
(Iv): PGMEA dispersion of carbon black 20.0% by mass and polymer dispersant 5.0% by mass (solid content 25.0%, average secondary particle size of carbon black 162 nm)
Solvent: Propylene glycol monomethyl ether acetate

  The above-described blending components were blended in the proportions shown in Table 1 to prepare photosensitive colored resin compositions of Example 1 and Comparative Example 1. In addition, all the numerical values in Table 1 represent parts by mass.

[Evaluation of Photosensitive Colored Resin Compositions of Example 1 and Comparative Example 1]
The photosensitive colored resin composition shown in Table 1 was applied on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post baking was 1.4 μm, and prebaked at 90 ° C. for 1 minute. A coated plate was prepared. Thereafter, an ultraviolet ray having a wavelength of 365 nm and an illuminance of 30 mW / cm ² was irradiated with an exposure amount of 100 mJ / cm ² through a 500 W / cm ² high-pressure mercury lamp through a photomask for pattern formation, and a photocuring reaction was performed on 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 0.15 wt% sodium carbonate aqueous solution and shower development at 23 ° C., further washed with spray water, and an unexposed portion of the coating film. Was removed. Then, the cured film which concerns on Example 1 and Comparative Example 1 was obtained by performing a heat-curing process for 30 minutes at 230 degreeC using a hot air dryer.

  The cured film obtained under the above conditions was evaluated as follows. In addition, at the time of preparation of the cured film for the film thickness test, development, washing with water, and heat-curing treatment were performed after the entire surface exposure not through the photomask.

(Film thickness)
A part 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.).

(Resolution)
When exposed and developed using a photomask for pattern formation, the pattern forming ability was measured with an optical microscope.
○: Pattern can be formed (5 μm to 30 μm line & space pattern remains)
×: Not dissolved in developer or pattern peeling

(Wrinkle resistance)
The photosensitive colored resin composition shown in Table 1 was applied on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post baking was 1.4 μm, and prebaked at 90 ° C. for 1 minute. A coated plate was prepared. Thereafter, UV light having a wavelength of 365 nm and an illuminance of 30 mW / cm ² was irradiated with an exposure amount shown in Table 2 with a 500 W / cm ² high-pressure mercury lamp without passing through a photomask to perform photocuring reaction on the entire surface. Then, the cured film which concerns on Example 1 and Comparative Example 1 was obtained by performing a heat-curing process for 30 minutes at 230 degreeC using a hot air dryer.

The presence or absence of wrinkles on the surface of the cured film after the heat curing treatment was evaluated visually.
○: Wrinkles are not confirmed ×: Wrinkles occur

  From Table 2, when the colored photosensitive resin composition of the present invention is used, a pattern with a smooth surface can be obtained without wrinkling the surface of the pattern even when the exposure amount is increased. For this reason, compared with the case where the photosensitive resin composition of Comparative Example 1 is used, the surface is wrinkled even when it is necessary to increase the exposure amount for patterning when a thick pattern is required. It is possible to meet various user-required characteristics by being able to obtain a cured film pattern free from any problem.

Claims (5)

(I) a polymerizable unsaturated group-containing alkali-soluble resin comprising a polymer having a structure represented by the general formula (1);
(Ii) a photopolymerizable monomer having at least two polymerizable unsaturated groups,
(Iii) a photopolymerization initiator, and (iv) a dispersoid,
Is contained as an essential component.

(In the general formula (1), 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 represented by the following general formula (2) or a hydrogen atom, and m is an average value of 1 to 20.)

(In general formula (2), M represents a divalent or trivalent carboxylic acid residue, and p is 1 or 2.)   (V) The photosensitive resin composition according to claim 1, further comprising an epoxy resin or an epoxy compound having two or more epoxy groups.   (Iii) 0.1-30 mass parts of (iii) component is contained with respect to a total of 100 mass parts of (i) component and (ii) component, and (iv) 1-95 mass% component is contained with respect to total solid content. The photosensitive resin composition according to claim 1, wherein:   (Iii) 0.1-30 mass parts of (iii) component, 10-40 mass parts of (v) component are contained with respect to a total of 100 mass parts of (i) component and (ii) component, It contains 1-95 mass% with respect to solid content, The photosensitive resin composition of Claim 2 characterized by the above-mentioned.   Hardened | cured material obtained by hardening the photosensitive resin composition of any one of Claims 1-4.