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

Abstract

The present invention provides a photocurable or thermocurable epoxy acrylate resin or alkali-soluble resin, a photosensitive resin composition that can be patterned by alkali development, a resin composition containing the same, and a cured product thereof. The epoxy acrylate resin is represented by the general formula (1) and is obtained by reacting (meth)acrylic acid with a resin obtained by epoxidizing a dicyclopentadiene-type phenolic resin. In addition, the alkali-soluble resin is obtained by reacting a polycarboxylic acid with the epoxy acrylate resin. Here, X is represented by the formula (1a). -CH2-CH(OH)-CH2-O-CO-CR 3 =CH2 (1a).

Description

Technical Field

[0001] The present invention relates to an epoxy acrylate resin, a curable resin composition using the same, an alkali-soluble resin containing an unsaturated group, a photosensitive resin composition containing the alkali-soluble resin as an essential component, and cured products thereof. The curable resin composition, the photosensitive resin composition, and the cured products thereof of the present invention can be applied to permanent protective films such as outer coatings, undercoatings, and insulating coatings for manufacturing circuit boards; solder resists, plating resistants, and etching resistants; insulating films for multilayer formation of wiring boards on which semiconductor elements are mounted, gate insulating films of semiconductors, photosensitive adhesives, and the like. Background Art

[0002] Solder resist inks are used for applications such as insulating protective films for exposed conductor circuits of printed wiring boards or preventing solder from adhering to portions of the circuit where solder is not required. As a film-forming method, screen printing has been commonly used since before, and solder heat resistance, moisture resistance, adhesion, chemical resistance, plating resistance, and electrolytic corrosion resistance are required for the cured film. This type of solder resist has two types: heat-curable type and ultraviolet-curable type. In most cases, the former mainly uses epoxy resins, and the latter uses epoxy acrylate resins. However, in recent years, due to the miniaturization of conductor circuit patterns and the improvement of positional accuracy of various printed wiring boards, and the miniaturization of mounting parts, in the formation of insulating films using solder resists, image formation using photolithography has gradually become the mainstream instead of screen printing. In addition, organic solvents have been used for developing resists using photolithography, but from the viewpoints of air pollution and safety, it is desirable to use a dilute alkali aqueous solution. Based on this background, there have been problems that existing epoxy resins and epoxy acrylate resins corresponding to screen printing are not satisfactory in solder resists.

[0003] As a countermeasure against photolithography and dilute alkali aqueous solution development, for example, phenol novolak type epoxy acrylate resins or bisphenol A epoxy acrylate resins, or half esters produced by the reaction of these epoxy acrylate resins with acid anhydrides are known (Patent Document 1, Patent Document 2). However, when these known epoxy acrylate resins or their acid anhydride-modified products are used as resin compositions for solder resists, although the developability with dilute alkali aqueous solutions is satisfied, in order to stabilize the physical properties, the curing temperature needs to be at least 180°C or higher, and the heating equipment is costly. Moreover, for example, when a glass epoxy substrate is used for a core substrate, the curing temperature is too high and there is a possibility of 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 high density of printed wiring boards, there are requirements for reliability, pressure cooker resistance, and heat cycle resistance for insulating layers used in chip mounting substrates such as build-up substrates for multichip modules (MCM) and chip scale packages (CSP). In the case where the known epoxy acrylate resin or its acid anhydride-modified product is used as the solder resist resin composition, there is also a problem that sufficient reliability cannot be achieved.

[0005] In addition, with the high performance and high fineness of electronic devices, display components, etc. in recent years, there are requirements for miniaturization or high density of electronic components used therein. Moreover, there are also requirements for miniaturization of the processability of insulating materials used therein and rationalization of the cross-sectional shape of the processed pattern. As an effective means for microfabrication of insulating materials, a method of patterning by exposure and development is known, in which a photosensitive resin composition is used, but there are requirements for many characteristics such as high sensitivity, adhesion to the substrate, reliability, heat resistance, and chemical resistance. In addition, various studies have been conducted on the use of organic insulating materials in gate insulating films for organic thin film transistors (TFT). However, it is necessary to thin the gate insulating film to reduce the operating voltage of the organic TFT. Here, in the case of an organic insulating material with a breakdown voltage of about 1 MV / cm for the insulating material, research has been conducted on the application of a thin film with a film thickness of about 0.2 μm for the insulating film.

[0006] Regarding existing insulating materials containing a photosensitive resin composition, a photocuring reaction caused by the reaction of a photo-reactive alkali-soluble resin and a photoinitiator is utilized, and mainly i-ray (365 nm), which is one of the line spectra of a mercury lamp, is used as the exposure wavelength for photocuring. However, this i-ray is absorbed by the photosensitive resin itself or a colorant, resulting in a decrease in the degree of photocuring. Moreover, if it is a thick film, the absorption amount will increase. Therefore, there will be a difference in the crosslink density in the film thickness direction for the exposed part. Therefore, even if photocuring is sufficiently performed on the coating film surface, it is difficult to perform photocuring on the bottom surface of the coating film. Thus, it is significantly difficult to create a difference in crosslink density between the exposed part and the unexposed part. Therefore, it is difficult to obtain a photosensitive insulating material that has the desired pattern size stability, development margin, pattern adhesion, edge shape, and cross-sectional shape of the pattern and can be developed with high resolution.

[0007] In addition, in Patent Document 3, it is disclosed that an alkali-soluble unsaturated compound having a polymerizable unsaturated group and a carboxyl group in one molecule is effective for forming a negative pattern such as a color filter. However, due to a wide distribution in the molecular weight of each molecule and the amount of carboxyl groups, the distribution of the alkali dissolution rate of the alkali-soluble resin becomes wide, and thus it is difficult to form a fine negative pattern.

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

[0009] In addition, the use of a photosensitive resin composition for an interlayer insulating film of a semiconductor device and a planarization film for coating a TFT electrode of a liquid crystal display device has also been studied. In such a case, the photosensitive resin composition is required to have a reduced dielectric constant so as not to hinder the functions of the device.

[0010] There is no such composition that can be cured at a low temperature in consideration of the heat resistance limitation of the substrate material or manufacturing equipment, etc., can be developed by lithography using dilute alkaline water, and can reduce the dielectric constant, and fully satisfies the reliability required for an insulating layer cured film such as a solder resist for a printed wiring board, including adhesion and chemical resistance.

[0011] Prior Art Documents

[0012] Patent Documents

[0013] Patent Document 1: Japanese Patent Laid-Open No. 61-243869

[0014] Patent Document 2: Japanese Patent Laid-Open No. 2003-026762

[0015] Patent Document 3: Japanese Patent Laid-Open No. 4-340965

[0016] Patent Document 4: Japanese Patent Laid-Open No. 9-325494 Summary of the Invention

[0017] Problems to be Solved by the Invention

[0018] Accordingly, an object of the present invention is to provide a novel epoxy acrylate resin that can be photocured or thermally cured and has good dielectric properties, or to provide a photosensitive resin composition that can be patterned by alkali development. Further, a curable resin composition and a cured product thereof that have good dielectric properties, excellent reliability such as adhesion and chemical resistance required for solder resist or insulating film of printed wiring boards, etc., and a cured product (cured film) that exhibits excellent chemical resistance when subjected to processing steps such as electrode formation are provided.

[0019] The inventors of the present invention made diligent studies to solve the above problems, and as a result, 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 phenolic resin having dicyclopentenyl as a substituent is preferable for obtaining a cured product (insulating film) with excellent reliability, and also found that a photosensitive resin composition using an alkali-soluble resin obtained by reacting a dicarboxylic acid, a tricarboxylic acid or an acid anhydride thereof with the epoxy acrylate resin is preferable for solder resist or insulating film of printed wiring boards, etc.

[0020] That is, the present invention is an epoxy acrylate resin represented by the following general formula (1).

[0021] [Chemical formula 1]

[0022]

[0023] -CH2-CH(OH)-CH2-O-CO-CR 3 =CH2(1a)

[0024] Here,

[0025] R 1 independently represents a hydrocarbon group having 1 to 8 carbon atoms,

[0026] R 2 independently represents a hydrogen atom or a dicyclopentenyl group, and one or more of them are dicyclopentenyl groups.

[0027] R 3 represents a hydrogen atom or a methyl group.

[0028] X is an unsaturated bond-containing group represented by the formula (1a).

[0029] n represents the number of repetitions, and its average value is 1 to 5.

[0030] In addition, the present invention is an alkali-soluble resin represented by the following general formula (2) and having a carboxyl group and a polymerizable unsaturated group in one molecule.

[0031] [Chemical formula 2]

[0032]

[0033] -CH2-CH(OL)-CH2-O-CO-CR 3 =CH2(2a)

[0034] -CO-M-(COOH)p(3)

[0035] Here, R 1 、R 2 、R 3 is respectively synonymous with the general formula (1).

[0036] Y is a group containing an unsaturated bond represented by the said formula (2a), L represents a hydrogen atom or a group containing a carboxyl group represented by the said formula (3), and 50 mol% or more of L is a group containing a carboxyl group. M represents a carboxylic acid residue of p + 1 valency, and p is 1 or 2.

[0037] In addition, the present invention is a curable resin composition, characterized by containing the said epoxy acrylate resin and a polymerization initiator.

[0038] In addition, the present invention is a photosensitive resin composition, characterized by containing the said alkali-soluble resin, a photopolymerizable monomer having at least one polymerizable unsaturated group, and a photopolymerization initiator. The said photosensitive resin composition preferably further contains an epoxy resin.

[0039] In addition, other embodiments of the present invention relate to a cured product obtained by curing the said curable resin composition or the said photosensitive resin composition.

[0040] The epoxy acrylate resin of the present invention can be cured by light or heat, and can also be effectively used as an intermediate of an alkali-soluble resin which is an acid anhydride adduct thereof. The alkali-soluble resin of the present invention can provide a photosensitive resin composition capable of forming a fine cured film pattern by photolithography.

[0041] Furthermore, according to the present invention, since the chemical resistance (such as alkali resistance), adhesion to a substrate, heat resistance, electrical reliability, etc. are excellent, it is also possible to provide a cured film pattern such as a solder resist for a printed wiring board, an insulating film that requires photopatterning, etc. Detailed Description of the Invention

[0042] Hereinafter, the present invention will be described in detail.

[0043] The epoxy acrylate resin of the present invention is represented by the said general formula (1).

[0044] In the general formula (1), R 1represents a hydrocarbon group having 1 to 8 carbon atoms, 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. As the alkyl group having 1 to 8 carbon atoms, it can be any of linear, branched, or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, methylbutyl, n-hexyl, dimethylbutyl, n-heptyl, methylhexyl, trimethylbutyl, n-octyl, dimethylpentyl, ethylpentyl, isooctyl, ethylhexyl and other hydrocarbon groups, or cycloalkyl groups having 5 to 8 carbon atoms such as cyclohexyl, cycloheptyl, cyclooctyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, methylcycloheptyl, but are not limited thereto. As the aryl group having 6 to 8 carbon atoms, phenyl, tolyl, xylyl, ethylphenyl and the like can be mentioned, but are not limited thereto. As the aralkyl group having 7 to 8 carbon atoms, benzyl, α-methylbenzyl and the like can be mentioned, but are not limited thereto. Among these substituents, from the viewpoints of ease of acquisition and reactivity during formation of a cured product, methyl or phenyl is preferred, and methyl is particularly preferred.

[0045] Said R 2 independently represents a hydrogen atom or dicyclopentenyl, and one or more thereof are dicyclopentenyl. Dicyclopentenyl is a group derived from dicyclopentadiene and is represented by the following formula (1b) or formula (1c). By the presence of said group, the cured product of the epoxy acrylate resin of the present invention can have a reduced dielectric constant.

[0046] [Chemical formula 3]

[0047]

[0048] n is the number of repetitions, represents a number of 1 or more, and represents a number of 1 to 5 as its average value, preferably 1.1 to 4.0, more preferably 1.2 to 3.0, and still more preferably 1.3 to 2.0. The average value is the number average.

[0049] X is an unsaturated bond-containing group represented by formula (1a), and R 3 represents a hydrogen atom or a methyl group. In formula (1a), formula (2a) and formula (3), CO is a carbonyl group (C=O), which can be represented by CO or OC.

[0050] The epoxy acrylate resin of general formula (1) can be advantageously obtained by reacting an epoxy resin represented by the following general formula (4) with (meth)acrylic acid. The epoxy resin is obtained by epoxidizing a dicyclopentadiene-type phenol resin obtained by reacting 2,6-disubstituted phenols with dicyclopentadiene.

[0051] [Chemical formula 4]

[0052]

[0053] Here, R1 , R 2 and n have the same meanings as defined in the general formula (1). G represents a glycidyl group.

[0054] The reaction between the epoxy resin and (meth)acrylic acid can be carried out by a known method. For example, an equimolar amount of (meth)acrylic acid is used for the epoxy group to carry out the reaction. In order to react (meth)acrylic acid with all of the epoxy groups, a slightly excessive amount of (meth)acrylic acid compared to the equimolar amount of the epoxy group and the carboxyl group can also be used. Generally, the reaction temperature is 50°C to 150°C, and the reaction time is 1 hour to 20 hours. In addition, the solvent, catalyst, and other reaction conditions used at this time are not particularly limited.

[0055] As the solvent, for example, it is preferably 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 containing ethyl cellosolve acetate and butyl cellosolve acetate; high-boiling ether-based or ester-based solvents containing diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; ketone-based solvents containing cyclohexanone and diisobutyl ketone; aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene.

[0056] As the catalyst, for example, the following can be cited: amines such as triethylamine and 1,4-diazabicyclo[5,4,0]undec-7-ene; ammonium salts containing tetraethylammonium bromide and triethylbenzylammonium chloride; phosphines containing triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine; known catalysts such as imidazoles like 2-methylimidazole and 2-ethyl-4-methylimidazole.

[0057] Furthermore, when carrying out this reaction, hydroquinone, 4-methylquinoline, phenothiazine, etc. can also be added as polymerization inhibitors. In addition, in order to inhibit the polymerization reaction caused by the unsaturated bond, the reaction is carried out under a gas flow such as air according to circumstances.

[0058] In addition, for example, the manufacturing method of the epoxy resin as a raw material of the epoxy acrylate resin can refer to the manufacturing method described in Japanese Patent Laid-Open No. 5-339341.

[0059] Regarding the epoxy resin, first, a phenol resin represented by the following general formula (5) is synthesized by reacting a 2,6-disubstituted phenol compound with dicyclopentadiene in the presence of a catalyst such as boron trifluoride-ether complex. Then, it can be obtained by reacting the obtained phenol resin with an epihalohydrin such as epichlorohydrin for epoxidation.

[0060] [Chemical formula 5]

[0061]

[0062] Here, R 1 , R 2 and n have the same meanings as defined in the general formula (1), respectively.

[0063] The phenolic resin can be obtained by reacting dicyclopentadiene with a 2,6-disubstituted phenol at a specified ratio, or dicyclopentadiene can be added in several stages (added batchwise more than twice) to carry out the reaction intermittently. The ratio is 0.28 to 2 moles of dicyclopentadiene per mole of the 2,6-disubstituted phenol. When dicyclopentadiene is continuously added for reaction, the ratio is 0.25 to 1 mole of dicyclopentadiene per mole of the 2,6-disubstituted phenol, preferably 0.28 to 1 mole, more preferably 0.3 to 0.5 mole. In the case of adding dicyclopentadiene batchwise for reaction, the overall is preferably 0.8 to 2 moles, more preferably 0.9 to 1.7 moles. Furthermore, the usage ratio of dicyclopentadiene in each stage in the said case is preferably 0.28 to 1 mole.

[0064] In addition to becoming the crosslinking group connecting the 2,6-disubstituted phenol, a part of dicyclopentadiene forms part or all of R 2 .

[0065] In R 2 in one molecule, on average, there is at least one or more, preferably 0.5 to 1 dicyclopentadienyl group per phenolic ring. This is not limited to the general formula (5), and the same applies to R 2 in the general formula (1) and the general formula (2).

[0066] Examples of the phenols as the raw materials of the phenolic resin represented by the 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(tert-butyl)phenol, 2,6-dihexylphenol, 2,6-dicyclohexylphenol, 2,6-diphenylphenol, etc. From the viewpoints of ease of acquisition and reactivity when forming a cured product, 2,6-diphenylphenol or 2,6-dimethylphenol is preferred, and 2,6-dimethylphenol is particularly preferred.

[0067] The acid catalyst used when reacting phenols with dicyclopentadiene is a Lewis acid, specifically boron trifluoride compounds such as boron trifluoride, boron trifluoride-phenol complex, boron trifluoride-ether complex; metal chlorides such as aluminum chloride, tin chloride, zinc chloride, tetrachloroethane, iron chloride; organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, etc. Among them, in terms of ease of operation, boron trifluoride-ether complex is preferred. Regarding the usage amount of the acid catalyst, in the case of boron trifluoride-ether complex, it is 0.001 to 20 parts by mass relative to 100 parts by mass of dicyclopentadiene, and preferably 0.5 to 10 parts by mass.

[0068] As a method for confirming that the dicyclopentenyl group represented by the formula (1b) or the formula (1c) is introduced into the phenol resin represented by the general formula (5), mass spectrometry and Fourier transform-infrared (FT-IR) measurement can be used.

[0069] In the case of using mass spectrometry, electrospray ionization mass spectrometry (ESI-MS), field desorption mass spectrometry (FD-MS), etc. can be used. By subjecting a sample after separating components with different nucleosome numbers by gel permeation chromatography (GPC) etc. to mass spectrometry, it can be confirmed that the dicyclopentenyl group is introduced.

[0070] In the case of using the FT-IR measurement method, a sample dissolved in an organic solvent such as tetrahydrofuran (THF) is coated on a KRS-5 cell, and the organic solvent is dried to obtain a cell with a sample film. If it is measured by FT-IR, a peak derived from the C-O stretching vibration in the phenol nucleus appears near 1210 cm -1 . Only when the dicyclopentenyl group is introduced, a peak derived from the C-H stretching vibration of the olefin part of the dicyclopentadiene skeleton appears near 3040 cm -1 . When the start and end of the target peak are connected by a straight line to form a baseline, and the length from the peak apex to the baseline is taken as the peak height, the ratio (A -1 ) of the peak near 3040 cm 3040 to the peak near 1210 cm -1 (A 1210 ) can be used to quantify the introduction amount of the dicyclopentenyl group. It can be confirmed that the larger the ratio, the more preferable the physical property value, and the preferable ratio (A 3040 / A 1210 ) required to meet the target physical properties.3040 / A 1210 ) is 0.05 or more, more preferably 0.1 or more.

[0071] As a reaction method, it can be as follows: load 2,6-disubstituted phenol and a catalyst into a reactor, and dropwise add dicyclopentadiene over 1 hour to 10 hours.

[0072] As the reaction temperature, it is preferably 50°C to 200°C, more preferably 100°C to 180°C, and further preferably 120°C to 160°C. The reaction time is preferably 1 hour to 10 hours, more preferably 3 hours to 10 hours, and further preferably 4 hours to 8 hours.

[0073] After the reaction is completed, add an alkali such as sodium hydroxide, potassium hydroxide, or calcium hydroxide to deactivate the catalyst. Then, add a solvent such as an aromatic hydrocarbon like toluene or xylene; a ketone such as methyl ethyl ketone or methyl isobutyl ketone for dissolution and perform water washing, and then recover the solvent under reduced pressure, whereby the target phenolic resin can be obtained. Furthermore, it is preferable to react as much of the dicyclopentadiene as possible, and leave a part of the 2,6-disubstituted phenols unreacted, preferably 10% or less unreacted, and recover it under reduced pressure.

[0074] Furthermore, when carrying out the reaction, solvents such as aromatic hydrocarbons like benzene, toluene, or xylene; halogenated hydrocarbons such as chlorobenzene or dichlorobenzene; ethers such as ethylene glycol dimethyl ether or diethylene glycol dimethyl ether can also be used as needed for viscosity adjustment, etc.

[0075] The epoxy resin represented by the general formula (4) can be advantageously obtained by reacting an epihalohydrin such as epichlorohydrin with the phenolic resin. The reaction can be carried out according to a known method.

[0076] For example, it can be obtained as follows: add an alkali metal hydroxide such as sodium hydroxide in the form of a solid or concentrated aqueous solution to a mixture of the phenolic resin and an epihalohydrin in an excess molar amount relative to the hydroxyl group of the phenolic resin, and react at a reaction temperature of 30°C to 120°C for 0.5 hour to 10 hours; or add a quaternary ammonium salt such as tetraethylammonium chloride as a catalyst to the phenolic resin and an excess molar amount of epihalohydrin, and react at a temperature of 50°C to 150°C for 1 hour to 5 hours to obtain a polyhalohydrin ether, and then add an alkali metal hydroxide such as sodium hydroxide in the form of a solid or concentrated aqueous solution to the obtained polyhalohydrin ether and react at a temperature of 30°C to 120°C for 1 hour to 10 hours.

[0077] In the said reaction, the usage amount of the epihalohydrin is in the range of 1-fold molar to 10-fold molar, preferably 2-fold molar to 5-fold molar relative to the hydroxyl group of the phenolic resin, and in addition, the usage amount of the alkali metal hydroxide is in the range of 0.85-fold molar to 1.1-fold molar relative to the hydroxyl group of the phenolic resin.

[0078] The epoxy resin obtained through the above reaction contains unreacted epichlorohydrin and alkali metal halides. Therefore, the unreacted epichlorohydrin is removed by evaporation from the reaction mixture, and then the alkali metal halides are removed by methods such as extraction with water and filtration separation, whereby the target epoxy resin can be obtained.

[0079] The epoxy equivalent (g / eq.) of the dicyclopentadiene-type epoxy resin is preferably 244 to 3700, more preferably 260 to 2000, and still more preferably 270 to 700.

[0080] The molecular weight distribution of the dicyclopentadiene-type epoxy resin can be changed by varying the feeding ratio of the phenolic resin and epichlorohydrin during the epoxidation reaction. The closer the amount of epichlorohydrin used is to equimolar relative to the hydroxyl groups of the phenolic resin, the higher the molecular weight distribution is formed. The closer the amount of epichlorohydrin used is to 20-fold molar relative to the hydroxyl groups of the phenolic resin, the lower the molecular weight distribution is formed. In addition, the phenolic resin can be made to act on the obtained epoxy resin again to make it high molecular weight.

[0081] By reacting acrylic acid or methacrylic acid with the dicyclopentadiene-type epoxy resin, an epoxy acrylate resin represented by the general formula (1) can be produced. The epoxy acrylate resin can be made into a curable resin composition as described later, and thus a cured product can be made.

[0082] The alkali-soluble resin represented by the general formula (2) of the present invention can be obtained from the epoxy acrylate resin represented by the general formula (1). In this sense, the epoxy acrylate resin represented by the general formula (1) is also an intermediate of the alkali-soluble resin represented by the general formula (2).

[0083] In the general formula (2), R 1 , R 2 and n have the same meanings as in the general formula (1), Y is a group containing an unsaturated bond represented by the formula (2a), and L represents a hydrogen atom or a group containing a carboxyl group represented by the formula (3). Here, 50 mol% or more of L is a group containing a carboxyl group represented by the formula (3). R 3 has the same meaning as in the formula (1a), M represents a carboxylic acid residue of p + 1 valence, and p is 1 or 2. Here, the carboxylic acid residue is a group generated by removing a carboxyl group or an acid anhydride group from a divalent or trivalent carboxylic acid or carboxylic anhydride.

[0084] L may all be carboxyl group-containing groups represented by the formula (3), or may have both a hydrogen atom and a carboxyl group-containing group. Among all L, the carboxyl group-containing group is 50 mol% or more, preferably 70 mol% to 100 mol%, more preferably 90 mol% to 100 mol%, and still more preferably 100 mol%. Since the carboxyl group-containing group is reactive with a base, alkali solubility is imparted to the alkali-soluble resin or its polymerization reactant (uncured product). By varying the presence ratio of the carboxyl group-containing group in L, the alkali solubility can be adjusted, and thus the alkali developability can be optimized. In addition, by varying the type of the carboxyl group-containing group represented by the formula (3), resin properties such as alkali developability can also be changed.

[0085] The alkali-soluble resin represented by the general formula (2) can be obtained by reacting the hydroxyl group of the epoxy acrylate resin represented by the general formula (1) with carboxylic acids selected from dicarboxylic acids, tricarboxylic acids, or acid anhydrides (mono-acid anhydrides) of these.

[0086] As the carboxylic acids, acid anhydrides are often used for the reaction, so they are exemplified in the form of acid anhydrides. The carboxylic acid residues derived from the carboxylic acids may be further substituted by substituents such as alkyl groups, cycloalkyl groups, and aromatic groups.

[0087] Examples of saturated chain hydrocarbon dicarboxylic acids or tricarboxylic acids include acid anhydrides 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.

[0088] Examples of saturated cyclic hydrocarbon dicarboxylic acids or tricarboxylic acids include acid anhydrides such as hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, and hexahydrotrimellitic acid.

[0089] Examples of unsaturated dicarboxylic acids or tricarboxylic acids include acid anhydrides such as maleic acid, itaconic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, and chlorendic acid.

[0090] Examples of other dicarboxylic acids or tricarboxylic acids include acid anhydrides such as phthalic acid and trimellitic acid. Among these, acid anhydrides of succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, or trimellitic acid are preferred, and acid anhydrides of succinic acid, itaconic acid, or tetrahydrophthalic acid are more preferred. Furthermore, one of these carboxylic acids may be used, or two or more may be used in combination.

[0091] When synthesizing the alkali-soluble resin, the reaction temperature is preferably 20°C to 120°C, more preferably 40°C to 90°C. The molar ratio of the epoxy acrylate resin to the carboxylic acid at this time can be selected in such a way that the proportion of the carboxyl group-containing groups in L falls within the above range.

[0092] The alkali-soluble resin can be made into a photosensitive resin composition, and the photosensitive resin composition can be cured to form a cured product.

[0093] The epoxy acrylate resin or alkali-soluble resin of the present invention has, on average, two or more polymerizable unsaturated groups, and thus can be made into a curable resin composition.

[0094] When using the epoxy acrylate resin, it does not have alkali developability, but when using the alkali-soluble resin, it can have alkali developability.

[0095] The curable resin composition of the present invention contains the epoxy acrylate resin of the present invention and a polymerization initiator. The photosensitive resin composition of the present invention contains the alkali-soluble resin of the present invention, a photopolymerizable monomer, and a photopolymerization initiator.

[0096] The curable resin composition of the present invention can be formulated with a photopolymerization initiator or a radical polymerization initiator as the initiator, and can also be formulated with other polyfunctional acrylates, etc. The resin component (excluding the solvent as the component of the epoxy acrylate resin and the cured resin) in the curable resin composition is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more.

[0097] As the photopolymerization initiator, various known photopolymerization initiators can be used. For example, the following can be cited: acetophenone, 2,2 - diethoxyacetophenone, p - dimethylacetophenone, p - dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p - tert - butylacetophenone and other acetophenone - based compounds; benzophenone, 2 - chlorobenzophenone, p,p' - bis(dimethylamino)benzophenone and other benzophenone - based compounds; benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ether - based compounds; 2 - (o - chlorophenyl)-4,5 - diphenylimidazole, 2 - (o - chlorophenyl)-4,5 - bis(m - methoxyphenyl)imidazole, 2 - (o - fluorophenyl)-4,5 - diphenylimidazole, 2 - (o - methoxyphenyl)-4,5 - diphenylimidazole, 2,4,5 - triaryl imidazole and other imidazole - based compounds; 2 - trichloromethyl - 5 - styryl - 1,3,4 - oxadiazole, 2 - trichloromethyl - 5 - (p - cyanostyryl)-1,3,4 - oxadiazole, 2 - trichloromethyl - 5 - (p - methoxystyryl)-1,3,4 - oxadiazole and other halomethyl thiazole compounds; 2,4,6 - tris(trichloromethyl)-1,3,5 - triazine, 2 - methyl - 4,6 - bis(trichloromethyl)-1,3,5 - triazine, 2 - phenyl - 4,6 - bis(trichloromethyl)-1,3,5 - triazine, 2 - (4 - chlorophenyl)-4,6 - bis(trichloromethyl)-1,3,5 - triazine, 2 - (4 - methoxyphenyl)-4,6 - bis(trichloromethyl)-1,3,5 - triazine, 2 - (4 - methoxynaphthyl)-4,6 - bis(trichloromethyl)-1,3,5 - triazine, 2 - (4 - methoxystyryl)-4,6 - bis(trichloromethyl)-1,3,5 - triazine, 2 - (3,4,5 - trimethoxystyryl)-4,6 - bis(trichloromethyl)-1,3,5 - triazine, 2 - (4 - methylthioystyryl)-4,6 - bis(trichloromethyl)-1,3,5 - triazine and other halomethyl - s - triazine - based compounds; 1,2 - octanedione, 1 - [4 - (phenylthio)phenyl]-, 2 - (o - benzoyl oxime), 1 - (4 - phenylthiophenyl)butane - 1,2 - dione - 2 - oxime - o - benzoate, 1 - (4 - methylthiophenyl)butane - 1,2 - dione - 2 - oxime - o - acetate, 1 - (4 - methylthiophenyl)butan - 1 - one oxime - o - acetate and other o - acyl oxime - based compounds; benzil dimethyl ketal, thioxanthone, 2 - chlorothioxanthone, 2,4 - diethylthioxanthone, 2 - methylthioxanthone, 2 - isopropylthioxanthone and other sulfur compounds; 2 - ethylanthraquinone, octamethylanthraquinone, 1,2 - benzanthraquinone, 2,3 - diphenylanthraquinone and other anthraquinone - based compounds; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide; thiol compounds such as 2 - mercaptobenzimidazole, 2 - mercaptobenzoxazole, 2 - mercaptobenzothiazole; tertiary amines such as triethanolamine, triethylamine, etc. Furthermore, these photopolymerization initiators can be used alone or in combination of two or more.

[0098] Furthermore, one or more of the above photoinitiators and known photosensitizers can be used simultaneously. Examples of photosensitizers include Michler's ketone, ethyl N,N-dimethylaminobenzoate, isopentyl N,N-dimethylaminobenzoate, triethanolamine, triethylamine, etc. With respect to 100 parts by mass of the epoxy acrylate resin, the amount of the photosensitizer used is preferably 0 to 20 parts by mass, more preferably 0.02 to 10 parts by mass, and still more preferably 0.05 to 2 parts by mass.

[0099] For thermal polymerization, it is preferable to blend a radical polymerization initiator, but in the case of only photocuring, the radical polymerization initiator may not be blended. Examples of preferred radical polymerization initiators include peroxides such as known benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, tert-butyl peroxypropionate, etc.; and azo compounds such as 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(methyl isobutyrate), α,α'-azobis(isobutyronitrile), 4,4'-azobis(4-cyanovaleric acid), etc.

[0100] With respect to 100 parts by mass of the epoxy acrylate resin, the amount of the polymerization initiator used is preferably 0.01 to 100 parts by mass, more preferably 0.5 to 40 parts by mass, and still more preferably 1 to 10 parts by mass.

[0101] The thermal polymerization initiator and the photoinitiator can be used simultaneously or only one of them can be used.

[0102] With respect to 100 parts by mass of the epoxy acrylate resin, the amount of the photoinitiator used is preferably 0.01 to 100 parts by mass, more preferably 0.5 to 40 parts by mass, and still more preferably 1 to 10 parts by mass. In addition, with respect to 100 parts by mass of the resin composition, it is usually 0.01 to 50 parts by mass, preferably 1 to 20 parts by mass.

[0103] With respect to 100 parts by mass of the epoxy acrylate resin, the amount of the thermal polymerization initiator used is preferably 0.01 to 100 parts by mass, more preferably 0.02 to 60 parts by mass, and still more preferably 0.05 to 2 parts by mass. In addition, with respect to 100 parts by mass of the curable resin composition, it is preferably 0.01 to 50 parts by mass, more preferably 0.01 to 30 parts by mass.

[0104] In the photosensitive resin composition of the present invention, in the solid components other than the solvent (the solid components include monomers that become solid components after curing), it is preferably contains 30% by mass or more of the alkali-soluble resin represented by the general formula (2), and more preferably contains 50% by mass or more.

[0105] In order to exhibit the characteristics of a photosensitive resin composition, it is preferably contains the following components (A) to (C) as essential components, and more preferably also contains component (D).

[0106] (A) The alkali-soluble resin

[0107] (B) A photopolymerizable monomer having at least one polymerizable unsaturated group

[0108] (C) A photoinitiator

[0109] (D) An epoxy resin

[0110] Examples of the photopolymerizable monomer as component (B) include: monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate; 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, glycerol (meth)acrylate and other (meth)acrylate esters. When it is necessary to form a crosslinked structure between molecules of the alkali-soluble resin, it is preferably to use a photopolymerizable monomer having two or more polymerizable unsaturated groups, and more preferably to use a photopolymerizable monomer having three or more polymerizable unsaturated groups. Furthermore, one of these compounds can be used, or two or more can be used in combination.

[0111] The blending ratio [(A) / (B)] (mass ratio) of the component (B) to the component (A) is preferably 20 / 80 to 90 / 10, more preferably 40 / 60 to 80 / 20. Here, if the blending ratio of the alkali-soluble resin is small, the cured product after the photocuring reaction becomes brittle. In addition, since the acid value of the coating film is low, the solubility of the unexposed portion in the alkali developer decreases, so problems such as pattern edge jitter and blurriness occur. On the contrary, if the blending ratio of the alkali-soluble resin is greater than the above range, the proportion of the photoreactive functional groups in the resin is small, so the formation of the crosslinked structure by the photocuring reaction may be insufficient. In addition, when the acid value of the resin component is too high, the solubility of the exposed portion in the alkali developer becomes high, so there may be problems such as the formed pattern being likely to become thinner than the target line width and the pattern being likely to be missing.

[0112] As the photopolymerization initiator as the component (C), the same photopolymerization initiators as those listed in the description of the curable resin composition of the present invention can be exemplified.

[0113] The addition amount of the component (C) is preferably 0.1 part by mass to 10 parts by mass, more preferably 2 parts by mass to 5 parts by mass, based on 100 parts by mass in total of the components (A) and (B). Here, if the addition amount of the photopolymerization initiator is less than 0.1 part by mass, sufficient sensitivity cannot be obtained. If the addition amount of the photopolymerization initiator exceeds 10 parts by mass, halation is likely to occur. Halation means that the conical shape (the film thickness direction shape of the developed pattern profile) becomes unclear and becomes a state with corners. Furthermore, when exposed to high temperature in subsequent processes, decomposition gas may be generated.

[0114] Examples of the (D) epoxy resin include: phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin and other epoxy resins; compounds having at least one epoxy group such as phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, glycidyl methacrylate. When it is necessary to increase the crosslinking density of the alkali-soluble resin, a compound having at least two or more epoxy groups is preferred.

[0115] When using the component (D), the addition amount of the component (D) is preferably in the range of 10 to 40 parts by mass relative to the total 100 parts by mass of the components (A) and (B). Here, as one of the purposes of adding an epoxy resin, sometimes the amount of carboxyl groups remaining when forming a cured film after patterning is reduced in order to improve the reliability of the cured film. In this case, if the amount of the epoxy resin used is less than 10 parts by mass, it may not be possible to ensure the moisture resistance reliability when used as an insulating film. On the other hand, when the amount of the epoxy resin used is more than 40 parts by mass, the amount of photosensitive groups of the resin component in the photosensitive resin composition is reduced, and it may not be possible to sufficiently obtain the sensitivity required for patterning.

[0116] The photosensitive resin composition containing the components (A) to (C) or the components (A) to (D) may be dissolved in a solvent or various additives may be formulated and used as needed. For example, when the photosensitive resin composition of the present invention is used for insulating material applications, etc., it is preferable to use a solvent in addition to the essential components. Examples of the solvent include: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α-terpineol or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and acetates 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 alone or in combination of two or more, a uniform solution-like composition can be prepared.

[0117] In addition, in the photosensitive resin composition of the present invention, additives such as a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a coupling agent, and a surfactant can be blended as needed. Among them, as the curing accelerator, for example, known compounds such as those commonly used as curing accelerators, curing catalysts, latent curing agents, etc. in epoxy resins can be used, including: tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borate esters, Lewis acids, organometallic compounds, imidazoles, diazabicyclic compounds, etc. Examples of the thermal polymerization inhibitor and antioxidant include: hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol-based compounds, phosphorus-based heat stabilizers, etc. Examples of the plasticizer include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. Examples of the filler include: glass fiber, silica, mica, alumina, etc. In addition, examples of the antifoaming agent and leveling agent include silicone-based, fluorine-based, and acrylic-based compounds, etc. Examples of the coupling agent include: vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-(glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-ureidopropyltriethoxysilane. Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, etc.

[0118] The photosensitive resin composition of the present invention preferably contains a total of 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more of the components (A) to (D) in the solid components excluding the solvent.

[0119] The amount of the solvent varies depending on the target viscosity, but is preferably 10% by mass to 80% by mass based on the total amount.

[0120] In addition, the coating film (cured product) of the present invention can be obtained, for example, by the following method: coating a solution of the photosensitive resin composition on a substrate or the like, drying the solvent, and irradiating light (including ultraviolet rays, radiation, etc.) for curing. A photomask or the like is used to set the portion irradiated with light and the portion not irradiated with light, and only the portion irradiated with light is cured, and the other portion is dissolved with an alkaline solution, whereby a coating film having a desired pattern can be obtained.

[0121] Regarding each process of the film-forming method by coating and drying a photosensitive resin composition, if specific examples are given, when coating the photosensitive resin composition on a substrate, any method such as a known solution dipping method, spraying method, method using a roll coater, land coater, slit coater, or spin coater can be adopted. After coating to a desired thickness using these methods, the solvent is removed (pre-baking), thereby forming a film. Pre-baking is carried out by heating using an oven, hot plate, etc., vacuum drying, or a combination of these. The heating temperature and heating time of pre-baking can be appropriately selected according to the solvent used. For example, it is preferably carried out at 80°C to 120°C for 1 minute to 10 minutes.

[0122] As the radiation used in exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, g-ray, i-ray, X-ray, etc. can be used. The wavelength range of the radiation is preferably 250 nm to 450 nm.

[0123] In addition, as a developer suitable for the alkali development, for example, an aqueous solution of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. can be used. 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°C to 35°C, and a commercially available developer or an ultrasonic cleaner, etc. can be used to precisely form a fine image. Furthermore, water washing is usually carried out after alkali development. As a development treatment method, a spray development method, a spraying development method, a dip development method, a puddle development method, etc. can be applied.

[0124] After developing in the above-described manner, heat treatment (post-baking) is carried out at 180°C to 250°C for 20 minutes to 100 minutes. This post-baking is carried out for the purpose of improving the adhesion between the patterned coating film and the substrate, etc. Similar to pre-baking, post-baking is carried out by heating using an oven, hot plate, etc. The patterned coating film is formed through each process based on photolithography. Then, polymerization or curing is completed by heat (sometimes both are collectively referred to as curing), thereby forming a cured film such as an insulating film with a desired pattern. The curing temperature at this time is preferably 160°C to 250°C. The cured product of the present invention can adopt a cured film and various other forms.

[0125] Component (A) of the photosensitive resin composition of the present invention has a large number of polymerizable unsaturated groups in one molecule, so the photocurability is improved, and the crosslinking density after curing can be increased without increasing the amount of photoinitiator. That is, when ultraviolet rays or electron beams are irradiated on a thick film, the cured part is cured to the bottom, so the solubility difference between the exposed part and the unexposed part with respect to the alkali developer becomes larger, so the pattern size stability, development margin, and pattern adhesion are improved, and pattern formation can be performed with high resolution. Moreover, even in the case of a thin film, by increasing the sensitivity, the residual film amount of the exposed part can be greatly improved, and peeling during development can be suppressed.

[0126] The photosensitive resin composition of the present invention can be extremely effectively used for solder resist, plating resist, etching resist for manufacturing circuit boards, insulating films for multilayerization of wiring boards for mounting semiconductor elements, gate insulating films of semiconductors, photosensitive adhesives (especially adhesives that require heat bonding performance even after pattern formation by photolithography), etc.

[0127] Examples

[0128] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto. In the examples, unless otherwise specified, "parts" means parts by mass, and "%" means mass%. In addition, unless otherwise specified, the evaluation of the resin in these examples is carried out as described below.

[0129] [Solid content concentration]

[0130] Precision weighing [W1 (g)] is carried out by impregnating a glass filter [mass: W0 (g)] with a resin solution, a photosensitive resin composition, etc. (about 1 g), and the value of the mass [W2 (g)] after heating at 160 °C for 2 hours is used to calculate by the following formula.

[0131] Solid content concentration (%) = 100 × (W2 - W0) / (W1 - W0)

[0132] [Acid value]

[0133] The measurement was carried out according to the Japanese Industrial Standard (JIS) K 0070 standard. Specifically, the resin solution was dissolved in dioxane, and a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) was used to titrate with 0.1N-KOH aqueous solution, and the amount of KOH required per 1 g of the solid component (mg) was used as the acid value.

[0134] [Molecular weight]

[0135] Measurement was carried out using gel permeation chromatography (GPC) (“HLC-8220GPC” manufactured by Tosoh Corporation, column: TSKgel SuperH2000 (2 pieces) + TSKgel SuperH3000 (1 piece) + TSKgel SuperH4000 (1 piece) + TSKgel SuperH5000 (1 piece) (all manufactured by Tosoh Corporation), solvent: tetrahydrofuran, temperature: 40 °C, speed: 0.6 mL / min), and the value obtained as the conversion value of standard polystyrene (“PS-Oligomer Kit” manufactured by Tosoh Corporation) was set as the weight average molecular weight (Mw).

[0136] [Relative dielectric constant, dielectric loss tangent]

[0137] Using the cavity resonance method (vector network analyzer (VNA) E8363B (manufactured by Agilent Technologies), cavity resonator perturbation method dielectric constant measurement device (manufactured by Kanto Electronics Application Development)), the value at 1 GHz was measured after storing for 24 hours in a room at 23 °C and 50% humidity after being completely dried.

[0138] [Adhesion]

[0139] On the film of the glass substrate with the cured film, cross cuts were made in a grid pattern of at least one hundred, and then a peeling test was performed using cellophane tape, and the state of the grid was visually evaluated.

[0140] ◎: No peeling was found at all

[0141] ○: Slight peeling could be confirmed on the coating film

[0142] △: Peeling could be confirmed on a part of the coating film

[0143] ×: Most of the film peeled off

[0144] [Alkali resistance]

[0145] The glass substrate with the cured film was immersed in a solution maintained at 80 °C in a mixture of 30 parts of 2-aminoethanol and 70 parts of glycol ether, lifted after 10 minutes, washed with pure water and dried to produce a sample after chemical impregnation, and the adhesion was evaluated.

[0146] [Acid resistance]

[0147] The glass substrate with a cured film was immersed in a solution of aqua regia (hydrochloric acid: nitric acid = 7:3) maintained at 50 °C, lifted after 10 minutes, washed with pure water and dried to produce a sample after chemical impregnation, and the adhesion was evaluated.

[0148] In addition, the codes of the materials used are as follows.

[0149] E1: Epoxy resin obtained in Synthesis Example 1

[0150] E2: Epoxy resin obtained in Synthesis Example 2

[0151] E3: Phenolic novolak epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., YDPN-638, epoxy equivalent 177 g / eq.)

[0152] E4: Bisphenol A liquid epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., YD-127, epoxy equivalent 182 g / eq.)

[0153] E5: Cresol novolak epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., YDCN-700-3, epoxy equivalent 203 g / eq., softening point 73 °C)

[0154] THPA: 1,2,3,6-Tetrahydrophthalic anhydride

[0155] TPP: Triphenylphosphine

[0156] HQ: Hydroquinone

[0157] TEAB: Tetraethylammonium bromide

[0158] MIBK: Methyl isobutyl ketone

[0159] PGMEA: Propylene glycol monomethyl ether acetate

[0160] B1: Dipentaerythritol hexaacrylate

[0161] BPDA: 3,3',4,4'-Biphenyltetracarboxylic dianhydride

[0162] C1: Photoinitiator (manufactured by BASF, Irgacure 184)

[0163] C2: Photoinitiator (4,4'-Bis(dimethylamino)benzophenone (Michler's ketone))

[0164] Synthesis Example 1

[0165] In a reaction apparatus including a stirrer, a temperature control device, a nitrogen gas introduction device, a dropping device, and a reflux condenser, 970 parts of 2,6-xylenol and 14.5 parts of 47% BF3 ether complex were charged, and the mixture was heated to 70 °C while stirring. While maintaining the temperature, 300 parts of dicyclopentadiene (0.29 times the molar amount relative to 2,6-xylenol) was added dropwise over 2 hours. Further, the reaction was carried out at a temperature of 125 °C to 135 °C for 6 hours, and 2.3 parts of calcium hydroxide was added. Further, 4.6 parts of a 10% aqueous oxalic acid solution was added. Then, after heating to 160 °C and dehydrating, the temperature was raised to 200 °C under a reduced pressure of 5 mmHg to evaporate and remove the unreacted raw materials. 1000 parts of MIBK was added to dissolve the product, and 400 parts of warm water at 80 °C was added for washing with water, and the lower aqueous phase was separated and removed. Then, the temperature was raised to 160 °C under a reduced pressure of 5 mmHg to evaporate and remove MIBK, and 540 parts of a reddish-brown phenolic resin was obtained. The hydroxyl equivalent was 213, the softening point was 71 °C, and the absorption ratio (A 3040 / A 1210 ) was 0.11. The mass spectrum obtained by ESI-MS (negative) was measured, and as a result, M− = 253, 375, 507, and 629 were confirmed.

[0166] In a reaction apparatus including a stirrer, a temperature control device, a vacuum degree control device, a nitrogen gas introduction device, a dropping device, and a reflux condenser, 250 parts of the obtained phenolic resin, 544 parts of epichlorohydrin, and 163 parts of diethylene glycol dimethyl ether were added, and the mixture was heated to 65 °C. While maintaining the temperature of 63 °C to 67 °C under a reduced pressure of 125 mmHg, 108 parts of a 49% aqueous sodium hydroxide solution was added dropwise over 4 hours. During this period, epichlorohydrin and water were azeotroped, and the water flowing out was successively removed from the system. After the reaction was completed, epichlorohydrin was recovered under the conditions of 5 mmHg and 180 °C, and 948 parts of MIBK was added to dissolve the product. Then, 263 parts of water was added to dissolve the by-produced sodium chloride, and the mixture was allowed to stand, and the lower brine was separated and removed. After neutralization with an aqueous phosphoric acid solution, the resin solution was washed with water until the washing liquid became neutral, and then filtered. The temperature was raised to 180 °C under a reduced pressure of 5 mmHg to distill off MIBK, and 298 parts of a reddish-brown transparent 2,6-xylenol-dicyclopentadiene type epoxy resin (E1) was obtained. It was a resin having an epoxy equivalent of 282, a total chlorine content of 980 ppm, and being semi-solid at room temperature.

[0167] Synthesis Example 2

[0168] In the same reaction apparatus as in Synthesis Example 1, 95.0 parts of 2,6-xylenol and 6.3 parts of 47% BF3 ether complex were charged, and the mixture was heated to 70 °C while stirring. While maintaining the temperature, 58.8 parts of dicyclopentadiene (0.56 times the molar amount relative to 2,6-xylenol) were added dropwise over 1 hour. Further, after reacting at a temperature of 115 °C to 125 °C for 3 hours, 69.2 parts of dicyclopentadiene (0.67 times the molar amount relative to 2,6-xylenol) were added dropwise over 1 hour at the same temperature, and the reaction was carried out at a temperature of 115 °C to 125 °C for 2 hours. 1.0 part of calcium hydroxide was added. Further, 2.0 parts of a 10% aqueous oxalic acid solution were added. Then, after heating to 160 °C and dehydrating, the temperature was raised to 200 °C under a reduced pressure of 5 mmHg to evaporate and remove unreacted raw materials. 520 parts of MIBK were added to dissolve the product, and 150 parts of warm water at 80 °C were added for washing with water, and the lower aqueous phase was separated and removed. Then, the temperature was raised to 160 °C under a reduced pressure of 5 mmHg to evaporate and remove MIBK, and 221 parts of a reddish-brown phenolic resin were obtained. The hydroxyl equivalent was 377, the softening point was 102 °C, and the absorption ratio (A 3040 / A 1210 ) was 0.18. The mass spectrum obtained by ESI-MS (negative) was measured, and as a result, M− = 253, 375, 507, and 629 were confirmed.

[0169] In the same reaction apparatus as 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 the mixture was heated to 65 °C. While maintaining a temperature of 63 °C to 67 °C under a reduced pressure of 125 mmHg, 39 parts of a 49% aqueous sodium hydroxide solution were added dropwise over 4 hours. During this period, epichlorohydrin and water were azeotroped, and the water that flowed out was successively removed from the system. After the reaction was completed, epichlorohydrin was recovered under the conditions of 5 mmHg and 180 °C, and 482 parts of MIBK were added to dissolve the product. Then, 146 parts of water were added to dissolve the by-produced sodium chloride, and the mixture was allowed to stand, and the lower brine was separated and removed. After neutralization with an aqueous phosphoric acid solution, the resin solution was washed with water until the washings became neutral, and then filtered. The temperature was raised to 180 °C under a reduced pressure of 5 mmHg to distill off MIBK, and 200 parts of a reddish-brown transparent 2,6-xylenol-dicyclopentadiene type epoxy resin (E2) were obtained. It was a resin having an epoxy equivalent of 446, a total chlorine content of 431 ppm, and a softening point of 91 °C.

[0170] Example 1

[0171] In a reaction vessel including a stirrer, a temperature regulating device, a reflux cooler and an air introducing device, 282 parts of E1 was dissolved in 63 parts of PGMEA, and then 72 parts of acrylic acid, 3.5 parts of TPP and 0.1 part of HQ were added. While blowing air, the reaction was carried out at 110 °C for 8 hours, and then 293 parts of PGMEA was added to obtain a PGMEA solution of epoxy acrylate resin (R1). The solid content concentration of the obtained resin solution was 50%.

[0172] The obtained resin solution was removed of the solvent by vacuum distillation, and 100 parts of the obtained solid content was put into a fluororesin mold, 1 part of diisopropylbenzene peroxide was added, and it was heated in an oven at 100 °C for 30 minutes and at 170 °C for 1 hour to be cured to obtain a cured product. Using the cured product, a test piece with a thickness of 0.2 mm and a size of 0.2 cm × 10 cm was made, and the relative permittivity and the dielectric loss tangent were measured.

[0173] Example 2

[0174] In the same apparatus as in Example 1, 446 parts of E2 was dissolved in 97 parts of PGMEA, and then 72 parts of acrylic acid, 3.5 parts of TPP and 0.1 part of HQ were added. While blowing air, the reaction was carried out at 110 °C for 8 hours, and then 450 parts of PGMEA was added to obtain a PGMEA solution of epoxy acrylate resin (R2). The solid content concentration of the obtained resin solution was 50%. The relative permittivity and the dielectric loss tangent were measured in the same manner as in Example 1.

[0175] Comparative Example 1

[0176] In the same apparatus as in Example 1, 177 parts of E3 was dissolved in 44 parts of PGMEA, and then 72 parts of acrylic acid, 3.5 parts of TPP and 0.1 part of HQ were added. While blowing air, the reaction was carried out at 110 °C for 8 hours, and then 208 parts of PGMEA was added to obtain a PGMEA solution of epoxy acrylate resin (HR1). The solid content concentration of the obtained resin solution was 50%. The relative permittivity and the dielectric loss tangent were measured in the same manner as in Example 1.

[0177] The results are shown in Table 1.

[0178] [Table 1]

[0179] Example 1 Example 2 Comparative Example 1 Resin R1 R2 HR1 Relative dielectric constant 2.8 2.9 3.4 Dielectric loss tangent 0.014 0.015 0.021

[0180] Example 3

[0181] 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 the mixture was stirred at 120°C to 125°C for 6 hours to obtain an alkali-soluble resin solution (A1). The solid content concentration of the obtained resin solution was 55%.

[0182] 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 were blended to obtain a photosensitive resin composition.

[0183] Using a spin coater, the obtained photosensitive resin composition was coated on a 125 mm × 125 mm glass substrate such that the film thickness after post-baking became 30 μm, and pre-baked at 110°C for 5 minutes to prepare a coated plate. Then, ultraviolet light with a wavelength of 365 nm was irradiated using a high-pressure mercury lamp of 500 W / cm 2 to carry out a photocuring reaction for overall surface exposure. Next, for this exposed coated plate, treatment was carried out for 60 seconds by spray development with a 0.8% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23°C, and then spray water washing was performed. Then, heat curing treatment was carried out at 230°C for 30 minutes using a hot air dryer to obtain a glass substrate with a cured film.

[0184] Example 4

[0185] 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 the mixture was stirred at 120°C to 125°C for 6 hours to obtain an alkali-soluble resin solution (A2). The solid content concentration of the obtained resin solution was 55%.

[0186] Except for using A2 instead of A1, the same operations as in Example 3 were carried out to obtain a photosensitive resin composition and a glass substrate with a cured film.

[0187] Comparative Example 2

[0188] 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 the mixture was stirred at 120°C to 125°C for 6 hours to obtain an alkali-soluble resin solution (HA1). The solid content concentration of the obtained resin solution was 55%.

[0189] Except for using HA1 instead of A1, the same operations as in Example 3 were carried out to obtain a photosensitive resin composition and a glass substrate with a cured film.

[0190] Comparative Example 3

[0191] In the same apparatus as in Example 1, 182 parts of E4 was dissolved in 45 parts of PGMEA, and then 72 parts of acrylic acid, 3.5 parts of TPP, and 0.1 part of HQ were added. While blowing air, the reaction was carried out at 110 °C for 8 hours, and then 212 parts of PGMEA was added to obtain a PGMEA solution of an 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. Then, 61.8 parts of isophorone diisocyanate was added dropwise. After the addition dropwise was completed, stirring was carried out at 75 °C to 80 °C for 6 hours. Further, 21 parts of THPA was added, and stirring was carried out at 90 °C to 95 °C for 6 hours to obtain an alkali-soluble resin solution (HA2). The solid content concentration of the obtained resin solution was 55%.

[0192] Except that HA2 was used instead of A1, the same operations as in Example 3 were carried out to obtain a photosensitive resin composition and a glass substrate with a cured film.

[0193] The acid value (in terms of solid content) and molecular weight (Mw) of the obtained resin solution were measured, and adhesion, alkali resistance, and acid resistance tests were carried out on the obtained glass substrate with a cured film. The results are shown in Table 2.

[0194] [Table 2]

[0195] Example 3 Example 4 Comparative Example 2 Comparative Example 3 Resin A1 A2 HA1 HA2 Acid value (mgKOH / g) 110 80 135 39 Molecular weight (Mw) 890 1500 1450 12100 Adhesion 〇 ◎ 〇 ◎ Alkali resistance ◎ ◎ △ × Acid resistance ◎ ◎ △ ×

[0196] Industrial applicability

[0197] The curable resin composition, photosensitive resin composition, and cured product thereof of the present invention can be applied to solder resistants, plating resistants, etching resistants for manufacturing circuit boards, insulating films for multilayerization of wiring boards for mounting semiconductor elements, gate insulating films of semiconductors, photosensitive adhesives, and the like.

Claims

1. An epoxy acrylate resin is represented by the following general formula (1), and the ratio A of the peak A near 3040 cm -1 in Fourier transform-infrared spectrometry 3040 to the peak A near 1210 cm -1 in Fourier transform-infrared spectrometry 1210 is 0.11 or more, 3040 A 1210 / A -CH2-CH(OH)-CH2-O-CO-CR 3 =CH2(1a) Here, R 1 independently represents a hydrocarbon group having 1 to 8 carbon atoms, R 2 independently represents a hydrogen atom or a dicyclopentenyl group, and at least one is a dicyclopentenyl group; X is a group containing an unsaturated bond represented by the formula (1a), and R 3 represents a hydrogen atom or a methyl group; n represents the number of repetitions, and its average value is 1 to 5.

2. A curable resin composition, characterized in that, It contains the epoxy acrylate resin and a polymerization initiator as described in claim 1.

3. A cured product obtained by curing the curable resin composition as described in claim 2.

4. An alkali-soluble resin represented by the following general formula (2), wherein the ratio A -1 of the peak A -1 near 3040 cm -1 to the peak A -1 near 1210 cm -1 in Fourier transform-infrared spectrometry is 0.11 or more, and the resin has a carboxyl group and a polymerizable unsaturated group in the molecule. -1 near peak A 3040 and 1210 cm -1 near peak A 1210 is the ratio A 3040 3040 / A 1210 1210 is 0.11 or more, and has a carboxyl group and a polymerizable unsaturated group in the molecule. -CH2-CH(OL)-CH2-O-CO-CR 3 =CH2(2a) -CO-M-(COOH)p (3) Here, R 1 independently represents a hydrocarbon group having 1 to 8 carbon atoms, R 2 independently represents a hydrogen atom or a dicyclopentadienyl group, with at least one being a dicyclopentadienyl group; Y is a group containing an unsaturated bond represented by the formula (2a), and R 3 represents a hydrogen atom or a methyl group; n represents the number of repetitions, and its average value is 1 to 5; L represents a hydrogen atom or a carboxyl group-containing group represented by the formula (3), and 50 mol% or more of L is a carboxyl group-containing group; M represents a carboxylic acid residue having a valence of p + 1, and p is 1 or 2.

5. A photosensitive resin composition, characterized in that, It contains the alkali-soluble resin as described in claim 4, a photopolymerizable monomer having at least one polymerizable unsaturated group, and a photopolymerization initiator.

6. The photosensitive resin composition according to claim 5, wherein It further contains an epoxy resin.

7. The photosensitive resin composition according to claim 5 or 6, wherein With respect to a total of 100 parts by mass of the alkali-soluble resin and the photopolymerizable monomer, 0.1 part by mass to 10 parts by mass of a photopolymerization initiator is contained.

8. The photosensitive resin composition according to claim 6, wherein, With respect to a total of 100 parts by mass of the alkali-soluble resin and the photopolymerizable monomer, 10 parts by mass to 40 parts by mass of an epoxy resin is contained.

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

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