Polymerizable-unsaturated-group-containing alkali-soluble resin, method for producing the same, photosensitive resin composition, and cured product thereof

Abstract

To provide a photosensitive resin composition capable of patterning with exceptional resolution by alkaline development, the photosensitive resin composition yielding a cured product that can be applied to an insulating film, etc., having exceptional chemical resistance and also exceptional reliability such as seam folding resistance; a polymerizable-unsaturated-group-containing alkali-soluble resin used in the photosensitive resin composition; and a method for producing the resin.SOLUTION: The present invention provides a method for producing a polymerizable-unsaturated-group-containing alkali-soluble resin, wherein an epoxy (meth)acrylate resin represented by general formula (1) is reacted with a dicarboxylic acid, tricarboxylic acid, or acid anhydride thereof and a tetracarboxylic acid or an acid dianhydride thereof. Herein, R1 represents a C1-8 alkyl group, a phenyl group, or an allyl group, R2 represents a hydrogen atom or a dicyclopentenyl group, and R3 represents a hydrogen atom or a methyl group.SELECTED DRAWING: None

Description

[Technical field]

[0001] 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 polymerizable unsaturated group-containing alkali-soluble resin as an essential component, and a cured film obtained by curing the composition. The photosensitive resin composition containing the specific polymerizable unsaturated group-containing alkali-soluble resin of the present invention and its cured product can be used as 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 gas barrier film, a lens, and a sealing material for semiconductor light-emitting elements such as light-emitting diodes (LEDs), a top coat for paints and inks, a hard coat for plastics, and an anti-rust film for metals. [Background technology]

[0002] In recent years, with the high performance and high definition of electronic devices and display members, electronic components used therein are required to be smaller and more dense. In addition, the insulating materials used therein are also required to be finer and have a more suitable cross-sectional shape of the processed pattern. A patterning method by exposure and development is known as an effective means for fine processing of insulating materials, and a photosensitive resin composition has been used therein, but many characteristics such as high sensitivity, adhesion to the substrate, reliability, heat resistance, and chemical resistance are required. In addition, various studies have been conducted on the use of organic insulating materials in the gate insulating film for organic TFTs, but there is a need to reduce the operating voltage of the organic TFT by thinning the gate insulating film, and the application of a thin film of about 0.2 μm has been considered for organic insulating materials that generally have a dielectric strength of about 1 MV / cm.

[0003] In the conventional insulating material made of a photosensitive resin composition, a photocuring reaction caused by a reaction between a photoreactive alkali-soluble resin and a photopolymerization initiator is utilized, and i-rays (365 nm), which are one of the line spectra of mercury lamps, are mainly used as the exposure wavelength for photocuring. However, this i-ray is absorbed by the photosensitive resin itself and the colorant, causing a decrease in the degree of photocuring. Moreover, the amount of absorption increases if the film is thick. Therefore, a difference in crosslink density occurs in the film thickness direction in the exposed part, and even if the coating film surface is sufficiently photocured, it is difficult to photocur the bottom surface of the coating film, so it becomes extremely difficult to make a difference in crosslink density between the exposed part and the unexposed part, and the pattern dimensional stability, development margin, pattern adhesion, edge shape and cross-sectional shape of the pattern are deteriorated, making it difficult to obtain a photosensitive insulating material that can be developed with high resolution.

[0004] In general, photosensitive resin compositions for such applications contain polyfunctional photocurable monomers having polymerizable unsaturated bonds, alkali-soluble binder resins, photopolymerization initiators, etc., and photosensitive resin compositions disclosed technically as materials for color filters can be used. For example, Patent Document 1 and Patent Document 2 disclose copolymers containing a specific unsaturated organic acid ester and an unsaturated organic acid as binder resins. Patent Document 3 discloses that an alkali-soluble unsaturated compound having a polymerizable unsaturated double bond and a carboxyl group in one molecule is effective for forming negative patterns such as color filters.

[0005] On the other hand, Patent Documents 4, 5, 6 and 7 disclose liquid resins using reaction products of epoxy (meth)acrylates having a bisphenol fluorene structure and acid anhydrides. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 61-213213 [Patent Document 2] Japanese Patent Application Publication No. 1-152449 [Patent Document 3] Japanese Patent Application Publication No. 4-340965 [Patent Document 4] Japanese Patent Application Publication No. 4-345673 [Patent Document 5] Japanese Patent Application Publication No. 4-345608 [Patent Document 6] Japanese Patent Application Publication No. 4-355450 [Patent Document 7] Japanese Patent Application Publication No. 4-363311

[0007] However, the copolymers disclosed in Patent Documents 1 and 2 are random copolymers, and therefore distribution of alkali dissolution rate occurs in both the light-exposed and non-light-exposed areas, resulting in a narrow margin during development, making it difficult to obtain acute-angled pattern shapes and fine patterns. In particular, when a high concentration of pigment is contained, the exposure sensitivity is significantly reduced, making it impossible to obtain fine negative patterns.

[0008] In addition, the alkali-soluble unsaturated compound described in Patent Document 3 is insolubilized by light irradiation, and is therefore expected to have higher sensitivity than the combination of the binder resin and polyfunctional polymerizable monomer described above. However, the compounds exemplified therein are obtained by arbitrarily adding acrylic acid and acid anhydride, which are polymerizable unsaturated groups, to the hydroxyl groups of a phenol oligomer. In the case of such a proposal, a wide distribution can be formed in the molecular weight of each molecule and the amount of carboxyl groups, and therefore the distribution of the alkali dissolution rate of the alkali-soluble resin becomes wide, making it difficult to form a fine negative pattern.

[0009] In addition, the resins exemplified in Patent Documents 4, 5, 6, and 7 are reaction products of epoxy (meth)acrylate and acid anhydride, and therefore have small molecular weights, making it difficult to increase the difference in alkali solubility between exposed and unexposed areas, and thus making it impossible to form fine patterns.

[0010] As described above, photolithography methods using various photosensitive resin compositions are used as a method for microfabrication of insulating materials, but after the pattern is fined and the shape is optimized, the formed insulating film is required to have many properties such as adhesion to the substrate, reliability, heat resistance, chemical resistance, etc. For example, when used in flexible displays and touch panels, resistance to seam breakage may be required, and it is becoming necessary to provide a material that is also excellent in chemical resistance required for electrode processing processes after insulating film formation. Summary of the Invention [Problem to be solved by the invention]

[0011] The present invention provides a photosensitive resin composition that can be used for insulating films, etc., which is capable of patterning with excellent resolution by alkaline development, and also has excellent chemical resistance when a processing process such as electrode formation is required after forming an insulating film in a touch panel manufacturing process, etc., and is also excellent in reliability such as seam breakage resistance. Another object of the present invention is to provide a method for producing a polymerizable unsaturated group-containing alkali-soluble resin used in this photosensitive resin composition, a polymerizable unsaturated group-containing alkali-soluble resin produced by this production method, and a cured film obtained by curing this photosensitive resin composition. [Means for solving the problem]

[0012] The present inventors have found that, in order to solve the above problems, it is effective to use a photosensitive resin composition that includes an alkali-soluble resin containing a polymerizable unsaturated group having a specific alicyclic structure, and have completed the present invention.

[0013] The present invention relates to a method for producing an alkali-soluble resin containing a polymerizable unsaturated group, which comprises reacting an epoxy (meth)acrylate resin represented by the following general formula (1) with (a) a dicarboxylic acid, a tricarboxylic acid or an acid anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof:

[0014] [ka] Where: R 1 each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or an allyl group, R 2 each independently represents a hydrogen atom or a dicyclopentenyl group, and one or more of them are dicyclopentenyl groups. R 3 represents a hydrogen atom or a methyl group.

[0015] Another embodiment of the present invention relates to a polymerizable unsaturated group-containing alkali-soluble resin obtained by the above production method, the alkali-soluble resin having a polymerizable unsaturated group and a structure represented by general formula (2).

[0016] [ka] Where: X represents a tetravalent carboxylic acid residue, Y represents a carboxyl group-containing group represented by the above formula (3) or a hydrogen atom, Z represents a structure represented by the above formula (2a), m is a number with an average value between 1 and 20. R 1 represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or an allyl group, R 2 each independently represents a hydrogen atom or a dicyclopentenyl group, and one or more of them are dicyclopentenyl groups. R 3 represents a hydrogen atom or a methyl group. M represents a carboxylic acid residue having a valence of p+1, and p is 1 or 2.

[0017] In addition, another embodiment of the present invention is (A) the above-mentioned alkali-soluble resin containing a polymerizable unsaturated group, (B) a photopolymerizable monomer having at least two polymerizable unsaturated groups; (C) a photoinitiator, and (D) Solvent The present invention relates to a photosensitive resin composition comprising the above as an essential component.

[0018] Another embodiment of the present invention relates to a cured product obtained by curing the above-mentioned photosensitive resin composition. Effect of the Invention

[0019] The photosensitive resin composition using the alkali-soluble resin containing a polymerizable unsaturated group 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 crack folding characteristics, and can be used as an insulating film for flexible displays and touch panels. In addition, when a processing process such as electrode formation is required after forming an insulating film in a touch panel manufacturing process, etc., a cured product pattern having excellent chemical resistance can be obtained. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The present invention will be described in detail below. One embodiment of the present invention relates to a method for producing a polymerizable unsaturated group-containing alkali-soluble resin by reacting an epoxy (meth)acrylate resin represented by general formula (1) with (a) a dicarboxylic acid, a tricarboxylic acid, or an acid anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof, and to a polymerizable unsaturated group-containing alkali-soluble resin produced by the method.

[0021] In the general formula (1), R 1 independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or an allyl group. The alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, and examples thereof include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a hexyl group, a cyclohexyl group, and a methylcyclohexyl group. Among these substituents, from the viewpoints of availability and reactivity when formed into a cured product, a phenyl group and a methyl group are preferred, and a methyl group is particularly preferred.

[0022] R 2are independently a hydrogen atom or a dicyclopentenyl group, and one or more are dicyclopentenyl groups. The dicyclopentenyl group is a group derived from dicyclopentadiene and is represented by the following formula (1a) or formula (1b). [ka]

[0023] The raw material for the above epoxy (meth)acrylate resin is obtained by the reaction of a dicyclopentadiene-type epoxy resin with (meth)acrylic acid (referring to acrylic acid, methacrylic acid, or both). This epoxy resin can be obtained by reacting a diphenol compound represented by the following general formula (4) with an epihalohydrin such as epichlorohydrin to perform epoxidation. This diphenol compound can be obtained by reacting a 2,6-disubstituted phenol compound with dicyclopentadiene in the presence of a catalyst such as boron trifluoride ether complex. [ka] Where: R 1 and R 2 are the same as defined in the above general formula (1).

[0024] The diphenol compound can be obtained by adding preferably 0.28 to 2.0 mol, more preferably 0.28 to 1.0 mol, and even more preferably 0.3 to 0.5 mol of dicyclopentadiene to 1 mol of the 2,6-disubstituted phenol compound, and reacting them in the presence of a catalyst.

[0025] Examples of the 2,6-disubstituted phenol compound include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2,6-diisopropylphenol, 2,6-di(n-butyl)phenol, 2,6-di(t-butyl)phenol, 2,6-dihexylphenol, 2,6-dicyclohexylphenol, and 2,6-diphenylphenol. From the viewpoints of availability and reactivity when formed into a cured product, 2,6-dimethylphenol is preferred.

[0026] The acid catalyst used in the reaction of 2,6-disubstituted phenol compounds with dicyclopentadiene is a Lewis acid, specifically boron trifluoride compounds such as boron trifluoride, boron trifluoride-phenol complex, and boron trifluoride-ether complex, metal chlorides such as aluminum chloride, tin chloride, zinc chloride, titanium tetrachloride, and iron chloride, and organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and propanesulfonic acid, among which boron trifluoride-ether complex is preferred from the viewpoint of ease of handling. The amount of the acid catalyst used in the case of boron trifluoride-ether complex is 0.001 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of dicyclopentadiene.

[0027] A suitable reaction method is to charge a 2,6-disubstituted phenol compound and a catalyst in a reactor, and then add dicyclopentadiene dropwise over a period of 1 to 10 hours. The reaction temperature is preferably 50 to 200° C., more preferably 100 to 180° C., and further preferably 120 to 160° C. The reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, and further preferably 4 to 8 hours.

[0028] After the reaction is completed, an alkali such as sodium hydroxide or potassium hydroxide is added to deactivate the catalyst, and the unreacted 2,6-disubstituted phenol compound is recovered under reduced pressure.

[0029] Thereafter, in order to separate and purify the reaction product, a solvent such as toluene, xylene, methyl ethyl ketone, or methyl isobutyl ketone is added to dissolve it, and the mixture is washed with water. After that, the solvent and unreacted raw materials are recovered under reduced pressure, whereby the target diphenol compound can be obtained.

[0030] During the reaction, a solvent such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, ethylene glycol dimethyl ether, or diethylene glycol dimethyl ether may be used as necessary for adjusting the viscosity.

[0031] The introduction of the dicyclopentenyl group into the diphenol compound can be confirmed by mass spectrometry and FT-IR measurement.

[0032] When using mass spectrometry, electrospray ionization mass spectrometry (ESI-MS) or field desorption mass spectrometry (FD-MS) can be used. By subjecting a sample in which components with different nuclei numbers have been separated using GPC or the like to mass spectrometry, it is possible to confirm that the dicyclopentenyl group has been introduced.

[0033] When using the FT-IR measurement method, a sample dissolved in an organic solvent such as tetrahydrofuran is applied to a KRS-5 cell, and the organic solvent is dried to obtain a cell with a thin film of the sample. When this cell is measured by FT-IR, a peak due to the CO stretching vibration of the phenol nucleus is observed at 1210 cm -1 Only when a dicyclopentenyl group is introduced, a peak due to the CH stretching vibration of the olefin part of the dicyclopentadiene skeleton appears around 3040 cm -1 It appears around 3040 cm. The baseline is a straight line connecting the start and end of the peak, and the peak height is the distance from the peak to the baseline. -1 Nearby peaks (A 3040 ) and 1210cm -1 Nearby peaks (A 1210 ) ratio (A 3040 / A 1210The amount of dicyclopentenyl groups introduced can be quantified by the ratio. It has been confirmed that the higher the ratio, the better the physical properties. 3040 / A 1210 ) is 0.05 or more, more preferably 0.1 or more.

[0034] The diphenol compound obtained by the above method is reacted with epihalohydrin to obtain a dicyclopentadiene type epoxy resin. This reaction is carried out according to a conventional method.

[0035] For example, an alkali metal hydroxide such as sodium hydroxide is added as a solid or concentrated aqueous solution to a mixture of a diphenol compound and an excess molar amount of epihalohydrin relative to the hydroxyl groups of the diphenol compound, and the mixture is reacted at a reaction temperature of 30 to 120°C for 0.5 to 10 hours; alternatively, a quaternary ammonium salt such as tetraethylammonium chloride is added as a catalyst to a diphenol compound and an excess molar amount of epihalohydrin, and the mixture is reacted at a temperature of 50 to 150°C for 1 to 5 hours to obtain a polyhalohydrin ether, to which an alkali metal hydroxide such as sodium hydroxide is added as a solid or concentrated aqueous solution, and the mixture is reacted at a temperature of 30 to 120°C for 1 to 10 hours.

[0036] In the above reaction, the amount of epihalohydrin used is 1 to 10 times, and preferably 2 to 5 times, the molar amount of the hydroxyl groups of the diphenol compound, and the amount of alkali metal hydroxide used is 0.85 to 1.1 times the molar amount of the hydroxyl groups of the diphenol compound.

[0037] Since the epoxy resin obtained by these reactions contains unreacted epihalohydrin and alkali metal halide, the desired epoxy resin can be obtained by removing the unreacted epihalohydrin from the reaction mixture by evaporation, and then removing the alkali metal halide by extraction with water, filtration, etc. The epoxy resin obtained in this manner is a dicyclopentadiene type epoxy resin and is represented by the following general formula (5).

[0038] [ka] Where: R 1 and R 2 are the same as defined in the above general formula (1), n is the number of repetitions, and the average value is a number from 0 to 5.

[0039] The epoxy equivalent (g / eq.) of the epoxy resin is preferably from 244 to 3,700, more preferably from 260 to 2,000, and even more preferably from more than 270 to less than 700.

[0040] The molecular weight distribution of the obtained epoxy resin can be changed by changing the charging ratio of the diphenol compound and epihalohydrin during the epoxidation reaction, and the closer the amount of epihalohydrin used to the hydroxyl groups of the diphenol compound, the higher the molecular weight distribution, and the closer it is to 20 times the molar amount, the lower the molecular weight distribution. It is also possible to increase the molecular weight by reacting the obtained epoxy resin with a diphenol compound again. However, in order to appropriately control the molecular weight of the alkali-soluble resin containing a polymerizable unsaturated group of the present invention, the content of n=0 in the general formula (5) is preferably 50% or more, more preferably 70% or more, even more preferably 85% or more, and particularly preferably 95% or more. Furthermore, n is in the range of 0 to 5 on average, preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0 to 0.5. Within this range, it is easy to suppress excessive increase in molecular weight due to addition of acid dianhydride.

[0041] The above epoxy resin is reacted with (meth)acrylic acid to form an epoxy (meth)acrylate resin having a polymerizable unsaturated group. The epoxy resin and (meth)acrylic acid can be reacted by a known method. For example, an equimolar amount of (meth)acrylic acid is used for 1 mole of epoxy groups in the epoxy resin. However, in order to react all epoxy groups with (meth)acrylic acid, a slightly excess amount of (meth)acrylic acid may be used over the equimolar amount of epoxy groups and carboxyl groups. This reaction produces an epoxy (meth)acrylate resin in which the glycidyl group in the general formula (5) is replaced with a group represented by the following formula (6).

[0042] [ka] Where: R 3 is defined as in the above general formula (1).

[0043] The solvent and catalyst used in this reaction, as well as 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 cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling ether or ester-based solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and further ketone-based solvents such as cyclohexanone and diisobutyl ketone. Examples of the catalyst include known catalysts such as ammonium salts including tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine, tris(2,6-dimethoxyphenyl)phosphine, and the like.

[0044] This reaction produces an epoxy (meth)acrylate resin represented by general formula (1). This epoxy (meth)acrylate resin contains by-products resulting from side reactions and by-products contained during the synthesis of raw materials, but these may be purified and removed before use, or may be used with some of the by-products remaining as long as they do not impair the quality or application of the product.

[0045] The epoxy (meth)acrylate resin can be reacted with a carboxylic acid to obtain an alkali-soluble resin containing a polymerizable unsaturated group. As the carboxylic acids, (a) dicarboxylic acids or tricarboxylic acids and (b) tetracarboxylic acids are used. As the dicarboxylic acids or tricarboxylic acids, dicarboxylic acids or tricarboxylic acids or their anhydrides may be used, but acid anhydrides are preferred in terms of reactivity. Similarly, as the tetracarboxylic acids, tetracarboxylic acids or their dianhydrides may be used, but acid dianhydrides are preferred in terms of reactivity.

[0046] Examples of the (a) dicarboxylic acid, tricarboxylic acid or anhydride thereof include saturated chain hydrocarbon dicarboxylic acid or tricarboxylic acid or anhydride thereof, saturated cyclic hydrocarbon dicarboxylic acid or tricarboxylic acid or anhydride thereof, unsaturated hydrocarbon dicarboxylic acid or tricarboxylic acid or anhydride thereof, aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid or anhydride thereof, etc. Each hydrocarbon residue (structure excluding carboxyl group) of these dicarboxylic acids or tricarboxylic acids or anhydrides thereof may be further substituted with a substituent such as an alkyl group, a cycloalkyl group, or an aromatic group.

[0047] Examples of saturated chain hydrocarbon dicarboxylic acids or tricarboxylic acids include succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid. Examples of saturated cyclic hydrocarbon dicarboxylic acids or tricarboxylic acids include hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, and hexahydrotrimellitic acid. Examples of unsaturated hydrocarbon dicarboxylic acids or tricarboxylic acids include maleic acid, itaconic acid, tetrahydrophthalic acid, methyl end methylene tetrahydrophthalic acid, and chlorendic acid. Examples of aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids include phthalic acid and trimellitic acid. Acid anhydrides of these dicarboxylic acids or tricarboxylic acids 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 acid anhydrides are more preferred.

[0048] Examples of the (b) tetracarboxylic acid or its dianhydride include chain hydrocarbon tetracarboxylic acid or its dianhydride, alicyclic tetracarboxylic acid or its dianhydride, and aromatic polyvalent carboxylic acid or its dianhydride, etc. Each hydrocarbon residue (structure excluding carboxyl group) of these tetracarboxylic acids or their dianhydrides may be further substituted with a substituent such as an alkyl group, a cycloalkyl group, or an aromatic group.

[0049] Specific examples of tetracarboxylic acids include butane tetracarboxylic acid, pentane tetracarboxylic acid, and hexane tetracarboxylic acid. Examples of alicyclic tetracarboxylic acids include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, and norbornane tetracarboxylic acid. Examples of aromatic polycarboxylic acids 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.

[0050] The molar ratio (a) / (b) of the carboxyl group of (a) dicarboxylic acid, tricarboxylic acid or their acid anhydride (acid anhydride group is calculated as 2 moles of carboxyl group) used in the above reaction to the carboxyl group of (b) tetracarboxylic acid or its acid dianhydride (acid anhydride group is calculated as 2 moles of carboxyl group) is preferably 0.01 to 0.5, more preferably 0.02 to 0.3, and even more preferably 0.03 or more and less than 0.1. If the molar ratio (a) / (b) is within the above range, it becomes easier to obtain an optimal molecular weight for making a photosensitive resin composition having good photopatterning properties. Note that the smaller the molar ratio (a) / (b), the higher the alkali solubility and the higher the molecular weight.

[0051] The ratio of the epoxy (meth)acrylate resin (c) containing a polymerizable unsaturated group to the carboxylic acid components (a) and (b) is preferably such that the terminals of the compounds are carboxyl groups, and the components (c):(a):(b) are quantitatively reacted at 1:0.2-1.0:0.01-1.0, preferably 1:0.2-0.4:0.4-0.8. In this case, it is desirable to quantitatively react the components so that the molar ratio of the total amount of the acid components to the epoxy (meth)acrylate resin is (c) / [(a) / 2+(b)]=0.5-1.0. If this molar ratio is less than 0.5, the terminals of the alkali-soluble resin become acid anhydrides, and the content of unreacted acid dianhydrides increases, which may cause a decrease in the stability over time of the alkali-soluble resin composition. On the other hand, if the molar ratio exceeds 1.0, the content of hydroxyl-containing compounds containing unreacted polymerizable unsaturated groups increases, which may cause a decrease in the stability over time of the alkali-soluble resin composition. The molar ratio of each of the components (a), (b) and (c) can be changed freely within the above-mentioned ranges in order to adjust the acid value and molecular weight of the alkali-soluble resin. In another preferred embodiment, the epoxy (meth)acrylate resin (c) is reacted quantitatively with 0.1 to 1.0 mol, preferably 0.5 to 1.0 mol, of the total amount of carboxyl groups (acid anhydride groups are calculated as 2 mol of carboxyl groups) of the carboxylic acid components [(a)+(b)] relative to 1 mol of hydroxyl groups of the epoxy (meth)acrylate resin (c).

[0052] The reaction of the above (a) dicarboxylic acid, tricarboxylic acid, or anhydride thereof, and (b) tetracarboxylic acid or anhydride thereof can be carried out by heating and stirring at 90 to 130° C. in the presence of a catalyst such as triethylamine, tetraethylammonium bromide, or triphenylphosphine.

[0053] The acid value of the polymerizable unsaturated group-containing alkali-soluble resin produced by the above-mentioned production method is preferably 30 to 200 mgKOH / g, more preferably 50 to 150 mgKOH / g. If the acid value is less than 30 mgKOH / g, residues are likely to remain during alkaline development, and if it exceeds 200 mgKOH / g, the penetration of the alkaline developer becomes too fast, which may cause peeling development.

[0054] In the above-mentioned production method, from the viewpoint of reducing the viscosity of the produced polymerizable unsaturated group-containing alkali-soluble resin, the content of n=0 in the general formula (5) is preferably 50% or more, more preferably 70% or more, even more preferably 85% or more, and particularly preferably 95% or more. Furthermore, n is in the range of 0 to 5 on average, preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0 to 0.5.

[0055] In addition, the polymerizable unsaturated group-containing alkali-soluble resin produced by the above-mentioned production method preferably has a hydrolyzable halogen content of 0.2 mass% or less. If the hydrolyzable halogen content is 0.2 mass% or less, the hydrolyzable halogen is unlikely to inhibit the curing reaction, and the physical properties of the cured product, particularly the insulation reliability, are unlikely to decrease, making it preferable for use in the electrical and electronic fields. The hydrolyzable halogen content is preferably 0.1 mass% or less, and more preferably 0.05 mass% or less.

[0056] In the above-mentioned production method, for example, when n=0 in general formula (5), an epoxy (meth)acrylate resin represented by the above general formula (1) is obtained, and further, an alkali-soluble resin containing a polymerizable unsaturated group and having a structure represented by the above general formula (2) is produced. The polymerizable unsaturated group-containing alkali-soluble resin of the present invention is not limited to the resin having the structure represented by general formula (2), but may also be a resin containing resins with different degrees of polymerization produced at each stage of the above-mentioned production method or resins derived therefrom. In the general formula (2), m is a number of 1 to 20, preferably in the range of 1.5 to 10, and more preferably in the range of 2 to 5, on average.

[0057] Incidentally, the epoxy resin obtained by the above manufacturing method may also contain a component in which n=1 or more in the general formula (5). Since the epoxy (meth)acrylate resin obtained from these epoxy resins in which n=1 or more contains three or more hydroxyl groups, it may be difficult to control the increase in molecular weight by reaction with anhydrides, particularly reaction with (b) tetracarboxylic acid or its dianhydride. The polymerizable unsaturated group-containing alkali-soluble resin is represented by the following formula (7). The polymerizable unsaturated group-containing alkali-soluble resin is a mixture of oligomers of various molecular weights, and the L of the following formula (7a) 3 is the L of other molecules 1 Or L 2 Since the epoxy resin is bonded as one of the above, the polymerization proceeds with a structure other than that of the above general formula (2). However, as long as the content of the epoxy resin is within the range of the above-mentioned n=0 form, the effects of the present invention are not affected even if these components are contained.

[0058] [ka] Where: R 3 is defined as in the above general formula (1), X and Z are defined as in the above general formula (2), n is as defined in the above general formula (5), L 1 and L 2 are independently a hydrogen atom, the above formula (7a), or the above formula (3), but are not all hydrogen atoms. Formula (3) is the same as in formula (2) above. L 3 is the L of other molecules 1 Or L 2 Combine as:

[0059] [Photosensitive resin composition] The photosensitive resin composition of the present invention contains the following components (A) to (D): (A) an alkali-soluble resin containing a polymerizable unsaturated group, which has a structure represented by general formula (2), (B) a photopolymerizable monomer having at least two polymerizable unsaturated groups; (C) a photoinitiator, and (D) Solvent

[0060] Examples of (B) 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, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, glycerol Examples of the photopolymerizable monomer include (meth)acrylic acid esters including ethyl acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, alkylene oxide modified hexa(meth)acrylate of phosphazene, and caprolactone modified dipentaerythritol hexa(meth)acrylate, polyhydric alcohols including pentaerythritol and dipentaerythritol, vinyl benzyl ether compounds of polyhydric 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 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. Incidentally, (B) the photopolymerizable monomer having at least two polymerizable unsaturated groups does not have a free carboxy group.

[0061] The blending ratio of the (B) component is preferably 5 to 400 parts by mass, more preferably 10 to 150 parts by mass, per 100 parts by mass of the (A) component. If the blending ratio of the (B) component is more than 400 parts by mass per 100 parts by mass of the (A) component, the photocured product becomes brittle, and the acid value of the coating film is low in the unexposed area, so that the solubility in an alkaline developer is reduced, and the pattern edge becomes jagged and not sharp. On the other hand, if the blending ratio of the (B) component is less than 5 parts by mass per 100 parts by mass of the (A) component, the proportion of photoreactive functional groups in the resin is low, so that the formation of a crosslinked structure is insufficient, and furthermore, the acid value of the resin component is high, so that the solubility in an alkaline developer in the exposed area is high, so that the formed pattern may be narrower than the target line width, or the pattern may be easily missing.

[0062] Examples of the (C) photopolymerization initiator include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and pt-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethylaminobenzophenone; benzoin ethers such as benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Ethers, biimidazole compounds including 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-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-oxadiazo and halomethyldiazole compounds including 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3, Halomethyl-s-triazine compounds including 5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,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-carbazole-3 -yl]-,1-(0-acetyl oxime),methanone,(9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]-,O-acetyl oxime,methanone,(2-methylphenyl)(7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-,acetyl oxime,ethanone,1-[7-(2-methylbenzoyl)-9,9-dipropyl-9 O-acyloxime compounds including ethanone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-, 1-O-acetyloxime, and the like; sulfur compounds including benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone, and the like; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone, and the like; organic peroxides including azobisisobutylnitrile, benzoyl peroxide, and cumene peroxide, and the like; and thiol compounds including 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole, and the like. These photopolymerization initiators may be used alone or in combination of two or more. In the present invention, the photopolymerization initiator is used in the sense including a sensitizer.

[0063] In addition, as the (C) photopolymerization initiator, a compound that does not act as a photopolymerization initiator or sensitizer by itself but can enhance the ability of the photopolymerization initiator or sensitizer when used in combination can be added. Examples of such compounds include tertiary amines such as triethanolamine and triethylamine, which are effective when used in combination with benzophenone.

[0064] The blending ratio of component (C) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 25 parts by mass, based on 100 parts by mass of the total of components (A) and (B). If the blending ratio of component (C) is less than 0.1 parts by mass, the photopolymerization speed will be slow and the sensitivity will be reduced, while if it exceeds 30 parts by mass, the sensitivity will be too strong, causing problems such as the pattern line width being thicker than the pattern mask, making it impossible to reproduce the line width faithfully to the mask, or the pattern edges being jagged and not sharp.

[0065] Examples of the (D) solvent include alcohols including methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes including α- or β-terpineol; ketones including acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons including toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol monoethyl ether, dipropylene glycol, and the like. Examples of the solvent include glycol ethers including dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether, and esters including ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. These solvents may be used alone, or two or more of them may be used in combination to satisfy properties such as coating properties.

[0066] In addition, the photosensitive resin composition may contain additives such as a curing accelerator, a thermal polymerization inhibitor and an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a coupling agent, a surfactant, and a colorant, if necessary. As the curing accelerator, for example, a known compound known as a curing accelerator, a curing catalyst, a latent curing agent, etc., which are usually applied to epoxy resins, can be used, and includes tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, diazabicyclo compounds, etc. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine, hindered phenol compounds, phosphorus-based heat stabilizers, etc. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate, etc. Examples of fillers include glass fiber, silica, mica, and alumina, etc. Examples of the leveling agent and the defoaming agent include silicone-based, fluorine-based, and acrylic compounds. Examples of the coupling agent include silane coupling agents such as vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-(phenylamino)propyltrimethoxysilane, and 3-ureidopropyltriethoxysilane. Examples of the surfactant include fluorine-based surfactants and silicone-based surfactants. As the colorant, known pigments and dyes can be used without any restrictions.

[0067] The photosensitive resin composition may further contain (E) an epoxy resin having two or more epoxy groups in addition to (A) to (D). Examples of such epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, bisphenol fluorene type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, polymers containing glycidyl (meth)acrylate as a unit, alicyclic epoxy resins represented by 3,4-epoxycyclohexanecarboxylic acid [(3,4-epoxycyclohexyl)methyl], 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol (e.g., "EHPE3150", manufactured by Daicel Corporation), phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, epoxidized polybutadiene (e.g., "NISSO-PB·JP-100", manufactured by Nippon Soda Co., Ltd.), and epoxy resins 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. Only one type of compound may be used as the component (E), or two or more types 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 preferred.

[0068] When the epoxy resin (E) is used, the amount of the epoxy resin is preferably 10 to 40 parts by mass relative to 100 parts by mass of the total of the components (A) and (B). One purpose of adding the epoxy resin is to reduce the amount of carboxyl groups remaining when the cured film is formed after patterning in order to increase the reliability of the cured film. In this case, if the amount of the epoxy resin added is less than 10 parts by mass, there is a risk that the moisture resistance reliability cannot be ensured when used as an insulating film, for example. In addition, if the amount of the epoxy resin is more than 40 parts by mass, the amount of photosensitive groups in the resin component in the photosensitive resin composition is reduced, and there is a risk that sufficient sensitivity for patterning cannot be obtained.

[0069] The photosensitive resin composition contains the above components (A) to (D) or (A) to (E) as main components. The total content of the components (A) to (C) and (E) in the solid content is desirably 70 mass %, preferably 80 mass % or more. The amount of the (D) solvent varies depending on the target viscosity, but it is preferable that the amount of the (D) solvent is in the range of 60 to 90 mass % in the photosensitive resin composition.

[0070] [Cured product] The photosensitive resin composition can be applied to a substrate or the like, dried, and irradiated (exposed) with light (including ultraviolet light, radiation, etc.) to cure the composition, thereby forming a cured product (coating film). At this time, a photomask or the like is used to provide areas that are exposed to light and areas that are not exposed to light, and only the areas exposed to light are cured, while the other areas are dissolved in an alkaline solution, thereby obtaining a cured product (coating film) with a desired pattern.

[0071] Specifically, when applying the photosensitive resin composition to a substrate, any of the known methods such as a solution immersion method, a spray method, or a method using a roller coater, a land coater, a slit coater or a spinner can be used.

[0072] By these methods, the photosensitive resin composition is applied to a desired thickness, and then the solvent is removed (prebaked) to form a coating. Prebaking is performed by heating in an oven or a hot plate, vacuum drying, or a combination of these. The heating temperature and heating time in prebaking are appropriately selected depending on the solvent used, and are performed, for example, at a temperature of 80 to 120°C for 1 to 10 minutes.

[0073] Examples of radiation used for exposure include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays, with radiation having a wavelength in the range of 250 to 450 nm being preferred.

[0074] 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 developer. These developers are selected according to the characteristics of the resin layer, and a surfactant may be added as necessary. Development is preferably carried out at a temperature of 20 to 35°C. Fine images can be precisely formed by using a commercially available developing machine, ultrasonic cleaner, or the like. After alkaline development, the substrate is usually washed with water. Examples of development methods include shower development, spray development, dip (immersion) development, and puddle (liquid puddle) development.

[0075] After development in this manner, a heat treatment (post-baking) is performed at a temperature of 180 to 250° C. for 20 to 100 minutes. This post-baking is performed for the purpose of increasing the adhesion between the patterned coating film and the substrate. Like the pre-baking, the post-baking is performed by heating using an oven, a hot plate, or the like.

[0076] Thereafter, polymerization or curing (both may be collectively referred to as curing) is completed by heat to obtain a cured film such as an insulating film, etc. The curing temperature at this time is preferably in the range of 160 to 250°C.

[0077] The cured product can also be used as a resist layer such as a solder resist layer, a plating resist layer, or an etching resist layer; an interlayer insulating layer for a multilayer printed wiring board or the like; a gas barrier film; a sealant for lenses and semiconductor light-emitting elements such as light-emitting diodes (LEDs); a top coat for paints or inks; a hard coat for plastics; and an anti-rust film for metals. EXAMPLES

[0078] Hereinafter, the embodiment of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited thereto. In the examples, "parts" means parts by mass, and "%" means % by mass unless otherwise specified. In addition, the evaluation of the resin in the synthesis examples was performed as follows unless otherwise specified.

[0079] [Solid content concentration] 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)), weighed [W1(g)], and the mass after heating at 160°C for 2 hours [W2(g)] was calculated from the following formula. Solid content concentration (mass%) = 100 × (W2-W0) / (W1-W0)

[0080] [Acid value] The resin solution was dissolved in dioxane and titrated with a 0.1N aqueous KOH 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 was taken as the acid value.

[0081] [Molecular weight] Measurement was performed using gel permeation chromatography (GPC) (HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuperH-2000 (2 columns) + TSKgelSuperH-3000 (1 column) + TSKgelSuperH-4000 (1 column) + TSKgelSuper-H5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, rate: 0.6 mL / min), and the weight average molecular weight (Mw) was calculated as a value converted into standard polystyrene (PS-oligomer kit manufactured by Tosoh Corporation).

[0082] [IR] A Fourier transform infrared spectrophotometer (Perkin Elmer Precisely, Spectrum One FT-IR Spectrometer 1760X) was used, and a KRS-5 cell was used. A sample dissolved in THF was applied to the cell, dried, and then measured at a wave number of 650 to 4000 cm. -1 The absorbance was measured.

[0083] [ESI-MS] Mass spectrometry was performed using a mass spectrometer (Shimadzu Corporation, LCMS-2020) with acetonitrile and water as the mobile phase, by measuring the sample dissolved in acetonitrile.

[0084] Synthesis Example 1 970 parts of 2,6-xylenol and 14.5 parts of 47% BF3 ether complex were charged into a reaction apparatus consisting of a glass separable flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, a dropping funnel, and a cooling tube, and heated to 70 ° C. while stirring. While maintaining the same temperature, 300 parts of dicyclopentadiene (0.29 times the moles of 2,6-xylenol) were dropped over 2 hours. Further, the reaction was carried out at a temperature of 125 to 135 ° C. for 6 hours, and 2.3 parts of calcium hydroxide were added. Further, 4.6 parts of a 10% aqueous oxalic acid solution were added. After that, the mixture was heated to 160 ° C. for dehydration, and then heated to 200 ° C. under a reduced pressure of 5 mmHg to evaporate and remove the unreacted raw materials. 1000 parts of MIBK were added to dissolve the product, and 400 parts of 80 ° C. hot water was added to wash it, and the lower layer water tank was separated and removed. Thereafter, the mixture was heated to 160° C. under a reduced pressure of 5 mmHg to evaporate and remove the MIBK, thereby obtaining 540 parts of a reddish-brown phenolic resin according to the general formula (4). The hydroxyl equivalent was 213, the softening point was 71° C., and the absorption ratio (A 3040 / A 1210 ) was 0.11. Mass spectrum was measured by ESI-MS (negative), and M-=253, 375, 507, and 629 were confirmed. From these absorption ratios of the FT-IR measurement and the ESI-MS measurement, it was confirmed that at least R 2 It can be seen that a dicyclopentenyl group is introduced as the

[0085] In a reaction apparatus similar to that of Synthesis Example 1, 250 parts of the obtained phenolic resin, 544 parts of epichlorohydrin, and 163 parts of diethylene glycol dimethyl ether were added and heated to 65°C. Under a reduced pressure of 125 mmHg, while maintaining the temperature at 63 to 67°C, 108 parts of a 49% aqueous sodium hydroxide solution were dropped over 4 hours. During this time, epichlorohydrin was azeotroped with water, and the water that flowed out was sequentially removed from the system. After the reaction was completed, epichlorohydrin was recovered under conditions of 5 mmHg and 180°C, and 948 parts of MIBK were added to dissolve the product. Then, 263 parts of water were added to dissolve the by-produced salt, and the solution was left to stand and the lower layer of saline was separated and removed. After neutralization with an aqueous phosphoric acid solution, the resin solution was washed with water until the washing water became neutral, and filtered. The mixture was heated to 180°C under a reduced pressure of 5mmHg to distill off the MIBK, yielding 298 parts of a reddish-brown transparent 2,6-xylenol-dicyclopentadiene type epoxy resin of general formula (5). The epoxy equivalent was 282, the total chlorine content was 980ppm, and the resin was semi-solid at room temperature, with n (average value) of general formula (5) being 0.05.

[0086] In the same reaction apparatus as in Synthesis Example 1, 282 parts of the obtained 2,6-xylenol-dicyclopentadiene type epoxy resin was dissolved in 63 parts of PGMEA, and 72 parts of acrylic acid, 3.5 parts of triphenylphosphine, and 0.1 parts of hydroquinone were added. The mixture was reacted at 110°C for 8 hours while blowing in air, and then 293 parts of PGMEA was added to obtain a PGMEA solution of epoxy acrylate resin (DPXLEA). The solid content of the obtained resin solution was 50%. The obtained DPXLEA was subjected to GPC measurement by the above-mentioned method, and the content of n=0 was 95 area %, and the total content of n=1 and n=2 was 5 area %.

[0087] The abbreviations used in the examples and comparative examples are as follows. DPXLEA: epoxy acrylate resin obtained in Synthesis Example 1 above BPAEA: Reaction product of bisphenol A epoxy resin (epoxy equivalent weight 182) and acrylic acid (equivalent reaction product of epoxy group and carboxyl group) BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride THPA: 1,2,3,6-Tetrahydrophthalic anhydride TEAB: Tetraethylammonium bromide MIBK: Methyl isobutyl ketone PGMEA: Propylene glycol monomethyl ether acetate

[0088] Example 1 In a reaction vessel equipped with a stirrer, a temperature controller, a reflux condenser, and an air introduction device, 450 parts of a 50% PGMEA solution of DPXLEA, 49 parts of BPDA, 25 parts of THPA, 0.69 parts of TEAB, and 20 parts of PGMEA were charged and stirred for 6 hours under heating at 120 to 125°C to obtain an alkali-soluble resin (A1). The solid content of the obtained resin was 55%, the acid value (solid content equivalent) was 92 mgKOH / g, and the molecular weight (Mw) was 3600.

[0089] Comparative Example 1 In the same apparatus as in Example 1, 291 parts of 50% PGMEA solution of BPAEA, 4 parts of dimethylolpropionic acid, 11.8 parts of 1,6-hexanediol, and 84 parts of PGMEA were charged, and the temperature was raised to 45°C. Next, 61.8 parts of isophorone diisocyanate was dropped while paying attention to the temperature in the flask. After the dropwise addition was completed, the mixture was stirred for 6 hours under heating at 75 to 80°C. Furthermore, 21 parts of THPA was charged, and the mixture was stirred for 6 hours under heating at 90 to 95°C to obtain an alkali-soluble resin solution (HA1). The solid content concentration of the obtained resin was 66.5%, the acid value (solid content equivalent) was 38.4 mgKOH / g, and the molecular weight (Mw) was 12220.

[0090] Next, the present invention will be specifically described based on examples and comparative examples relating to a photosensitive resin composition and a 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.

[0091] A1: Alkali-soluble resin obtained in Example 1 above HA1: Alkali-soluble resin obtained in Comparative Example 1 HA2: 68.9% PGMEA solution of cresol novolac acid-modified epoxy acrylate resin (CCR-1172, manufactured by Nippon Kayaku Co., Ltd.) B: Dipentaerythritol hexaacrylate C1: Irgacure 184 (BASF) C2: 4,4'-bis(dimethylamino)benzophenone (Michler's ketone) D: Propylene glycol monomethyl ether acetate E: Cresol novolac epoxy resin (Nippon Steel Chemical & Material Co., Ltd., YDCN-700-3, epoxy equivalent 203g / eq., softening point 73°C)

[0092] The above-mentioned components were mixed in the ratios shown in Table 1 to prepare photosensitive resin compositions of Example 2 and Comparative Examples 2 and 3. All values ​​in Table 1 are in parts by mass.

[0093] [Table 1]

[0094] The photosensitive resin composition shown in Table 1 was applied to a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post-baking would be 30 μm, and the substrate was pre-baked at 110° C. for 5 minutes to prepare a coated plate. Then, the substrate was exposed to a photomask for pattern formation at 500 W / cm 2 The exposed portion was irradiated with ultraviolet light of 365 nm wavelength from a high pressure mercury lamp, and a photocuring reaction was carried out on the exposed portion. Next, the exposed coated plate was developed for another 30 seconds from the time when the pattern started to appear using a 0.8% tetramethylammonium hydroxide (TMAH) aqueous solution at 23°C shower development, and then spray washed with water to remove the unexposed portion of the coating. After that, a heat curing treatment was carried out at 230°C for 30 minutes using a hot air dryer, and the cured film according to Example 2 and Comparative Examples 2 to 3 was obtained.

[0095] The cured films obtained under the above conditions were evaluated as follows. When preparing the cured films for the film thickness test, alkali resistance test, and acid resistance test, the entire surface was exposed to light without using a photomask, and then the film was developed, washed with water, and cured by heating.

[0096] (Film thickness) A part of the applied film was scraped off and measured using a stylus-type step shape measuring device (KLA Tencol Corporation, product name P-10).

[0097] (Adhesion) At least 100 cross-cuts were made on the film of the cured film-attached glass substrate so as to form a grid pattern, and then a peeling test was carried out using cellophane tape, and the state of the grid patterns was visually evaluated. ◎: No peeling observed ○: Slight peeling of the coating film is observed △: Some peeling of the coating can be confirmed ×: The film is almost completely peeled off.

[0098] (Alkaline resistance) The glass substrate with the cured film was immersed in a mixed solution of 30 parts by mass of 2-aminoethanol and 70 parts by mass of glycol ether maintained at 80°C, and after 10 minutes it was removed, washed with pure water, and dried to prepare a chemically-immersed sample, and the adhesion was evaluated.

[0099] (Acid resistance) The glass substrate with the cured film was immersed in a solution of aqua regia (hydrochloric acid:nitric acid = 7:3) maintained at 50°C, and after 10 minutes it was removed, washed with pure water, and dried to create a chemically-immersed sample, and the adhesion was evaluated.

[0100] (Bending test) The photosensitive resin composition shown in Table 1 was applied to a 125 mm × 125 mm glass substrate with a release film attached using a spin coater so that the film thickness after post-baking would be 30 μm, and the substrate was pre-baked at 110°C for 5 minutes to prepare a coated plate. Then, the substrate was exposed to a photomask for pattern formation at 500 W / cm 2The exposed portion was irradiated with ultraviolet light of 365 nm wavelength from a high-pressure mercury lamp, and a photocuring reaction was carried out on the exposed portion. Next, the exposed coated plate was developed with a 0.8% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23°C for 30 seconds from the time when the pattern started to appear, and was then washed with water by spray to remove the unexposed portion of the coating. After that, a heat curing treatment was carried out at 230°C for 30 minutes using a hot air dryer, and the obtained pattern was peeled off from the release film to obtain the films according to Example 2 and Comparative Examples 2 to 3.

[0101] The film obtained under the above conditions was folded in half, and then pushed open with the top of the fold facing up. This test was repeated, and the number of times that cracks or breaks were observed was used for evaluation.

[0102] [Table 2]

[0103] The results of Example 2 and Comparative Examples 2 and 3 show that the use of a photosensitive resin composition containing the alkali-soluble resin containing a polymerizable unsaturated group of the present invention enables patterning with excellent resolution by alkaline development, and enables the production of a cured film that is also excellent in chemical resistance and reliability such as resistance to seam breakage.

Claims

1. A method for producing an alkali-soluble resin containing a polymerizable unsaturated group, comprising reacting an epoxy (meth)acrylate resin represented by the following general formula (1) with a dicarboxylic acid, a tricarboxylic acid or an acid anhydride thereof, and a tetracarboxylic acid or an acid dianhydride thereof: 【Chemistry 1】 Where: R １ each independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or an allyl group, R ２ each independently represents a hydrogen atom or a dicyclopentenyl group, and one or more of them are dicyclopentenyl groups. R ３ represents a hydrogen atom or a methyl group.

2. An alkali-soluble resin containing a polymerizable unsaturated group, which has a structure represented by general formula (2): 【Chemistry 2】 Where: X represents a tetravalent carboxylic acid residue; Y represents a carboxyl group-containing group represented by formula (3) or a hydrogen atom, Z represents a structure represented by formula (2a), m is a number having an average value of 1 to 20. R １ represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or an allyl group, R ２ each independently represents a hydrogen atom or a dicyclopentenyl group, and one or more of them are dicyclopentenyl groups. R ３ represents a hydrogen atom or a methyl group. M represents a carboxylic acid residue having a valence of p+1, and p is 1 or 2.

3. 3. A photosensitive resin composition comprising as essential components the polymerizable unsaturated group-containing alkali-soluble resin according to claim 2, a photopolymerizable monomer having at least two polymerizable unsaturated groups, a photopolymerization initiator, and a solvent.

4. 4. The photosensitive resin composition according to claim 3, further comprising an epoxy resin having two or more epoxy groups.

5. 5. The photosensitive resin composition according to claim 3, further comprising 0.1 to 30 parts by mass of a photopolymerization initiator and 10 to 40 parts by mass of a solvent, based on 100 parts by mass of the total of the polymerizable unsaturated group-containing alkali-soluble resin and the photopolymerizable monomer.

6. A cured product obtained by curing the photosensitive resin composition according to any one of claims 3 to 5.

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