Epoxy acrylate resin, alkali-soluble resin, resin composition containing the same, and cured product thereof

Abstract

Provided are: an epoxy acrylate resin or an alkali-soluble resin that can be cured by light or heat; and a photosensitive resin composition capable of patterning through alkaline development. This epoxy acrylate resin is represented by general formula (1) and obtained by reacting a (meth)acrylic acid with an epoxidized resin of dicyclopentadiene-type phenol resin. In addition, the alkali-soluble resin is obtained by reacting the epoxy acrylate resin with polyvalent carboxylic acids. Here, X is represented by formula (1a).

Description

[Technical Field]

[0001] The present invention relates to epoxy acrylate resin, a curable resin composition using the same, an unsaturated group-containing alkali-soluble resin, a photosensitive resin composition having the same as an essential component, and cured products thereof. The curable resin composition, photosensitive resin composition, and cured products thereof of the present invention are applicable to permanent protective films such as overcoats, undercoats, and insulating coats for circuit board fabrication, solder resists, plating resists, etching resists, insulating films for multilayer wiring boards on which semiconductor elements are mounted, semiconductor gate insulating films, photosensitive adhesives, and the like. [Background technology]

[0002] Solder resist inks are used for insulating protective coatings on exposed conductor circuits on printed circuit boards and to prevent solder from adhering to areas of the circuit where soldering is not required. Traditionally, screen printing has been used as the coating method, and the cured film requires solder heat resistance, moisture resistance, adhesion, chemical resistance, plating resistance, and electrolytic corrosion resistance. There are two types of solder resists: thermosetting and UV curing. The former mainly uses epoxy resin, while the latter uses epoxy acrylate resin. However, in recent years, with the miniaturization and improved positional accuracy of conductor circuit patterns on various printed circuit boards, and the miniaturization of mounted components, photocatalytic image formation is becoming the mainstream method for insulating coatings using solder resists, replacing screen printing. Furthermore, while organic solvents have traditionally been used for developing resists using photocatalytic methods, there is a growing demand for the use of dilute alkaline aqueous solutions due to concerns about air pollution and safety. Against this backdrop, conventional epoxy resins and epoxy acrylate resins suitable for screen printing are no longer sufficient for solder resist applications.

[0003] To address photodynamic development and development in dilute alkaline aqueous solutions, for example, phenol novolac type epoxy acrylate resins or bisphenol A epoxy acrylate resins, or half-esterified products obtained by the reaction of these epoxy acrylate resins with acid dianhydrides, are known (Patent Documents 1, 2). However, when these known epoxy acrylate resins or their acid anhydride modified products are used as solder resist resin compositions, although the developability in dilute alkaline aqueous solutions is satisfied, a curing temperature of at least 180°C is required to stabilize the physical properties. This not only increases the cost of heating equipment, but also, for example, when a glass epoxy substrate is used as the core substrate, the curing temperature may be too high, potentially causing discoloration or warping of the substrate. Furthermore, the cured films obtained from these known epoxy acrylate resins or their acid anhydride modified products have problems such as insufficient solder heat resistance, moisture resistance, adhesion, chemical resistance, plating resistance, or electrolytic corrosion resistance.

[0004] In recent years, with the increasing density of printed circuit boards, the insulating layers for chip mounting substrates such as build-up substrates for multi-chip modules (MCMs) and chip-size packages (CSPs) require reliability, pressure cooker resistance, and thermal cycle resistance. However, when the known epoxy acrylate resins or their acid anhydride modified compounds are used as solder resist resin compositions, they do not exhibit sufficient reliability.

[0005] Furthermore, with the increasing performance and resolution of electronic devices and display components in recent years, miniaturization and high density are required for the electronic components used therein. Consequently, the processability of the insulating materials used in these components is also being challenged, with demands for miniaturization and optimization of the cross-sectional shape of the processed patterns. Patterning by exposure and development is known as an effective means of microfabrication of insulating materials, and photosensitive resin compositions have been used in this method. However, there is a growing demand for many other properties, such as high sensitivity, adhesion to the substrate, reliability, heat resistance, and chemical resistance. In addition, various studies have been conducted on using organic insulating materials in gate insulating films for organic TFTs, but there is a need to reduce the operating voltage of the organic TFT by thinning the gate insulating film. Here, in the case of organic insulating materials with a dielectric breakdown voltage of approximately 1 MV / cm, the application of a thin film thickness of approximately 0.2 μm for the insulating film is being considered.

[0006] Conventional insulating materials made from photosensitive resin compositions utilize a photocuring reaction between a photoreactive alkali-soluble resin and a photopolymerization initiator. The i-line (365 nm), one of the line spectra of mercury lamps, is mainly used as the exposure wavelength for photocuring. However, this i-line is absorbed by the photosensitive resin itself and the colorant, resulting in a decrease in the degree of photocuring. Moreover, this absorption increases with thicker films. As a result, a difference in crosslinking density occurs in the film thickness direction in the exposed areas. Consequently, even if the surface of the coating is sufficiently photocured, photocuring is difficult at the bottom surface of the coating, making it extremely difficult to create a difference in crosslinking density between the exposed and unexposed areas. Consequently, it is difficult to obtain a photosensitive insulating material that can be developed at high resolution with the desired pattern dimensional stability, development margin, pattern adhesion, pattern edge shape, and cross-sectional shape.

[0007] Furthermore, Patent Document 3 discloses that an alkali-soluble unsaturated compound having both a polymerizable unsaturated group and a carboxyl group in one molecule is effective for forming negative patterns in color filters and the like. However, because there is a wide distribution in the molecular weight and the amount of carboxyl groups of each molecule, the distribution of the alkali dissolution rate of the alkali-soluble resin becomes wide, making it difficult to form fine negative patterns.

[0008] Furthermore, Patent Document 4 discloses the polyfunctionalization of an alkali-soluble resin composition to increase the molecular weight of a carboxyl group-containing copolymer. However, because the number of polymerizable unsaturated bonds is small and sufficient crosslinking density cannot be obtained, there is room for improvement of the copolymer structure, such as increasing the proportion of polymerizable unsaturated bonds in one molecule.

[0009] Furthermore, the use of photosensitive resin compositions as interlayer insulating films in semiconductor devices and as planarizing films covering TFT electrodes in liquid crystal displays is also being considered. In this case, the photosensitive resin composition is required to have a low dielectric constant so as not to impair the function of the device.

[0010] Due to limitations in the heat resistance of substrate materials and manufacturing equipment, there was no existing product that could be cured at low temperatures, developed using dilute alkaline water by photocatalysis, have a low dielectric constant, and fully satisfy the reliability required for hardened insulating layers of high-density mounting substrates, such as the adhesion and chemical resistance necessary for solder resist on printed circuit boards. [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] Japanese Patent Publication No. 61-243869 [Patent Document 2] Japanese Patent Publication No. 2003-026762 [Patent Document 3] Japanese Patent Application Publication No. 4-340965 [Patent Document 4] Japanese Patent Application Publication No. 9-325494 [Overview of the project]

[0012] Therefore, an object of the present invention is to provide a novel epoxy acrylate resin that can be cured by light or heat and has good dielectric properties, or to provide a photosensitive resin composition that can be patterned by alkali development. Furthermore, it is to provide a curable resin composition having good dielectric properties and excellent reliability such as adhesion and chemical resistance required for solder resist and insulating films of printed wiring boards, and a cured product thereof, and to provide a cured product (cured film) that exhibits excellent chemical resistance when subjected to a processing process such as electrode formation.

[0013] As a result of intensive studies to solve the above problems, the present inventors have found that a curable resin composition using an epoxy acrylate resin obtained by reacting (meth)acrylic acid with a resin obtained by epoxidizing a dicyclopentadiene-type phenol resin having a dicyclopentenyl group as a substituent is suitable for obtaining a cured product (insulating film) having excellent reliability, and that a photosensitive resin composition using an alkali-soluble resin obtained by reacting the epoxy acrylate resin with dicarboxylic acids, tricarboxylic acids or acid anhydrides thereof is suitable for solder resist and insulating films of printed wiring boards.

[0014] That is, the present invention is an epoxy acrylate resin represented by the following general formula (1).

Chemical formula

[0015] Furthermore, the present invention relates to an alkali-soluble resin represented by the following general formula (2), having a carboxyl group and a polymerizable unsaturated group in one molecule. [ka] Here, R 1 , R 2 , R 3 These are equivalent to general formula (1), respectively. Y is an unsaturated bond-containing group represented by formula (2a) above, L represents a hydrogen atom or a carboxyl group-containing group represented by formula (3) above, and 50 mol% or more of L is a carboxyl group-containing group. M represents a p+1 valent carboxylic acid residue, and p is 1 or 2.

[0016] Furthermore, the present invention relates to a curable resin composition characterized by containing the above-mentioned epoxy acrylate resin and a polymerization initiator.

[0017] Furthermore, the present invention relates to a photosensitive resin composition characterized by containing the above-mentioned alkali-soluble resin, a photopolymerizable monomer having at least one polymerizable unsaturated group, and a photopolymerization initiator. Preferably, this photosensitive resin composition further contains an epoxy resin.

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

[0019] The epoxy acrylate resin of the present invention is curable by light or heat and is also useful as an intermediate for an alkali-soluble resin, which is an acid anhydride adduct thereof. The alkali-soluble resin of the present invention provides a photosensitive resin composition that can form a fine cured film pattern by photolithography. Furthermore, according to the present invention, since it has excellent chemical resistance (alkali resistance, etc.), excellent adhesion to substrates, heat resistance, and electrical reliability, it is possible to provide cured film patterns such as solder resists for printed circuit boards and insulating films that require optical patterning. [Modes for carrying out the invention]

[0020] The present invention will be described in detail below. The epoxy acrylate resin of the present invention is represented by the above general formula (1). In general formula (1), R 1 The group represents a hydrocarbon group having 1 to 8 carbon atoms, and preferably an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, or an allyl group. C1-C8 alkyl groups can be linear, branched, or cyclic. Examples include hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, methylbutyl, n-hexyl, dimethylbutyl, n-heptyl, methylhexyl, trimethylbutyl, n-octyl, dimethylpentyl, ethylpentyl, isooctyl, and ethylhexyl, as well as cycloalkyl groups with C5-C8 such as cyclohexyl, cycloheptyl, cyclooctyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, and methylcycloheptyl. However, the group is not limited to these. Examples of C6-C8 aryl groups include phenyl, tolyl, xylyl, and ethylphenyl. Examples of aralkyl groups having 7 to 8 carbon atoms include, but are not limited to, benzyl groups and α-methylbenzyl groups. Among these substituents, methyl groups or phenyl groups are preferred from the viewpoint of ease of availability and reactivity when cured, and methyl groups are particularly preferred.

[0021] The above R 2 Each of the following independently represents a hydrogen atom or a dicyclopentenyl group, with 1 or more being dicyclopentenyl groups. The dicyclopentenyl group is a group derived from dicyclopentadiene and is represented by the following formula (1b) or formula (1c). The presence of this group allows the cured epoxy acrylate resin of the present invention to have a low dielectric constant. [ka]

[0022] n is the number of repetitions, indicating a number of 1 or more, with an average value indicating a number from 1 to 5, preferably 1.1 to 4.0, more preferably 1.2 to 3.0, and even more preferably 1.3 to 2.0. The average value is a number average.

[0023] X is an unsaturated bond-containing group represented by the formula (1a), and R 3 represents a hydrogen atom or a methyl group. In the formulas (1a), (2a) and (3), CO is a carbonyl group (C=O), and it may be represented by CO or OC.

[0024] The epoxy acrylate resin of the general formula (1) can be advantageously obtained by reacting an epoxy resin represented by the following general formula (4) with (meth)acrylic acid. The above epoxy resin is obtained by epoxidizing a dicyclopentadiene-type phenol resin obtained by reacting 2,6-disubstituted phenols with dicyclopentadiene.

[0025]

Chemical formula

[0026] For the reaction of the epoxy resin and (meth)acrylic acid, known methods can be used. For example, it is carried out using equimolar (meth)acrylic acid with respect to the epoxy group. In order to react (meth)acrylic acid with all the epoxy groups, (meth)acrylic acid may be used slightly in excess of the equimolar amount of the epoxy group and the carboxyl group. Usually, the reaction temperature is 50 to 150°C and the reaction time is 1 to 20 hours. Also, the solvent, catalyst and other reaction conditions used at this time are not particularly limited.

[0027] Preferably, the solvent is one that does not have hydroxyl groups and has a boiling point higher than the reaction temperature. Examples of such solvents include cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling-point ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate and propylene glycol monomethyl ether acetate, ketone solvents such as cyclohexanone and diisobutyl ketone, and aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene.

[0028] Examples of known catalysts include amines such as triethylamine and 1,4-diaza[5,4,0]bicycloundecene-7, ammonium salts including tetraethylammonium bromide and triethylbenzylammonium chloride, phosphines including triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine, and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole.

[0029] Furthermore, during the reaction, polymerization inhibitors such as hydroquinone, 4-methylquinoline, and phenothiazine can be added. In addition, to suppress polymerization reactions due to unsaturated bonds, the reaction may be carried out under an airflow.

[0030] Furthermore, the method for producing epoxy resin, which is a raw material for epoxy acrylate resin, can be based on, for example, the manufacturing method described in Japanese Patent Publication No. 5-339341. The epoxy resin described above is first synthesized by reacting a 2,6-disubstituted phenol compound with dicyclopentadiene in the presence of a catalyst such as a boron trifluoride ether complex to produce a phenol resin represented by the following general formula (5). Then, the resulting phenol resin can be epoxidized by reacting it with an epihalohydrin such as epichlorohydrin.

[0031] [ka] Here, R 1 , R 2 , and n are equivalent to their definitions in general formula (1), respectively.

[0032] The above phenolic resin can be obtained by reacting 2,6-disubstituted phenol with dicyclopentadiene in a predetermined ratio. Dicyclopentadiene may be added in several stages (two or more sequential additions) and reacted intermittently. The ratio is 0.28 to 2 moles of dicyclopentadiene relative to 2,6-disubstituted phenol. When dicyclopentadiene is added continuously, the ratio is 0.25 to 1 mole, preferably 0.28 to 1 mole, and more preferably 0.3 to 0.5 moles, relative to 2,6-disubstituted phenol. When dicyclopentadiene is added sequentially in parts, the total amount is preferably 0.8 to 2 moles, and more preferably 0.9 to 1.7 moles. In this case, the ratio of dicyclopentadiene used at each stage is preferably 0.28 to 1 mole. Dicyclopentadiene acts as a bridging group that links 2,6-disubstituted phenols, and some of it also acts as a dicyclopentadienyl group, R 2 It becomes part or all of it. R in a single molecule 2 Some of these compounds have, on average, at least one dicyclopentadienyl group, preferably 0.5 to 1 per phenol ring. This is not limited to general formula (5), but also applies to R in general formulas (1) and (2). 2 The same applies to this case as well.

[0033] Examples of phenols used as raw materials for the phenol resin represented by the above general formula (5) 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. However, from the viewpoint of ease of availability and reactivity when cured, 2,6-diphenylphenol or 2,6-dimethylphenol is preferred, and 2,6-dimethylphenol is particularly preferred.

[0034] The acid catalyst used when reacting phenols with dicyclopentadiene is a Lewis acid, specifically a boron trifluoride compound such as boron trifluoride, boron trifluoride-phenol complex, or boron trifluoride-ether complex; metal chlorides such as aluminum chloride, tin chloride, zinc chloride, titanium tetrachloride, and iron chloride; or organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and propanesulfonic acid. Among these, boron trifluoride-ether complex is preferred due to its ease of handling. The amount of acid catalyst used is 0.001 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of dicyclopentadiene in the case of boron trifluoride-ether complex.

[0035] To confirm that a dicyclopentenyl group represented by formula (1b) or formula (1c) has been introduced into the phenol resin represented by the general formula (5) above, mass spectrometry and FT-IR measurement can be used.

[0036] When using mass spectrometry, electrospray mass spectrometry (ESI-MS) or field desorption (FD-MS) can be employed. By subjecting samples separated by GPC or other methods to components with different numbers of nuclei to mass spectrometry, the introduction of dicyclopentenyl groups can be confirmed.

[0037] When using the FT-IR measurement method, a sample dissolved in an organic solvent such as THF is coated onto a KRS-5 cell, and the sample thin film attached to the cell, obtained by drying the organic solvent, is measured by FT-IR. A peak originating from the CO stretching vibration in the phenol nucleus is observed at 1210 cm⁻¹. -1 Appearing in the vicinity, and only when a dicyclopentenyl group is introduced, a peak originating from the CH stretching vibration of the olefin moiety of the dicyclopentadiene skeleton is present at 30-40 cm⁻¹. -1 It appears in the vicinity. Using a straight line connecting the beginning and end of the target peak as the baseline, and the distance from the peak's summit to the baseline as the peak height, the result is 3040 cm. -1 Nearby peak (A 3040 ) and 1210cm -1 Nearby peak (A 1210 ) ratio (A 3040 / A 1210 The amount of dicyclopentenyl group introduced can be quantified by ). It has been confirmed that the higher the ratio, the better the physical properties, and a preferred ratio (A) is obtained to satisfy the desired physical properties. 3040 / A 1210 ) is 0.05 or greater, and more preferably 0.1 or greater.

[0038] A suitable reaction method involves charging 2,6-disubstituted phenol and a catalyst into a reactor and gradually adding dicyclopentadiene dropwise over 1 to 10 hours.

[0039] The reaction temperature is preferably 50 to 200°C, more preferably 100 to 180°C, and even more preferably 120 to 160°C. The reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, and even more preferably 4 to 8 hours.

[0040] After the reaction is complete, alkalis such as sodium hydroxide, potassium hydroxide, and calcium hydroxide are added to deactivate the catalyst. Then, solvents such as aromatic hydrocarbons like toluene and xylene, or ketones like methyl ethyl ketone and methyl isobutyl ketone are added to dissolve the mixture. After washing with water, the solvent is recovered under reduced pressure to obtain the desired phenol resin. It is preferable to react as much of the dicyclopentadiene as possible, leaving a portion of the 2,6-disubstituted phenols unreacted, preferably 10% or less, and recovering them under reduced pressure.

[0041] Furthermore, during the reaction, solvents such as aromatic hydrocarbons like benzene, toluene, and xylene, halogenated hydrocarbons like chlorobenzene and dichlorobenzene, and ethers like ethylene glycol dimethyl ether and diethylene glycol dimethyl ether may be used as needed to adjust viscosity.

[0042] The epoxy resin represented by general formula (4) can be advantageously obtained by reacting the above-mentioned phenol resin with an epihalohydrin such as epichlorohydrin. This reaction is carried out according to conventionally known methods.

[0043] For example, it can be obtained by adding an alkali metal hydroxide such as sodium hydroxide in solid form or as a concentrated aqueous solution to a mixture of phenol resin and an excess molar amount of epihalohydrin relative to the hydroxyl groups of the phenol resin, and reacting at a reaction temperature of 30 to 120°C for 0.5 to 10 hours, or by adding a quaternary ammonium salt such as tetraethylammonium chloride as a catalyst to a polyhalohydrin ether obtained by reacting a phenol resin and an excess molar amount of epihalohydrin at a temperature of 50 to 150°C for 1 to 5 hours, and then adding an alkali metal hydroxide such as sodium hydroxide in solid form or as a concentrated aqueous solution, and reacting at a temperature of 30 to 120°C for 1 to 10 hours.

[0044] In the above reaction, the amount of epihalohydrin used is 1 to 10 times the molar amount relative to the hydroxyl groups of the phenol resin, preferably in the range of 2 to 5 times the molar amount, and the amount of alkali metal hydroxide used is in the range of 0.85 to 1.1 times the molar amount relative to the hydroxyl groups of the phenol resin.

[0045] Since the epoxy resin obtained from these reactions contains unreacted epihalohydrins and alkali metal halides, the unreacted epihalohydrins can be removed from the reaction mixture by evaporation, and the alkali metal halides can be removed by methods such as extraction with water or filtration to obtain the desired epoxy resin.

[0046] The epoxy equivalent (g / eq.) of the dicyclopentadiene type epoxy resin is preferably 244 to 3700, more preferably 260 to 2000, and even more preferably 270 to 700.

[0047] The molecular weight distribution of dicyclopentadiene-type epoxy resins can be altered by changing the ratio of phenol resin to epihalohydrin used in the epoxidation reaction. The closer the amount of epihalohydrin used is to equimolar relative to the hydroxyl groups of the phenol resin, the higher the molecular weight distribution becomes, while the closer it is to 20 times the equimolar ratio, the lower the molecular weight distribution becomes. Furthermore, it is possible to increase the molecular weight of the resulting epoxy resin by reacting it again with phenol resin.

[0048] A dicyclopentadiene-type epoxy resin can be reacted with acrylic acid or methacrylic acid to produce an epoxy acrylate resin represented by general formula (1). This epoxy acrylate resin can be used as a curable resin composition and a cured product, as described below.

[0049] The alkali-soluble resin represented by general formula (2) of the present invention can be obtained from the epoxy acrylate resin represented by general formula (1). In this sense, the epoxy acrylate resin represented by general formula (1) is also an intermediate of the alkali-soluble resin represented by general formula (2).

[0050] In general formula (2), R 1 , R 2 , and n are synonymous with general formula (1), Y is an unsaturated bond-containing group represented by formula (2a), and L represents a hydrogen atom or a carboxyl group-containing group represented by formula (3). Here, 50 mol% or more of L is a carboxyl group-containing group represented by formula (3). 3 This is equivalent to formula (1a), where M represents a p+1 valent carboxylic acid residue and p is 1 or 2. Here, the carboxylic acid residue is a group obtained by removing a carboxyl group or an acid anhydride group from a divalent or trivalent carboxylic acid or carboxylic anhydride. L may consist entirely of carboxyl group-containing groups represented by formula (3), or it may contain both hydrogen atoms and carboxyl group-containing groups. The carboxyl group-containing groups constitute 50 mol% or more of the total L, preferably 70-100 mol%, more preferably 90-100 mol%, and even more preferably 100 mol%. Since carboxyl group-containing groups are reactive with alkali, they impart alkali solubility to alkali-soluble resins or their polymerization reaction products (uncured products). By changing the ratio of carboxyl group-containing groups in L, alkali solubility can be adjusted, and alkali developability can be optimized. Furthermore, by changing the type of carboxyl group-containing group represented by formula (3), resin properties, including alkali developability, can also be changed.

[0051] Alkali-soluble resins represented by general formula (2) can be obtained by reacting the hydroxyl group of an epoxy acrylate resin represented by general formula (1) with carboxylic acids selected from dicarboxylic acids, tricarboxylic acids, or their acid anhydrides (acid monoanhydrides).

[0052] Since acid anhydrides are often used as the carboxylic acids mentioned above, they are given as examples. The carboxylic acid residues resulting from the carboxylic acids may be further substituted with substituents such as alkyl groups, cycloalkyl groups, or aromatic groups. Examples of saturated chain hydrocarbon dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as 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 acid monoanhydrides such as hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, and hexahydrotrimellitic acid. Unsaturated dicarboxylic acids or tricarboxylic acids include acid monoanhydrides such as maleic acid, itaconic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, and chloridenic acid. Other dicarboxylic acids or tricarboxylic acids include acid anhydrides such as phthalic acid and trimellitic acid. Among these, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, or the acid anhydride of trimellitic acid are preferred, and the acid anhydride of succinic acid, itaconic acid, or tetrahydrophthalic acid is more preferred. These carboxylic acids can be used individually or in combination of two or more.

[0053] The reaction temperature for synthesizing the alkali-soluble resin described above is preferably 20 to 120°C, and more preferably 40 to 90°C. The molar ratio of epoxy acrylate resin to carboxylic acids should be selected so that the proportion of carboxyl group-containing groups in L is within the above range.

[0054] This alkali-soluble resin can be used to form a photosensitive resin composition, which can then be cured to produce a cured product.

[0055] The epoxy acrylate resin or alkali-soluble resin of the present invention has an average of two or more polymerizable unsaturated groups, and can therefore be used to make a curable resin composition. When epoxy acrylate resin is used, it does not exhibit alkali developability, but when alkali-soluble resin is used, it may exhibit alkali developability. The curable resin composition of the present invention comprises the epoxy acrylate resin of the present invention and a polymerization initiator. The photosensitive resin composition of the present invention comprises the alkali-soluble resin of the present invention, a photopolymerizable monomer and a photopolymerization initiator.

[0056] The curable resin composition of the present invention may contain photopolymerization initiators or radical polymerization initiators as initiators, and may also contain other polyfunctional acrylates, etc. The resin component in the curable resin composition (epoxy acrylate resin and the component that becomes the cured resin, which does not contain solvents) is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more.

[0057] Various known photopolymerization initiators can be used as photopolymerization initiators. For example, 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 benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; and 2-(o- Biimidazole compounds such as 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, 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-tri Halomethylthiazole compounds such as chloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole, as well as 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, and 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-tri Halomethyl-s-triazine compounds such as azine, 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, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,o-acyloxime compounds such as 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, and 1-(4-methylsulfanylphenyl)butane-1-one oxime-o-acetate, as well as benzyldimethylketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, and 2-I Examples include sulfur compounds such as sopropylthioxanthone, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, and cumene peroxide, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine. These photopolymerization initiators can be used individually or in combination of two or more.

[0058] Furthermore, these photopolymerization initiators and one or more known photosensitizers can be used simultaneously. Examples of photosensitizers include Michlar's ketone, ethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, triethanolamine, and triethylamine. The amount of photosensitizer used is preferably 0 to 20 parts by mass, more preferably 0.02 to 10 parts by mass, and even more preferably 0.05 to 2 parts by mass, per 100 parts by mass of epoxy acrylate resin.

[0059] To induce thermal polymerization, it is preferable to incorporate a radical polymerization initiator, but it is not necessary to incorporate one if only photocuring is to be performed. Preferred radical polymerization initiators include, for example, known peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, and t-butyl peroxypiparate, and azo compounds such as 1,1'-azobiscyclohexane-1-carbonitride, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-(methylisobutyrate), α,α-azobis-(isobutyronitrile), and 4,4'-azobis-(4-cyanovaleic acid).

[0060] The amount of polymerization initiator used is preferably 0.01 to 100 parts by mass, more preferably 0.5 to 40 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of epoxy acrylate resin. Thermal polymerization initiators and photopolymerization initiators may be used simultaneously, or either one may be used alone. The amount of photopolymerization initiator used is preferably 0.01 to 100 parts by mass, more preferably 0.5 to 40 parts by mass, and even more preferably 1 to 10 parts by mass, per 100 parts by mass of epoxy acrylate resin. Alternatively, it is usually 0.01 to 50 parts by mass, preferably 1 to 20 parts by mass, per 100 parts by mass of the resin composition. The amount of thermal polymerization initiator used is preferably 0.01 to 100 parts by mass, more preferably 0.02 to 60 parts by mass, and even more preferably 0.05 to 2 parts by mass, per 100 parts by mass of epoxy acrylate resin. Furthermore, it is preferably 0.01 to 50 parts by mass, and more preferably 0.01 to 30 parts by mass, per 100 parts by mass of curable resin composition. stomach.

[0061] The photosensitive resin composition of the present invention preferably contains 30% by mass or more, and more preferably 50% by mass or more, of an alkali-soluble resin represented by general formula (2) in the solid content (the solid content includes monomers that become solid after curing) excluding the solvent.

[0062] In order to take advantage of the characteristics of the photosensitive resin composition, it is preferable to include the following components (A) to (C) as essential components, and it is even more preferable to include component (D). (A) The alkali-soluble resin mentioned above, (B) A photopolymerizable monomer having at least one polymerizable unsaturated group, (C) Photopolymerization initiator, (D) Epoxy resin

[0063] Examples of photopolymerizable monomers that are component (B) include monomers having hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, as well as (meth)acrylic acid esters such as 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, dipentaerythritol hexa(meth)acrylate, and glycerol (meth)acrylate. When it is necessary to form crosslinked structures between molecules of alkali-soluble resins, it is preferable to use a photopolymerizable monomer having two or more polymerizable unsaturated groups, and more preferable to use a photopolymerizable monomer having three or more polymerizable unsaturated groups. These compounds can be used individually or in combination of two or more.

[0064] The mixing ratio of these components (B) and (A) [(A) / (B)] (mass ratio) is preferably 20 / 80 to 90 / 10, and more preferably 40 / 60 to 80 / 20. If the proportion of alkali-soluble resin is too low, the cured product after the photocuring reaction will be brittle. Also, in the unexposed areas, the acid value of the coating film is low, which reduces solubility in the alkaline developer, leading to problems such as jagged and unsharp pattern edges. Conversely, if the proportion of alkali-soluble resin is higher than the above range, the proportion of photoreactive functional groups in the resin decreases, which may result in insufficient formation of the cross-linked structure by the photocuring reaction. Furthermore, if the acid value of the resin component is too high, the exposed areas will have high solubility in the alkaline developer, which may result in the formed pattern being thinner than the target line width, and problems such as pattern loss may occur.

[0065] Examples of the photopolymerization initiator for component (C) include those similar to the photopolymerization initiators mentioned in the description of the curable resin composition of the present invention. (C) The amount of component added is preferably 0.1 to 10 parts by mass, and more preferably 2 to 5 parts by mass, relative to 100 parts by mass of the total of components (A) and (B). If the amount of photopolymerization initiator added is less than 0.1 parts by mass, sufficient sensitivity cannot be obtained, and if the amount of photopolymerization initiator added exceeds 10 parts by mass, halation is likely to occur, resulting in a tapered shape (the shape of the film thickness in the cross-section of the developed pattern) that is not sharp and has a trailing edge. Furthermore, there is a risk of decomposition gas being generated if exposed to high temperatures in subsequent processes.

[0066] (D) Examples of epoxy resins include epoxy resins such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, and alicyclic epoxy resin, as well as compounds having at least one epoxy group, such as phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, and glycidyl methacrylate. When it is necessary to increase the crosslinking density of alkali-soluble resins, compounds having at least two or more epoxy groups are preferred.

[0067] When using component (D), the amount added is preferably in the range of 10 to 40 parts by mass per 100 parts by mass of the total of components (A) and (B). One purpose of adding epoxy resin is to reduce the amount of carboxyl groups remaining after the cured film is formed following patterning in order to improve the reliability of the cured film. In this case, if the amount of epoxy resin used is less than 10 parts by mass, the moisture resistance reliability when used as an insulating film may not be ensured. Also, if the amount of epoxy resin used is more than 40 parts by mass, the amount of photosensitive groups in the resin component of the photosensitive resin composition decreases, and sufficient sensitivity for patterning may not be obtained.

[0068] The photosensitive resin composition containing components (A) to (C) above, or components (A) to (D), may be dissolved in a solvent or used with various additives as needed. For example, when using the photosensitive resin composition of the present invention for insulating material applications, it is preferable to use a solvent in addition to the essential components mentioned above. Examples of solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, and propylene glycol mono This includes glycol ethers such as ethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether, as well as acetate esters such as ethyl acetate, 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. By dissolving and mixing these individually or in combination of two or more, a homogeneous solution-like composition can be obtained.

[0069] Furthermore, the photosensitive resin composition of the present invention may contain additives such as curing accelerators, thermal polymerization inhibitors, antioxidants, plasticizers, leveling agents, defoamers, coupling agents, and surfactants, as needed. Among these, known compounds such as curing accelerators, curing catalysts, and latent curing agents commonly applied to epoxy resins can be used as curing accelerators, and include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organometallic compounds, imidazoles, and diazabicyclo compounds. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine, hindered phenol compounds, and phosphorus-based heat stabilizers. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fiber, silica, mica, and alumina. Examples of defoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic compounds. Examples of coupling agents include vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-(phenylamino)propyltrimethoxysilane, and 3-ureidopropyltriethoxysilane. Examples of surfactants include fluorine-based surfactants and silicone-based surfactants.

[0070] The photosensitive resin composition of the present invention preferably contains a total of 70% by mass or more, preferably 80% by mass, and more preferably 90% by mass or more, of the above components (A) to (D) in the solid content excluding the solvent. The amount of solvent varies depending on the target viscosity, but 10 to 80% by mass of the total amount is preferable.

[0071] Furthermore, the coating film (cured product) of the present invention can be obtained, for example, by applying a solution of a photosensitive resin composition to a substrate or the like, drying the solvent, and curing it by irradiating it with light (including ultraviolet light, radiation, etc.). By using a photomask or the like to create areas that are exposed to light and areas that are not, curing only the areas exposed to light and dissolving the other areas with an alkaline solution, a coating film with a desired pattern can be obtained.

[0072] To give specific examples of each step in the film formation method by coating and drying a photosensitive resin composition, when coating the photosensitive resin composition onto the substrate, any known method such as the solution immersion method, spray method, roller coater, land coater, slit coater, or spinner can be used. After coating to the desired thickness using these methods, the film is formed by removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, hot plate, vacuum drying, or a combination thereof. The heating temperature and heating time in pre-baking can be appropriately selected depending on the solvent used, but for example, it is preferable to heat at 80 to 120°C for 1 to 10 minutes.

[0073] Examples of radiation that can be used for exposure include visible light, ultraviolet light, far ultraviolet light, electron beams, g-rays, i-rays, and X-rays, but the wavelength range of the radiation is preferably 250 to 450 nm. Furthermore, suitable developers for this alkaline development include aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. These developers can be appropriately selected according to the characteristics of the resin layer, and it is also effective to add a surfactant as needed. The development temperature is preferably 20 to 35°C, and fine images can be precisely formed using commercially available developers or ultrasonic cleaners. After alkaline development, the image is usually washed with water. As for development methods, shower development, spray development, dip development, paddle development, etc. can be applied.

[0074] After development in this manner, heat treatment (post-bake) is performed at 180-250°C for 20-100 minutes. This post-bake is performed to improve the adhesion between the patterned coating and the substrate, among other purposes. Similar to pre-bake, this is done by heating using an oven, hot plate, etc. The patterned coating is formed through each step of the photolithography method. Then, polymerization or curing (sometimes referred to as curing collectively) is completed by heat to form a cured film such as an insulating film with the desired pattern. The curing temperature at this time is preferably 160-250°C. The cured product of the present invention can take various forms other than a cured film.

[0075] The photosensitive resin composition of the present invention has improved photocurability because component (A) has a large number of polymerizable unsaturated groups in one molecule, and the crosslinking density after curing can be increased without increasing the amount of photopolymerization initiator. That is, when a thick film is irradiated with ultraviolet light or electron beam, the cured portion hardens to the bottom, resulting in a large difference in solubility in alkaline developer between the exposed and unexposed portions. This improves pattern dimensional stability, development margin, and pattern adhesion, enabling high-resolution pattern formation. Furthermore, even in the case of thin films, the increased sensitivity allows for a significant improvement in the amount of residual film in the exposed portion and suppression of peeling during development.

[0076] The photosensitive composition of the present invention is extremely useful for solder resists, plating resists, and etching resists for circuit board fabrication, as well as insulating films for multilayer wiring boards on which semiconductor elements are mounted, semiconductor gate insulating films, and photosensitive adhesives (especially adhesives that require heat bonding performance even after pattern formation by photolithography). [Examples]

[0077] The present invention will be described in detail below based on examples, but the present invention is not limited thereto. In the examples, unless otherwise specified, "parts" refers to parts by mass, and "%" refers to mass percent. Furthermore, unless otherwise specified, the resins in these examples were evaluated as follows.

[0078] [Solid content concentration] The resin solution, photosensitive resin composition, etc. (approximately 1 g) was impregnated into a glass filter [mass: W0 (g)] and weighed accurately [W1 (g)]. The mass after heating at 160°C for 2 hours [W2 (g)] was used to calculate the mass using the following formula. Solid content concentration (%) = 100 × (W2 - W0) / (W1 - W0)

[0079] [Acid value] The measurement was performed in accordance with JIS K 0070 standard. Specifically, the resin solution was dissolved in dioxane and titrated with a 0.1N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.). The amount of KOH required per gram of solid content (mg) was defined as the acid value.

[0080] [Molecular weight] The molecular weight was measured using gel permulation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation; columns: TSKgelSuperH2000 (2) + TSKgelSuperH3000 (1) + TSKgelSuperH4000 (1) + TSKgelSuperH5000 (1) (all manufactured by Tosoh Corporation); solvent: tetrahydrofuran; temperature: 40°C; rate: 0.6 mL / min). The weight-average molecular weight (Mw) was determined by converting it to standard polystyrene (PS-Oligomakit, manufactured by Tosoh Corporation).

[0081] [Relative permittivity, dielectric loss tangent] The 1 GHz value was measured using the cavity resonance method (Vector Network Analyzer (VNA) E8363B (Agilent Technologies), Cavity Resonator Perturbation Method Dielectric Constant Measurement Device (Kanto Electronics Applied Development Co., Ltd.)) after being completely dried and stored in a room at 23°C and 50% humidity for 24 hours.

[0082] [Adhesion] At least 100 cross-cuts were made on a glass substrate with a hardened film, creating a grid pattern. Then, a peeling test was performed using cellophane tape, and the grid pattern was visually evaluated. ◎: No peeling observed at all ○: Slight peeling of the paint film is visible. △: Some areas of the paint film show signs of peeling. ×: Products where the film almost completely peels off.

[0083] [Alkali resistance] A glass substrate with a cured film was immersed in a solution of 30 parts 2-aminoethanol and 70 parts glycol ether, maintained at 80°C. After 10 minutes, it was removed, washed with pure water, and dried to prepare a chemically immersed sample, and the adhesion properties described above were evaluated.

[0084] [Acid resistance] A glass substrate with a hardened film was immersed in a solution of aqua regia (hydrochloric acid:nitric acid = 7:3) maintained at 50°C. After 10 minutes, it was removed, washed with pure water, and dried to prepare a sample that had been immersed in the chemicals, and the adhesion properties described above were evaluated.

[0085] The abbreviations for the materials used are as follows: E1: Epoxy resin obtained in Synthesis Example 1 E2: Epoxy resin obtained in synthesis example 2 E3: Phenol novolac type epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., YDPN-638, epoxy equivalent 177g / eq.) E4: Bisphenol A type liquid epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., YD-127, epoxy equivalent 182 g / eq.) E5: Cresol novolac type epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., YDCN-700-3, epoxy equivalent 203 g / eq., softening point 73°C) THPA:1,2,3,6-tetrahydrophthalic anhydride TPP: Triphenylphosphine HQ: Hydroquinone TEAB: Tetraethylammonium bromide MIBK: Methyl isobutyl ketone PGMEA: Propylene glycol monomethyl ether acetate B1: Dipentaerythritol hexaacrylate C1: Photopolymerization initiator (BASF, Irgacure 184) C2: Photopolymerization initiator (4,4'-bis(dimethylamino)benzophenone (Michler's ketone))

[0086] Synthesis Example 1 In a reactor equipped with a stirrer, temperature control device, nitrogen introduction device, dropper, and reflux condenser, 970 parts of 2,6-xylenol and 14.5 parts of 47% BF3 ether complex were charged and heated to 70°C with stirring. While maintaining the same temperature, 300 parts of dicyclopentadiene (0.29 molars relative to 2,6-xylenol) were added dropwise over 2 hours. The reaction was further carried out at a temperature of 125-135°C for 6 hours, and 2.3 parts of calcium hydroxide were added. Then, 4.6 parts of 10% oxalic acid aqueous solution were added. After that, the mixture was heated to 160°C to dehydrate it, and then heated to 200°C under reduced pressure of 5 mmHg to evaporate and remove unreacted starting materials. 1000 parts of MIBK were added to dissolve the product, and 400 parts of 80°C warm water were added for washing, and the lower layer of water was separated and removed. Subsequently, MIBK was evaporated and removed by heating to 160°C under reduced pressure of 5 mmHg, yielding 540 parts of a reddish-brown phenolic resin. The hydroxyl group equivalent was 213, the softening point was 71°C, and the absorption ratio (A 3040 / A 1210) The value was 0.11. Mass spectra measured by ESI-MS (negative) revealed M-=253, 375, 507, and 629.

[0087] In a reaction apparatus equipped with a stirrer, temperature control device, vacuum control device, nitrogen introduction device, dropper, and reflux condenser, 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 reduced pressure of 125 mmHg, 108 parts of 49% sodium hydroxide aqueous solution were added dropwise over 4 hours while maintaining a temperature of 63-67°C. During this time, the epichlorohydrin was azeotropically mixed with water, and the resulting water was sequentially removed from the system. After the reaction was complete, the epichlorohydrin was recovered under conditions of 5 mmHg and 180°C, and the product was dissolved by adding 948 parts of MIBK. Then, 263 parts of water were added to dissolve the by-product sodium chloride, and the mixture was allowed to stand to separate and remove the lower layer of saline solution. After neutralization with phosphoric acid aqueous solution, the resin solution was washed with water until the rinse solution was neutral, and then filtered. Under reduced pressure of 5 mmHg, the mixture was heated to 180°C to remove MIBK by distillation, yielding 298 parts of a reddish-brown transparent 2,6-xylenol-dicyclopentadiene type epoxy resin (E1). The epoxy equivalent was 282, the total chlorine content was 980 ppm, and the resin was semi-solid at room temperature.

[0088] Synthesis Example 2 In a reaction apparatus similar to that used in Synthesis Example 1, 95.0 parts of 2,6-xylenol and 6.3 parts of 47% BF3 ether complex were charged and heated to 70°C with stirring. While maintaining the same temperature, 58.8 parts of dicyclopentadiene (0.56 molars relative to 2,6-xylenol) were added dropwise over 1 hour. After reacting at 115-125°C for 3 hours, another 69.2 parts of dicyclopentadiene (0.67 molars relative to 2,6-xylenol) were added dropwise over 1 hour at the same temperature, and the reaction was carried out at 115-125°C for 2 hours. 1.0 part of calcium hydroxide was added. Then, 2.0 parts of 10% oxalic acid aqueous solution were added. After that, the mixture was heated to 160°C to dehydrate it, and then heated to 200°C under reduced pressure of 5 mmHg to evaporate and remove any unreacted starting materials. The product was dissolved by adding 520 parts of MIBK, then washed with 150 parts of 80°C hot water, and the lower layer of water was separated and removed. Subsequently, the MIBK was evaporated and removed by heating to 160°C under reduced pressure of 5 mmHg, yielding 221 parts of reddish-brown phenolic resin. The hydroxyl group equivalent was 377, the softening point was 102°C, and the absorption ratio (A) 3040 / A 1210The value was 0.18. Mass spectra measured by ESI-MS (negative) revealed M-=253, 375, 507, and 629.

[0089] In a reaction apparatus similar to that used in Synthesis Example 1, 180 parts of the obtained phenolic resin, 221 parts of epichlorohydrin, and 33 parts of diethylene glycol dimethyl ether were added and heated to 65°C. Under reduced pressure of 125 mmHg, 39 parts of 49% sodium hydroxide aqueous solution were added dropwise over 4 hours while maintaining a temperature of 63-67°C. During this time, the epichlorohydrin was azeotropically mixed with water, and the resulting water was sequentially removed from the system. After the reaction was complete, the epichlorohydrin was recovered under conditions of 5 mmHg and 180°C, and the product was dissolved by adding 482 parts of MIBK. Then, 146 parts of water were added to dissolve the by-product sodium chloride, and the mixture was allowed to stand to separate and remove the lower layer of saline solution. After neutralization with phosphoric acid aqueous solution, the resin solution was washed with water until the rinse solution was neutral, and then filtered. Under reduced pressure of 5 mmHg, the mixture was heated to 180°C to remove MIBK by distillation, yielding 200 parts of a reddish-brown transparent 2,6-xylenol-dicyclopentadiene type epoxy resin (E2). The resin had an epoxy equivalent of 446, a total chlorine content of 431 ppm, and a softening point of 91°C.

[0090] Example 1 In a reaction vessel equipped with a stirrer, temperature control device, reflux condenser, and air introduction device, 282 parts of E1 were dissolved in 63 parts of PGMEA. Then, 72 parts of acrylic acid, 3.5 parts of TPP, and 0.1 parts of HQ were added, and the mixture was reacted at 110°C for 8 hours while blowing in air. After that, 293 parts of PGMEA were added to obtain a PGMEA solution of epoxy acrylate resin (R1). The solid content concentration of the obtained resin solution was 50%.

[0091] The obtained resin solution was desoldered by vacuum distillation, and 100 parts of the resulting solids were placed in a fluororesin mold. 1 part of dicumyl peroxide was added, and the mixture was heated in an oven at 100°C for 30 minutes and then at 170°C for 1 hour to cure it and obtain a cured product. A test specimen measuring 0.2 mm thick and 0.2 cm × 10 cm was prepared from this cured product, and the relative permittivity and dielectric loss tangent were measured.

[0092] Example 2 In the same apparatus as in Example 1, 446 parts of E2 were dissolved in 97 parts of PGMEA, and then 72 parts of acrylic acid, 3.5 parts of TPP, and 0.1 parts of HQ were added. The mixture was reacted at 110°C for 8 hours while blowing in air, and then 450 parts of PGMEA were added to obtain a PGMEA solution of epoxy acrylate resin (R2). The solid content concentration of the obtained resin solution was 50%. The dielectric constant and dielectric loss tangent were measured in the same manner as in Example 1.

[0093] Comparative Example 1 In the same apparatus as in Example 1, 177 parts of E3 were dissolved in 44 parts of PGMEA, and then 72 parts of acrylic acid, 3.5 parts of TPP, and 0.1 parts of HQ were added. The mixture was reacted at 110°C for 8 hours while blowing in air, and then 208 parts of PGMEA were added to obtain a PGMEA solution of epoxy acrylate resin (HR1). The solid content concentration of the obtained resin solution was 50%. The dielectric constant and dielectric loss tangent were measured in the same manner as in Example 1. The results are shown in Table 1.

[0094] [Table 1]

[0095] Example 3 In the same apparatus as in Example 1, 450 parts of a 50% PGMEA solution of R1, 95 parts of THPA, 1.8 parts of TEAB, and 38 parts of PGMEA were charged and stirred at 120-125°C for 6 hours to obtain an alkali-soluble resin solution (A1). The solid content concentration of the obtained resin solution was 55%.

[0096] A photosensitive resin composition was obtained by blending 53 parts of A1, 12.5 parts of B1, 1.3 parts of C1, 0.2 parts of C2, 6.3 parts of E5, and 28 parts of PGMEA.

[0097] The obtained photosensitive resin composition was applied to a 125 mm × 125 mm glass substrate using a spin coater to a post-baking film thickness of 30 μm, and a coated plate was prepared by pre-baking at 110°C for 5 minutes. Subsequently, a coating was applied at 500 W / cm². 2The entire surface was exposed to ultraviolet light at a wavelength of 365 nm using a high-pressure mercury lamp to perform a photocuring reaction. Next, the exposed coated plate was treated with a 0.8% tetramethylammonium hydroxide (TMAH) aqueous solution in a shower developer at 23°C for 60 seconds, followed by spray rinsing. After that, a heat curing treatment was performed using a hot air dryer at 230°C for 30 minutes to obtain a glass substrate with a cured film.

[0098] Example 4 In the same apparatus as in Example 1, 450 parts of a 50% PGMEA solution of R2, 62 parts of THPA, 1.8 parts of TEAB, and 11 parts of PGMEA were charged and stirred at 120-125°C for 6 hours to obtain an alkali-soluble resin solution (A2). The solid content concentration of the obtained resin solution was 55%.

[0099] Except for using A2 instead of A1, the same procedure as in Example 3 was followed to obtain a photosensitive resin composition and a glass substrate with a cured film.

[0100] Comparative Example 2 In the same apparatus as in Example 1, 450 parts of a 50% PGMEA solution of HR1, 135 parts of THPA, 1.8 parts of TEAB, and 70 parts of PGMEA were charged and stirred at 120-125°C for 6 hours to obtain an alkali-soluble resin solution (HA1). The solid content concentration of the obtained resin solution was 55%.

[0101] Except for using HA1 instead of A1, the same procedure as in Example 3 was followed to obtain a photosensitive resin composition and a glass substrate with a cured film.

[0102] Comparative Example 3 In the same apparatus as in Example 1, 182 parts of E4 were dissolved in 45 parts of PGMEA, and then 72 parts of acrylic acid, 3.5 parts of TPP, and 0.1 parts of HQ were added. The mixture was reacted at 110°C for 8 hours while blowing in air, and then 212 parts of PGMEA were added to obtain a PGMEA solution of epoxy acrylate resin. The solid content concentration of the obtained resin solution was 50%. 291 parts of the obtained resin solution, 4.0 parts of dimethylolpropionic acid, 11.8 parts of 1,6-hexanediol, and 104 parts of PGMEA were charged and the temperature was raised to 45°C. Next, 61.8 parts of isophorone diisocyanate were added dropwise. After the dropwise addition was complete, the mixture was stirred at 75-80°C for 6 hours. Furthermore, 21 parts of THPA were added and the mixture was stirred at 90-95°C for 6 hours to obtain an alkali-soluble resin solution (HA2). The solid content concentration of the obtained resin solution was 55%.

[0103] Except for using HA2 instead of A1, the same procedure as in Example 3 was followed to obtain a photosensitive resin composition and a glass substrate with a cured film.

[0104] Table 2 shows the results of measuring the acid value (based on solid content) and molecular weight (Mw) of the obtained resin solution, as well as the results of adhesion, alkali resistance, and acid resistance tests performed on the obtained cured film-coated glass substrate.

[0105] [Table 2] Potential for industrial use

[0106] The curable resin composition, photosensitive resin composition, and cured product thereof of the present invention can be applied to solder resists, plating resists, and etching resists for the fabrication of circuit boards, as well as insulating films for multilayer wiring boards on which semiconductor elements are mounted, gate insulating films for semiconductors, and photosensitive adhesives.

Claims

1. Represented by the general formula (1) below, this represents the 3040 cm² derived from the C-H stretching vibration of the olefin moiety of the dicyclopentadiene skeleton in the dicyclopentenyl group in the FT-IR measurement method. －１ Peak height of nearby peaks (A ３０４０ ) and 1210 cm² originating from C-O stretching vibrations in the phenol nucleus (phenol residues) －１ Peak height of nearby peaks (A １２１０ A is the ratio of ) ３０４０ / A １２１０ An epoxy acrylate resin having a value of 0.11 or higher. 【Chemistry 1】 Here, R １ These independently represent hydrocarbon groups having 1 to 8 carbon atoms. R ２ Each element independently represents a hydrogen atom or a dicyclopentenyl group, and at least one of them is a dicyclopentenyl group. X is an unsaturated bond-containing group represented by the above formula (1a), and R ３ represents a hydrogen atom or a methyl group. n represents the number of repetitions, and its average value is between 1 and 5.

2. A curable resin composition characterized by containing the epoxy acrylate resin described in claim 1 and a polymerization initiator.

3. A cured product obtained by curing the curable resin composition according to claim 2.

4. Represented by the general formula (2) below, this represents the 3040 cm² derived from the C-H stretching vibration of the olefin moiety of the dicyclopentadiene skeleton in the dicyclopentenyl group in the FT-IR measurement method. －１ Peak height of nearby peaks (A ３０４０ ) and 1210 cm² originating from C-O stretching vibrations in the phenol nucleus (phenol residues) －１ Peak height of nearby peaks (A １２１０ A is the ratio of ) ３０４０ / A １２１０ An alkali-soluble resin having a molecular weight of 0.11 or higher and containing carboxyl groups and polymerizable unsaturated groups. 【Chemistry 2】 Here, R １ These independently represent hydrocarbon groups having 1 to 8 carbon atoms. R ２ Each element independently represents a hydrogen atom or a dicyclopentenyl group, and at least one of them is a dicyclopentenyl group. Y is an unsaturated bond-containing group represented by the above formula (2a), and R ３ represents a hydrogen atom or a methyl group. n represents the number of repetitions, and its average value is between 1 and 5. L represents a hydrogen atom or a carboxyl group-containing group represented by the above formula (3), and 50 mol% or more of L is a carboxyl group-containing group. M represents a p+1 valent carboxylic acid residue, where p is 1 or 2.

5. A photosensitive resin composition characterized by containing the alkali-soluble resin described in claim 4, a photopolymerizable monomer having at least one polymerizable unsaturated group and being different from the alkali-soluble resin, and a photopolymerization initiator.

6. The photosensitive resin composition according to claim 5, further characterized by containing an epoxy resin.

7. The photosensitive resin composition according to claim 5 or 6, comprising 0.1 to 10 parts by mass of a photopolymerization initiator per 100 parts by mass of the total of the alkali-soluble resin and the photopolymerizable monomer.

8. The photosensitive resin composition according to claim 6 or 7, comprising 10 to 40 parts by mass of epoxy resin with respect to a total of 100 parts by mass of alkali-soluble resin and photopolymerizable monomer.

9. A cured product obtained by curing the photosensitive resin composition according to any one of claims 5 to 8.

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