Reactive epoxy carboxylate resin, reactive polycarboxylic acid resin, active-energy-ray-curable resin composition using the same, cured product thereof, and use thereof

Abstract

To provide a reactive polycarboxylic acid resin that achieves good developing properties while maintaining high insulation reliability, and an active-energy-ray-curable resin composition including the same.SOLUTION: A reactive epoxy acrylate resin (A) is produced by reacting an epoxy resin (d), which is resulting from reaction between a phenolic resin (c) obtained by reacting a compound represented by formula (a) and a compound represented by formula (b) and an epihalohydrin, with a carboxylic acid compound (e) having both a polymerizable ethylenically unsaturated group and a carboxyl group in one molecule, and, as required, a compound (f) having both a hydroxyl group and a carboxyl group in one molecule. In formula (a), a plurality of R each independently represent a hydrocarbon group having 1-5 carbon atoms, a total number of carbon atoms of the plurality of R being 2-8, and k is an integer of 1-4.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a reactive epoxy carboxylate resin, a reactive polycarboxylic acid resin, an active energy ray-curable resin composition using the same, a cured product thereof, and uses thereof. [Background technology]

[0002] In recent years, the increasing performance of electronic devices (smaller size, lighter weight, and more multifunctionality) has led to the increasing integration of semiconductor components. This has led to the development of increasingly dense and precise semiconductor elements, semiconductor packages, printed wiring boards, flexible wiring boards, and other components. Various component-embedded substrates with embedded chips and chip capacitors are being investigated. Surface protection films or interlayer insulating films used in semiconductor components must be able to develop via opening patterns for interlayer connections using weak alkaline solutions such as sodium carbonate solutions. They must also be heat-resistant and thermally stable while maintaining substrate adhesion and high insulation properties. Therefore, there is a demand for film-forming materials with tougher curing properties.

[0003] Among these materials, unsaturated group-containing polycarboxylic acid resins, which are the reaction products of a general epoxy resin with acrylic acid, a carboxylic acid compound having a hydroxyl group, and a polybasic acid anhydride, are known as materials that have excellent developability despite their low acid value, and it is also known that these resins are suitable for use in resist inks (Patent Document 1).

[0004] On the other hand, reactive polycarboxylic acid resins based on trisphenolmethane-type epoxy (e.g., EPPN-502H manufactured by Nippon Kayaku) are also generally known, and their use as surface protective films or interlayer insulating films is also being investigated (Patent Document 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 06-324490 [Patent Document 2] Japanese Patent Application Publication No. 2024-036514 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the conventional build-up method for forming via holes using laser processing requires forming each via one by one, which takes a lot of time when a large number of vias are required for high density. Therefore, forming a surface protection film using photolithography has been studied as a method that can form a large number of vias at once, but it has not been possible to maintain high insulation reliability. Therefore, an object of the present invention is to provide a reactive polycarboxylic acid resin that overcomes the above-mentioned problems of the conventional art and has good development properties without sacrificing high insulation reliability, and an active energy ray-curable resin composition containing the same. [Means for solving the problem]

[0007] In order to solve the above-mentioned problems, the present inventors have developed a reactive epoxy carboxylate resin (A) obtainable by reacting a phenolic resin (c) obtained by reacting a compound represented by compound (a) with a compound represented by compound (b), with an epihalohydrin to obtain an epoxy resin (d), with a carboxylic acid compound (e) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and, if necessary, a compound (f) having both a hydroxyl group and a carboxy group in one molecule. Furthermore, the present inventors have found that a reactive epoxy carboxylate resin (A) is obtained by reacting a phenolic resin (c) obtained by reacting a compound (a) with a compound represented by the following formula (b), with an epihalohydrin, and then reacting the resulting epoxy resin (d) with a carboxylic acid compound (e) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and, if necessary, a compound (f) having both a hydroxyl group and a carboxy group in one molecule, to produce a reactive polycarboxylic acid compound (B) which is obtained by reacting a polybasic acid anhydride (g) with the resulting reactive epoxy carboxylate resin (A). The present inventors have found that the reactive polycarboxylic acid compound (B) has excellent resin properties. Furthermore, the present inventors have found that the reactive epoxy carboxylate compound (A) has excellent hardness and impact resistance, and that the reactive polycarboxylic acid compound (B) has high developability and high insulating reliability, and have also found that compositions containing these compounds can be used as resist materials and the like having good developability without sacrificing high insulating reliability.

[0008] The present invention relates to a reactive epoxy carboxylate resin (A) obtained by reacting a phenolic resin (c) obtained by reacting a compound represented by the following compound (a) with a compound represented by the following compound (b) with an epihalohydrin to obtain an epoxy resin (d), with a carboxylic acid compound (e) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and, if necessary, a compound (f) having both a hydroxyl group and a carboxy group in one molecule.

[0009] [ka]

[0010] (In formula (a), each of the multiple R's independently represents a hydrocarbon group having 1 to 5 carbon atoms. The total number of carbon atoms in the multiple R's is 2 to 8. k is an integer of 1 to 4.) The present invention further relates to a reactive polycarboxylic acid compound (B) obtained by reacting the carboxylate compound (A) with a polybasic acid anhydride (g). The present invention further relates to the epoxy acrylate resin (A) and / or polycarboxylic acid resin (B), wherein the phenol resin (c) is represented by the following general formula (c):

[0011] [ka]

[0012] (In formula (c), each of the multiple R's independently represents a hydrocarbon group having 1 to 5 carbon atoms. In each benzene ring substituted with R, the total number of carbon atoms of the multiple R's is 2 to 8. k is an integer of 1 to 4. n is the average number of repetitions and is 1 to 20.) The present invention further relates to an active energy ray-curable resin composition containing the carboxylate compound (A). The present invention further relates to an active energy ray-curable resin composition containing the reactive polycarboxylic acid compound (B). The present invention further relates to an active energy ray-curable resin composition containing the carboxylate compounds (A) and (B). The present invention further relates to the active energy ray-curable resin composition, which contains a reactive compound (C). The present invention further relates to the active energy ray-curable resin composition containing a pigment. The present invention further relates to the active energy ray-curable resin composition as a molding material. Furthermore, the present invention relates to the active energy ray-curable resin composition as a film-forming material. Furthermore, the present invention relates to the active energy ray-curable resin composition, which is a resist material composition. The present invention also relates to a cured product of the active energy ray-curable resin composition. The present invention also relates to an article overcoated with the cured product. Furthermore, a printed wiring board is provided with at least one of a surface protective film and an interlayer insulating film formed from the active energy ray-curable resin composition. The present invention also relates to a method for producing a reactive epoxy carboxylate resin (A) obtained by reacting a phenolic resin (c) obtained by reacting the compound (a) shown below with a compound (b) shown below with an epihalohydrin to produce an epoxy resin (d), with a carboxylic acid compound (e) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and, if necessary, a compound (f) having both a hydroxyl group and a carboxy group in one molecule. The present invention also relates to a method for producing a reactive polycarboxylic acid compound (B) by reacting the carboxylate compound (A) with a polybasic acid anhydride (g). [Effects of the Invention]

[0013] The active energy ray-curable resin composition of the present invention containing a reactive polycarboxylic acid resin having a polycyclic hydrocarbon group of a specific structure not only gives a cured product having good insulating reliability but also has good developability. Furthermore, the cured product obtained by curing the active energy ray-curable resin composition of the present invention with active energy rays such as ultraviolet rays can be suitably used as a film-forming material having thermal and mechanical toughness, good storage stability, and further high insulating reliability.

[0014] The composition can be suitably used in applications requiring particularly high insulation reliability, such as solder resists for printed wiring boards, protective films for multilayer printed wiring boards, interlayer insulating materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists, and photosensitive optical waveguides. DETAILED DESCRIPTION OF THE INVENTION

[0015] The epoxy resin (d) used in the present invention is obtained by reacting a phenol resin (c) obtained by reacting a compound represented by the following formula (a) with a compound represented by the following formula (b), and then reacting the phenol resin (c) with epihalohydrin.

[0016] [ka]

[0017] In the formula (a), each R independently represents a hydrocarbon group having 1 to 5 carbon atoms, preferably 1 to 4. If the carbon number is 6 or more, heat resistance may be impaired. Furthermore, if a hydrocarbon group is not introduced, the cured product may be prone to water absorption, potentially resulting in swelling during solder reflow. The total number of carbon atoms in each independently present R is 2 to 8, preferably 2 to 6, and more preferably 2 to 5. If the total number of carbon atoms in each independently present R is 1, the effect of reducing water absorption may not be sufficient. If the total number is 9 or more, heat resistance may be reduced. Therefore, the total number of carbon atoms in each independently present R is preferably 2 to 8. k represents an integer from 1 to 4, preferably 2 to 4. For example, if k=2 and each R is a methyl group, the total number of carbon atoms in each independently present R is 2.

[0018] A preferred compound represented by the above formula (a) has alkyl groups at the 2- and 5-positions (or 3- and 6-positions) relative to the phenolic hydroxyl group. By introducing hydrocarbon groups into these substitution positions, it is possible to obtain phenolic resins with narrow molecular weight distributions and epoxy resins derived therefrom. There are no particular limitations on the compound as long as it has alkyl groups at the 2- and 5-positions (or 3- and 6-positions) relative to the phenolic hydroxyl group, but preferred compounds include, for example, 3-methyl-6-t-butylphenol, thymol, carvacrol, and 2,5-dimethylphenol.

[0019] The compound represented by the above formula (b) has a hydroxyl group at the ortho position of the aldehyde group, and after being derived into a reactive epoxy acrylate or a reactive polycarboxylic acid compound, steric hindrance occurs, which makes it possible to exhibit low water absorption in the cured product. The reaction between the compound represented by the formula (a) and the compound represented by the formula (b) may be carried out by any known synthesis method, for example, a method in which the reaction is carried out in a solvent in the presence of an acid catalyst.

[0020] The compound of formula (a) is preferably added in an amount 1.1 to 8 times by mole relative to the compound of formula (b), more preferably 1.25 to 6 times by mole, and even more preferably 1.5 to 4 times by mole. If the amount is less than 1.1 times by mole, the resulting polymer becomes too high, making water washing difficult and significantly reducing the fluidity of the resin. If the amount is more than 8 times by mole, the yield per batch significantly decreases and waste increases, which is undesirable. During the reaction, acid catalysts that can be used include hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid, as well as Lewis acids such as aluminum chloride and zinc chloride, activated clay, acid clay, white carbon, zeolite, and silica alumina, and acidic ion exchange resins. These may be used alone or in combination. The amount of catalyst used is 0.01 to 25 wt %, preferably 0.1 to 15 wt %, based on the total weight of the reaction substrates, phenols (compounds of the above formula (a)) and salicylaldehyde (compounds of the above formula (b)). Using too much catalyst is undesirable because stirring during the synthesis reaction may become difficult and unnecessary waste may increase. Examples of solvents that can be used include water-insoluble solvents such as aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl isobutyl ketone and cyclopentanone, as well as alcoholic solvents such as methanol, ethanol, and isopropanol. However, the solvents are not limited to these, and two or more of these solvents may be used in combination. Furthermore, aprotic polar solvents may be used in combination with the water-insoluble solvents. Examples of suitable solvents include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone, and two or more of these may be used in combination. The reaction temperature is preferably 20 to 180°C, more preferably 40 to 160°C, and even more preferably 50 to 130°C. If the reaction temperature is too high, the methine structure of the trisphenolmethane structure may decompose, and if the reaction temperature is too low, the reaction may not proceed sufficiently.After the reaction is complete, the acidic catalyst may be neutralized with an alkaline aqueous solution or the like, followed by solvent recovery to obtain the target phenolic resin together with the neutralized salt. Alternatively, a water-insoluble organic solvent may be added to the oil layer and repeatedly washed with water until the wastewater becomes neutral, after which the solvent may be removed under heating and reduced pressure to obtain the target phenolic resin. When activated clay or ion exchange resin is used, the reaction solution is filtered after the reaction is complete to remove the catalyst, and the solvent is recovered to obtain the target phenolic resin. The residual monomer content of the compound represented by formula (a) is preferably 0.01 to 10 wt%, more preferably 0.05 to 7.5 wt%, and even more preferably 0.1 to 5 wt%. The amount of this monomer affects the amount of residual low-molecular-weight epoxy resin, which in turn affects heat resistance and other properties.

[0021] A typical structure of the phenolic resin obtained by reacting the compound represented by the above formula (a) with the compound represented by the above formula (b) can be represented by the following formula (c).

[0022] [ka]

[0023] In the above formula (c), R has the same meaning as in the above formula (a). In each benzene ring substituted with R, the total number of carbon atoms in the multiple Rs is 2 to 8. The value and preferred range of k are the same as in the above formula (a). n is the average number of repeating units, and is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. If n is less than 1, there is a risk of a large amount of residual monomer, resulting in reduced heat resistance. n can be determined by GPC analysis and may be calculated from the area % of each peak or from the number average molecular weight (Mn).

[0024] The phenolic resin obtained by reacting the compound represented by the above formula (a) with the compound represented by the above formula (b) contains 75 to 95 area % of a compound represented by the following formula (c') where n=1 in the above formula (c), as detected by a differential refractometer in a gel permeation chromatography analysis:

[0025] [ka]

[0026] In the formula (c'), R and k have the same meanings as in the formula (a). In each benzene ring substituted with R, the total number of carbon atoms of the multiple Rs is 2 to 8.

[0027] The number average molecular weight (Mn) of the phenolic resin obtained by reacting the compound represented by the formula (a) with the compound represented by the formula (b) is preferably 300 to 1500, more preferably 325 to 1000, and even more preferably 350 to 800. If the number average molecular weight is less than 300, there is a risk that the heat resistance will decrease due to residual raw materials, etc. The weight average molecular weight (Mw) of the phenolic resin obtained by reacting the compound represented by the formula (a) with the compound represented by the formula (b) is preferably 300 to 3000, more preferably 325 to 1500, and even more preferably 350 to 1200. If the weight average molecular weight is less than 300, there is a risk that the heat resistance will decrease due to residual raw materials, etc.

[0028] The hydroxyl equivalent of the phenolic resin obtained by reacting the compound represented by formula (a) with the compound represented by formula (b) is preferably 100 to 300 g / eq., more preferably 110 to 200 g / eq., and even more preferably 120 to 180 g / eq. The hydroxyl equivalent may be calculated from the area percentage of gel permeation chromatography (GPC) analysis or measured by titration. When measuring by titration, for example, a sample is acetylated using acetic anhydride in a pyridine solution, and after acetylation is complete, the remaining acid anhydride is decomposed with water. The resulting sample is titrated with a 0.5 N KOH ethanol solution using a potentiometric titrator to measure the amount of free acetic acid, and the hydroxyl equivalent can be determined from the results.

[0029] The epoxy resin (d) used in this embodiment will be described below. The epoxy resin (d) used in this embodiment can be obtained by reacting a phenolic resin obtained by reacting a compound represented by the above formula (a) with a compound represented by the above formula (b), with epihalohydrin. For example, it can be obtained by subjecting the phenolic resin (c) used in this embodiment to an addition or ring-closing reaction with epihalohydrin in the presence of a solvent and a catalyst. The amount of epihalohydrin used is usually 1.0 to 20.0 mol, preferably 1.5 to 10.0 mol, per mol of phenolic hydroxyl groups in the phenolic resin.

[0030] The typical structure of the epoxy resin (d) used in this embodiment can be represented by the following formula (d).

[0031] [ka]

[0032] In the above formula (d), R has the same meaning as in the above formula (a), and the values ​​and preferred ranges of k and n are the same as in the above formula (a).

[0033] Examples of alkali metal hydroxides that can be used in the epoxidation reaction include sodium hydroxide and potassium hydroxide. The alkali metal hydroxide may be a solid or an aqueous solution. When an aqueous solution is used, the alkali metal hydroxide may be continuously added to the reaction system while continuously distilling water and epihalohydrin under reduced pressure or normal pressure, followed by liquid separation to remove water and continuously returning the epihalohydrin to the reaction system. The amount of alkali metal hydroxide used is typically 0.9 to 2.5 mol, preferably 0.95 to 1.5 mol, per mol of phenolic hydroxyl groups in the phenolic resin. If the amount of alkali metal hydroxide used is too small, the reaction will not proceed sufficiently. On the other hand, excessive use of more than 2.5 mol of alkali metal hydroxide per mol of phenolic hydroxyl groups in the phenolic resin will result in the production of unnecessary waste by-products.

[0034] To accelerate the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, or trimethylbenzylammonium chloride may be added as a catalyst. The amount of quaternary ammonium salt used is typically 0.1 to 15 g, and preferably 0.2 to 10 g, per mole of phenolic hydroxyl groups in the phenolic resin. If the amount used is too small, a sufficient reaction acceleration effect cannot be obtained, while if the amount used is too large, the amount of quaternary ammonium salt remaining in the epoxy resin increases, which may cause a deterioration in electrical reliability.

[0035] In order to advance the epoxidation reaction, it is preferable to add an alcohol such as methanol, ethanol, or isopropyl alcohol, or an aprotic polar solvent such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, or dioxane. When an alcohol is used, the amount used is usually 2 to 50% by weight, preferably 4 to 20% by weight, based on the amount of epihalohydrin used. When an aprotic polar solvent is used, the amount used is usually 5 to 100% by weight, preferably 10 to 80% by weight, based on the amount of epihalohydrin used. The reaction temperature is usually 30 to 90°C, preferably 35 to 80°C. The reaction time is usually 0.5 to 100 hours, preferably 1 to 30 hours.

[0036] After the reaction is complete, the reaction product is washed with water, or heated under reduced pressure to remove the epihalohydrin and solvent. To further reduce the hydrolyzable halogen content of the epoxy resin, the recovered epoxy resin can be dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be added to the reaction mixture to ensure ring closure. In this case, the amount of alkali metal hydroxide used is typically 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per mol of phenolic hydroxyl groups in the phenolic resin used for glycidylation. The reaction temperature is typically 50 to 120°C, and the reaction time is typically 0.5 to 24 hours. After the reaction is complete, the resulting salt is removed by filtration, washing with water, or the like, and the solvent is then distilled off under reduced pressure with heating to obtain the epoxy resin (d) used in this embodiment.

[0037] The softening point of the epoxy resin (d) used in this embodiment is preferably 40 to 150°C, more preferably 45 to 125°C, and even more preferably 50 to 100°C. If the softening point is higher than 150°C, the solvent is likely to remain when the resin is removed, which can easily lead to voids during curing. Furthermore, significant production issues arise, such as increased foaming during solvent distillation. On the other hand, if the softening point is 40°C or lower, heat resistance and thermal decomposition resistance are adversely affected. Furthermore, the epoxy equivalent is preferably 100 to 300 g / eq., more preferably 160 to 275 g / eq., and even more preferably 170 to 250 g / eq. If the epoxy equivalent is less than 150 g / eq., residual epichlorohydrin and a large amount of epoxidized impurities remain, potentially resulting in deterioration of properties. Furthermore, if the softening point exceeds 300 g / eq., reduced heat resistance becomes an issue.

[0038] The epoxy resin (d) used in this embodiment contains a compound represented by the following formula (d') derived from the compound represented by the above formula (c').

[0039] [ka]

[0040] In the above formula (d'), R has the same meaning as in the above formula (a), and the value and preferred range of k are the same as in the above formula (a).

[0041] The reactive epoxy acrylate compound (A) of the present invention can be obtained by reacting an epoxy resin (d) represented by the above formula (d) with a compound (e) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and, if necessary, a compound (f) having both a hydroxyl group and a carboxy group in one molecule. That is, the features of the present invention are exhibited by simultaneously introducing ethylenically unsaturated groups and hydroxyl groups into the molecular chain of an epoxy carboxylate compound in any ratio.

[0042] The compound (e) used in the present invention, which has one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule, is reacted to impart reactivity to actinic rays. Examples of such compounds include monocarboxylic acid compounds and polycarboxylic acid compounds.

[0043] Examples of monocarboxylic acid compounds containing one carboxy group per molecule include (meth)acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid with an unsaturated group-containing monoglycidyl compound. Examples of acrylic acids include (meth)acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth)acrylic acid dimer, half esters which are equimolar reaction products of a saturated or unsaturated dibasic acid anhydride with a (meth)acrylate derivative having one hydroxyl group per molecule, and half esters which are equimolar reaction products of a saturated or unsaturated dibasic acid with a monoglycidyl (meth)acrylate derivative.

[0044] Further, examples of polycarboxylic acid compounds having multiple carboxy groups in one molecule include half esters which are equimolar reaction products with (meth)acrylate derivatives having multiple hydroxyl groups in one molecule, and half esters which are equimolar reaction products between saturated or unsaturated dibasic acids and glycidyl (meth)acrylate derivatives having multiple epoxy groups.

[0045] Among these, (meth)acrylic acid, a reaction product of (meth)acrylic acid and ε-caprolactone, or cinnamic acid are most preferred in terms of sensitivity when made into an active energy ray-curable resin composition. The compound (e) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule is preferably one having no hydroxyl groups in the compound.

[0046] The compound (f) used in the present invention, which has one or more hydroxyl groups and one or more carboxyl groups in one molecule, is reacted with a carboxylate compound to introduce hydroxyl groups into the compound. These compounds include compounds having one hydroxyl group and one carboxyl group in one molecule, compounds having two or more hydroxyl groups and one carboxyl group in one molecule, and compounds having one or more hydroxyl groups and two or more carboxyl groups in one molecule.

[0047] Examples of compounds having one hydroxyl group and one carboxyl group in one molecule include hydroxypropionic acid, hydroxybutanoic acid, hydroxystearic acid, etc. Examples of compounds having two or more hydroxyl groups and one carboxyl group in one molecule include dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, etc. Examples of compounds having one or more hydroxyl groups and two or more carboxyl groups in one molecule include hydroxyphthalic acid, etc.

[0048] Of these, those containing two or more hydroxyl groups per molecule are preferred in consideration of the effects of the present invention. Furthermore, those containing one carboxyl group per molecule are preferred in consideration of the stability of the carboxylation reaction. Most preferred are those containing two hydroxyl groups and one carboxyl group per molecule. In consideration of the availability of raw materials, dimethylolpropionic acid and dimethylolbutanoic acid are particularly suitable. As the compound (f) having both one or more hydroxyl groups and one or more carboxyl groups per molecule, those not containing polymerizable ethylenically unsaturated groups are preferred.

[0049] Of these, in consideration of the stability of the reaction between the epoxy resin (d) and the carboxylic acid compounds (e) and (f), it is preferable that (e) and (f) are monocarboxylic acids, and even when a monocarboxylic acid and a polycarboxylic acid are used in combination, it is preferable that the value expressed by the total molar amount of monocarboxylic acids / the total molar amount of polycarboxylic acids is 15 or more.

[0050] The ratio of the epoxy resin (d) to the total carboxylic acid of the carboxylic acid compounds (e) and (f) used in this reaction should be adjusted depending on the intended use. In other words, if all epoxy groups are carboxylated, no unreacted epoxy groups remain, resulting in high storage stability as a reactive carboxylate compound. In this case, only the reactivity of the introduced double bond is utilized.

[0051] On the other hand, by intentionally reducing the amount of carboxylic acid compound charged and leaving unreacted residual epoxy groups, it is possible to utilize the reactivity of the introduced unsaturated bond and the reaction of the residual epoxy groups, such as a photocationic polymerization reaction or a thermal polymerization reaction, in combination. However, in this case, care should be taken to store the reactive carboxylate compound and to consider the production conditions.

[0052] When producing a reactive carboxylate compound (A) that does not leave any residual epoxy groups, the total amount of the carboxylic acid compounds (e) and (f) is preferably 90 to 120 equivalent percent relative to 1 equivalent of the epoxy resin (d). This range allows for production under relatively stable conditions. If the amount of the carboxylic acid compound charged is greater than this, excess carboxylic acid compound (e) will remain, which is not preferred.

[0053] Furthermore, when epoxy groups are intentionally left behind, the total amount of the carboxylic acid compounds (e) and (f) is preferably 20 to 90 equivalent percent relative to 1 equivalent of the epoxy resin (d). Outside this range, the combined curing effect is diminished. Of course, in this case, sufficient care must be taken to prevent gelation during the reaction and the stability of the carboxylate compound (A) over time.

[0054] The molar ratio of compound (e) having one or more polymerizable ethylenically unsaturated groups and one or more carboxy groups to compound (f) having one or more hydroxyl groups and one or more carboxy groups relative to carboxylic acid is preferably 9:1 to 1:9, more preferably 4:6 to 8:2. This range can prevent a decrease in sensitivity when (e) is too little, and can also prevent the effect of (f) from being diluted when (f) is too little.

[0055] This carboxylation reaction can be carried out without a solvent or diluted with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the carboxylation reaction. The amount of solvent used should be adjusted appropriately depending on the viscosity and use of the resulting resin, but the solvent is preferably used so that the solid content is 90 to 30 wt %, more preferably 80 to 50 wt %.

[0056] Specific examples of solvents that can be used as the above solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane, and decane; and mixtures thereof such as petroleum ether, white gasoline, and solvent naphtha. Examples of ester-based solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters such as γ-butyrolactone; mono- or polyalkylene glycol monoalkyl ether monoacetates such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, and butylene glycol monomethyl ether acetate; and polycarboxylic acid alkyl esters such as dialkyl glutarate, dialkyl succinate, and dialkyl adipate. Examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene glycol diethyl ether, and cyclic ethers such as tetrahydrofuran. Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

[0057] In addition, the reaction can be carried out in a single organic solvent containing a reactive compound (C) other than (A) and (B) or a mixture thereof. In this case, when used as a curable composition, it can be used directly as a composition, which is preferable.

[0058] A catalyst is preferably used during the reaction to promote the reaction, and the amount of catalyst used is 0.1 to 10 wt % based on the total amount of the reactants, i.e., the epoxy compound (d), the carboxylic acid compound (e), and optionally a solvent and other components. The reaction temperature is 60 to 150°C, and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include known general basic catalysts such as triethylamine, benzyldimethylamine, triethylammonium chloride, quaternary ammonium salts, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, and zirconium octanoate.

[0059] As the thermal polymerization inhibitor, it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene, or the like.

[0060] The reaction is terminated when the acid value of the sample reaches 5 mgKOH / g or less, preferably 2 mgKOH / g or less, while sampling is carried out as appropriate.

[0061] The preferred molecular weight range of the reactive carboxylate compound (A) thus obtained is 1,000 to 30,000, more preferably 1,500 to 20,000, in terms of polystyrene equivalent weight average molecular weight as measured by GPC. If the molecular weight is smaller than this range, the toughness of the cured product will not be sufficient, and if it is larger than this range, the viscosity will be too high, making coating difficult.

[0062] Next, the acid addition step will be described in detail. The acid addition step is carried out for the purpose of introducing a carboxy group, as necessary, into the reactive carboxylate compound (A) obtained in the previous step to obtain a reactive polycarboxylic acid (B). The reason for introducing a carboxy group is to impart solubility in alkaline water to the non-irradiated area of ​​the active energy ray in applications requiring resist patterning, for example, or to impart adhesion to metals, inorganic substances, etc. Specifically, a carboxyl group is introduced via an ester bond by adding a polybasic acid anhydride (g) to the hydroxyl group generated by the carboxylation reaction.

[0063] Specific examples of the polybasic acid anhydride (g) include, for example, any compound having an acid anhydride structure in one molecule, but particularly preferred are succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, trimellitic anhydride, and maleic anhydride, which are excellent in alkaline aqueous solution developability, heat resistance, hydrolysis resistance, and the like.

[0064] The reaction of adding the polybasic acid anhydride (g) can be carried out by adding the polybasic acid anhydride (g) to the carboxylation reaction solution. The amount of addition should be appropriately changed depending on the application.

[0065] However, when the polycarboxylic acid compound (B) of the present invention is intended to be used as an alkali-developable resist, it is preferable to charge an amount of polybasic acid anhydride (g) calculated so that the final reactive polycarboxylic acid compound (B) has a solids acid value (according to JIS K5601-2-1:1999) of 30 to 120 mg KOH / g, more preferably 40 to 105 mg KOH / g. When the solids acid value is within this range, the active energy ray-curable resin composition of the present invention exhibits good aqueous alkaline developability. That is, it has good patterning properties, a wide control range for overdevelopment, and does not leave excess acid anhydride.

[0066] A catalyst is preferably used during the reaction to promote the reaction, and the amount of the catalyst used is 0.1 to 10 wt % based on the total amount of the reactants, i.e., the epoxy compound (d), the carboxylate compound obtained from the carboxylic acid compounds (e) and (f), and the other basic acid anhydride (g), and optionally a solvent and other components. The reaction temperature is 60 to 150°C, and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octanoate, and zirconium octanoate.

[0067] This acid addition reaction can be carried out without a solvent or after dilution with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the acid addition reaction. Furthermore, when a solvent is used in the preceding carboxylation reaction, the product can be directly subjected to the subsequent acid addition reaction without removing the solvent, provided that the solvent is inert for both reactions. The preferred amount of solvent used should be adjusted appropriately depending on the viscosity and use of the resulting resin, but the solvent is used so that the solid content is preferably 90 to 30% by weight, more preferably 80 to 50% by weight.

[0068] aliphatic hydrocarbon solvents such as hexane, octane, and decane, and mixtures thereof such as petroleum ether, white gasoline, and solvent naphtha. Examples of ester-based solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters such as γ-butyrolactone; mono- or polyalkylene glycol monoalkyl ether monoacetates such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, and butylene glycol monomethyl ether acetate; and polycarboxylic acid alkyl esters such as dialkyl glutarate, dialkyl succinate, and dialkyl adipate. Examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene glycol diethyl ether, and cyclic ethers such as tetrahydrofuran. Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

[0069] In addition, the curing can be carried out in a single organic solvent or a mixed organic solvent containing the reactive compound (C) described below. In this case, when used as a curable composition, it can be used directly as a composition, which is preferable.

[0070] It is preferable to use the same thermal polymerization inhibitors as those exemplified in the carboxylation reaction.

[0071] The reaction is terminated when the acid value of the reaction product falls within a range of ±10% of the set acid value, while sampling is carried out as appropriate.

[0072] Specific examples of the reactive compound (C) that can be used in the present invention include so-called reactive oligomers such as radical reaction type acrylates, other cationic reaction type epoxy compounds, and vinyl compounds that react with both of these.

[0073] Examples of acrylates that can be used include monofunctional (meth)acrylates, polyfunctional (meth)acrylates, as well as epoxy acrylates, polyester acrylates, and urethane acrylates.

[0074] Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.

[0075] Examples of polyfunctional (meth)acrylates include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, glycol di(meth)acrylate, diethylene di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate, polypropylene glycol di(meth)acrylate, adipic acid epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide (meth)acrylate, bisphenol di( di(meth)acrylate of an ε-caprolactone adduct of hydroxypivalic acid neopen glycol, poly(meth)acrylate of a reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane tri(meth)acrylate and its ethylene oxide adduct, pentaerythritol tri(meth)acrylate and its ethylene oxide adduct, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate and its ethylene oxide adduct, and the like.

[0076] Usable vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methylstyrene, and ethylstyrene. Examples of other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

[0077] Furthermore, examples of so-called reactive oligomers include urethane acrylates having both a functional group capable of functioning with active energy rays and a urethane bond in the same molecule, polyester acrylates having both a functional group capable of functioning with active energy rays and an ester bond in the same molecule, Other examples include epoxy acrylates which are derived from epoxy resins and have functional groups capable of reacting with active energy rays in the same molecule, and reactive oligomers in which these bonds are used in combination.

[0078] The cationic reactive monomer is not particularly limited as long as it is a compound having an epoxy group. For example, glycidyl (meth)acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (e.g., "Cyracure UVR-6110" manufactured by Union Carbide), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (e.g., "ELR-4206" manufactured by Union Carbide), limonene dioxide (e.g., "Celloxide 3000" manufactured by Daicel Chemical Industries, Ltd.), acrylate, acrylates ... Examples of epoxy groups include 3,4-epoxycyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl) adipate (such as Union Carbide's "Cyracure UVR-6128"), bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxycyclohexyl) ether, bis(3,4-epoxycyclohexylmethyl) ether, and bis(3,4-epoxycyclohexyl)diethylsiloxane.

[0079] Of these, radical curing acrylates are most preferred as the reactive compound (C). In the case of cationic types, carboxylic acid and epoxy react with each other, so a two-part mixture is required.

[0080] The active energy ray-curable resin composition of the present invention can be obtained by mixing the reactive epoxy acrylate compound (A) and / or the reactive polycarboxylic acid compound (B) of the present invention with a reactive compound (C) other than (A) and (B) as needed. At this time, other components may be added as appropriate depending on the application.

[0081] The active energy ray-curable resin composition of the present invention contains 97 to 5 wt %, preferably 87 to 10 wt %, of a reactive epoxy acrylate compound (A) and / or a reactive polycarboxylic acid compound (B), and 3 to 95 wt %, more preferably 3 to 90 wt %, of a reactive compound (C) other than (A) and (B). If necessary, other components may be contained up to about 70 wt %.

[0082] In the active energy ray-curable resin composition of the present invention, the reactive epoxy acrylate compound (A) or the reactive polycarboxylic acid compound (B) can be appropriately selected depending on the application. For example, even in the same solder resist application, when a pattern is formed by a printing method without development or when unreacted sites are washed away with a solvent or the like, a so-called solvent development type, a reactive epoxy acrylate compound (A) is used, and when development is performed with alkaline water, a reactive polycarboxylic acid compound (B) is used. In general, alkaline water development type is more likely to produce fine patterns, so a reactive polycarboxylic acid compound (B) is often used for this application. Of course, there is no problem in using both (A) and (B) together.

[0083] The active energy ray-curable resin composition of the present invention is easily cured by active energy rays. Specific examples of active energy rays include ultraviolet rays, visible light, infrared rays, X-rays, gamma rays, laser beams, and other electromagnetic waves, as well as alpha rays, beta rays, and electron beams. Among these, ultraviolet rays, laser beams, visible light, and electron beams are preferred in consideration of the preferred uses of the present invention.

[0084] The pigment usable in the present invention is used to color the active energy ray-sensitive resin composition of the present invention. It is presumed that the balance between the hydroxyl groups of the reactive carboxylate compound (A) and the reactive polycarboxylic acid compound (B) used in the present invention is within a specific range, and therefore the pigment exhibits particularly excellent affinity, i.e., dispersibility.

[0085] Although the mechanism behind this is not clear, the dispersion proceeds well, which results in a high pigment concentration. In addition, in compositions that require development, the dispersion is in a more favorable state, which results in good patterning properties and less development residue in the developer-dissolved area, making this method suitable.

[0086] Examples of pigments include organic pigments such as phthalocyanine, azo and quinacridone pigments, and inorganic pigments such as carbon black and titanium oxide. Of these, carbon black is most preferred due to its high dispersibility.

[0087] In the present invention, the molding material refers to a material used in applications in which an uncured composition is placed in a mold or pressed against a mold to form an object, and then a curing reaction is caused by exposure to active energy rays to form an object, or in which an uncured composition is irradiated with focused light such as a laser to cause a curing reaction to form an object.

[0088] Specific examples of suitable applications include sheets formed into a flat shape, sealing materials for protecting elements, so-called nanoimprint materials in which a finely processed "mold" is pressed against an uncured composition to perform fine molding, and peripheral sealing materials for light-emitting diodes, photoelectric conversion elements, and the like, which have particularly strict thermal requirements.

[0089] In the present invention, a film-forming material is used for the purpose of coating the surface of a substrate. Specific applications include ink materials such as gravure ink, flexographic ink, silkscreen ink, and offset ink; coating materials such as hard coats, top coats, overprint varnishes, and clear coats; adhesive materials such as various adhesives and pressure-sensitive adhesives for lamination and optical disks; and resist materials such as solder resists, etching resists, and resists for micromachines. Furthermore, so-called dry films, which are formed by temporarily coating a film-forming material on a peelable substrate and then laminating it to the intended substrate to form a film, also fall under the category of film-forming material.

[0090] Among these, the introduction of a carboxy group into the reactive polycarboxylic acid compound (B) enhances adhesion to the substrate. Therefore, it is also preferred to use the reactive polycarboxylic acid compound (B) in the reaction for coating a plastic substrate or a metal substrate as an alkaline water-developable resist material composition, taking advantage of the fact that the reactive polycarboxylic acid compound (B) is soluble in an alkaline aqueous solution.

[0091] In the present invention, the resist material composition refers to an active energy ray-sensitive composition that is prepared by forming a film layer of the composition on a substrate, then partially irradiating the substrate with active energy rays such as ultraviolet rays, and utilizing the difference in physical properties between the irradiated and unirradiated areas to perform patterning. Specifically, the composition is used for the purpose of removing the irradiated or unirradiated areas by some method, such as dissolving them with a solvent or alkaline solution, and then performing patterning.

[0092] The active energy ray-curable resin composition for resists of the present invention can be applied to various materials that can be patterned, and is particularly useful, for example, as a solder resist material and an interlayer insulating material for build-up methods. It can also be used as an optical waveguide in electrical, electronic, and optical substrates such as printed wiring boards, optoelectronic boards, and optical boards.

[0093] Particularly suitable applications include permanent resist applications such as solder resist, taking advantage of the ability to obtain a tough cured product, and resist applications for displays, taking advantage of the transparency.

[0094] It is particularly suitable for use in dry films that require mechanical strength before the curing reaction due to energy rays.

[0095] The method for forming the film is not particularly limited, and any of various coating methods can be used, including intaglio printing methods such as gravure, relief printing methods such as flexography, stencil printing methods such as silk screen printing, lithographic printing methods such as offset printing, and methods using a roll coater, knife coater, die coater, curtain coater, spin coater, etc.

[0096] The cured product of the active energy ray-curable resin composition of the present invention refers to a product obtained by irradiating the active energy ray-curable resin composition of the present invention with active energy rays and curing it.

[0097] In addition, in order to adapt the active energy ray-curable resin composition of the present invention to various applications, other components can be added to the resin composition in an amount of up to 70% by weight. Examples of other components include photopolymerization initiators, other additives, coloring materials, and volatile solvents added to adjust viscosity for the purpose of imparting coatability, etc. Examples of other components that can be used are listed below.

[0098] Examples of the radical photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenones such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-ethylanthraquinone, 2-t-butylanthraquinone, and the like. Examples of known general radical photoinitiators include anthraquinones such as thioxanthone, 2-chloroanthraquinone, and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone; and phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0099] Examples of the cationic photopolymerization initiator include diazonium salts of Lewis acids, iodonium salts of Lewis acids, sulfonium salts of Lewis acids, phosphonium salts of Lewis acids, other halides, triazine initiators, borate initiators, and other photoacid generators.

[0100] Examples of diazonium salts of Lewis acids include p-methoxyphenyldiazonium fluorophosphonate and N,N-diethylaminophenyldiazonium hexafluorophosphonate (e.g., San-Aid SI-60L / SI-80L / SI-100L manufactured by Sanshin Chemical Industry Co., Ltd.). Examples of iodonium salts of Lewis acids include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate. Examples of sulfonium salts of Lewis acids include triphenylsulfonium hexafluorophosphonate (e.g., Cyracure UVI-6990 manufactured by Union Carbide) and triphenylsulfonium hexafluoroantimonate (e.g., Cyracure UVI-6974 manufactured by Union Carbide). Examples of phosphonium salts of Lewis acids include triphenylphosphonium hexafluoroantimonate.

[0101] Other halides include 2,2,2-trichloro-[1-4'-(dimethylethyl)phenyl]ethanone (e.g., Trigonal PI manufactured by AKZO), 2,2-dichloro-1-4-(phenoxyphenyl)ethanone (e.g., Sandray 1000 manufactured by Sandoz), and α,α,α-tribromomethylphenyl sulfone (e.g., BMPS manufactured by Seitetsu Kagaku Co., Ltd.). Examples of the triazine initiator include 2,4,6-tris(trichloromethyl)-triazine, 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine (Triazine A manufactured by Panchim, etc.), 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine (Triazine PMS manufactured by Panchim, etc.), 2,4-trichloromethyl-(pipronyl)-6-triazine (Triazine PP manufactured by Panchim, etc.), 2,4-trichloromethyl-(4'-methoxynaphthyl)-6-triazine (Triazine B manufactured by Panchim, etc.), 2[2'(5''-methylfuryl)ethylidene]-4,6-bis(trichloromethyl)-s-triazine (manufactured by Sanwa Chemical Co., Ltd., etc.), and 2(2'-furylethylidene)-4,6-bis(trichloromethyl)-s-triazine (manufactured by Sanwa Chemical Co., Ltd.).

[0102] Examples of the borate initiator include NK-3876 and NK-3881 manufactured by Nippon Kanko Dyes Co., Ltd. Other examples of the photoacid generator include 9-phenylacridine, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole (e.g., Biimidazole manufactured by Kurogane Chemicals Co., Ltd.), 2,2-azobis(2-amino-propane) dihydrochloride (e.g., V50 manufactured by Wako Pure Chemical Industries, Ltd.), 2,2-azobis[2-(imidazolin-2-yl)propane] dihydrochloride (e.g., VA044 manufactured by Wako Pure Chemical Industries, Ltd.), [eta-5-2-4-(cyclopentadecyl)(1,2,3,4,5,6,eta)-(methylethyl)-benzene]iron(II) hexafluorophosphonate (e.g., CIBA Geigy) Irgacure 261, etc.), bis(y5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyr-1-yl)phenyl]titanium (CGI-784, manufactured by CibaGeigy, etc.), and the like.

[0103] In addition, azo-based initiators such as azobisisobutyronitrile, and heat-sensitive peroxide-based radical initiators such as benzoyl peroxide may be used in combination. Also, both radical and cationic initiators may be used in combination. One type of initiator may be used alone, or two or more types may be used in combination.

[0104] Other additives that can be used include, for example, a thermosetting catalyst such as melamine, a thixotropy-imparting agent such as Aerosil, a silicone-based or fluorine-based leveling agent or defoaming agent, a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether, a stabilizer, an antioxidant, and the like.

[0105] Other pigment materials that may be used include those not intended for coloring, so-called extender pigments, such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, and clay.

[0106] In addition, resins that do not exhibit reactivity to active energy rays (so-called inert polymers), such as other epoxy resins, phenolic resins, urethane resins, polyester resins, ketone-formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof, can also be used, preferably in an amount of up to 40% by weight.

[0107] In particular, when using a reactive polycarboxylic acid compound (B) for solder resist applications, it is preferable to use a known general epoxy resin, which is a resin that does not exhibit reactivity to active energy rays. This means that carboxy groups derived from (B) remain even after reaction and curing with active energy rays, resulting in poor water resistance and hydrolysis resistance of the cured product. Therefore, by using an epoxy resin, the remaining carboxy groups are further carboxylated, forming a stronger crosslinked structure.

[0108] Furthermore, a volatile solvent may be added to the resin composition in an amount of up to 50% by weight, more preferably up to 35% by weight, for the purpose of adjusting the viscosity depending on the intended use. [Example]

[0109] The present invention will now be described in more detail with reference to examples. Unless otherwise specified, all parts are by weight. It should be noted that the present invention is not limited to these examples.

[0110] The various analytical methods used in the examples are described below. GPC (gel permeation chromatography) analysis used in Production Examples 1 and 2 Equipment: DGU-20A, LC-20AD, SIL-20A, RID-20A, SPD-M40, CTО-20A, CBM-20A Columns: SHODEX GPC KF-601 (2 columns), KF-602, KF-602.5, KF-603 Flow rate: 1.5ml / min. Column temperature: 40℃ Solvent used: THF (tetrahydrofuran) Detector: RI (differential refractive index detector) GPC (gel permeation chromatography) analysis used in Example 3 and Comparative Example 3 Equipment: TOSOH HLC-8220GPC Column: TSKGEL Super HZM-N Flow rate: 0.35ml / min. Column temperature: 40℃ Solvent used: THF (tetrahydrofuran) Detector: RI (differential refractive index detector) Molecular weight standard: polystyrene ICI viscosity (150°C): Measured according to JIS K-7117-2. Softening point: Measured using a METLER TOLEDO softening point tester FP90. Epoxy equivalent (WPE): Measured according to the method of JIS K 7236:2001. Acid value: Measured according to JIS K 0070:1992.

[0111] [Manufacturing Example 1] A flask equipped with a thermometer, condenser, and stirrer was purged with nitrogen. 311.6 parts of 3-methyl-6-t-butylphenol, 0.4 parts of 4-methyl-2-t-butylphenol, 122 parts of salicylaldehyde, 217 parts of methanol, and 5 parts of methanesulfonic acid were added, heated to 60°C, and reacted for 13 hours. The mixture was allowed to cool to room temperature, neutralized with 4.4 parts of 48% aqueous sodium hydroxide, and the solvent was recovered under reduced pressure at 60°C to obtain phenolic resin (c) represented by formula (c-1) below as a yellow powder. The GPC chart is shown in Figure 1 (the number-average molecular weight Mn was 581, and the weight-average molecular weight Mw was 601). The hydroxyl equivalent calculated from the GPC area percentage was 144 g / eq. (The yield was 417 parts, of which 7 g of salt was contained). The total area of ​​the peaks derived from the raw materials 3-methyl-6-t-butylphenol and 4-methyl-2-t-butylphenol was 0.5 area %, the peak area derived from the component of the compound represented by the following formula (c-1) where n=1 was 91.6 area %, and the peak area derived from compounds higher in molecular weight than the compound represented by the following formula (c-1) where n=1 was 7.9 area %.

[0112] [ka]

[0113] [Manufacturing Example 2] A flask equipped with a thermometer, a condenser, and a stirrer was purged with nitrogen. 407 parts of the phenolic resin (c-1) obtained in Production Example 1 was added with 1305 parts of epichlorohydrin, 386 parts of dimethyl sulfoxide, and 23 parts of water, and the internal temperature was raised to 45°C. 114 parts of sodium hydroxide was added in portions over 3 hours, and the mixture was allowed to react at 45°C for 1.5 hours and at 70°C for 0.5 hours. The solvent and excess epichlorohydrin were removed by distillation under reduced pressure, and 1280 parts of methyl isobutyl ketone was added. The organic layer was washed with 670 parts of water, and then 25.3 parts of a 30 wt% aqueous sodium hydroxide solution, 26.9 parts of methanol, and 25 parts of water were added. The mixture was allowed to react at 75°C for 1 hour. The organic layer was washed with water until the drainage was neutral. The solvent was removed from the resulting solution by distillation under reduced pressure, yielding 525 parts of epoxy resin (d) represented by the following formula (d-1) as a yellow solid. The epoxy equivalent was 216 g / eq., the ICI viscosity at 150°C was 0.04 Pa·s, and the softening point was 72.4°C. (The number average molecular weight Mn was 593, and the weight average molecular weight Mw was 644.)

[0114] [ka]

[0115] [Example 1 and Comparative Example 1] Synthesis of reactive epoxy acrylate resins (A) and (A') The epoxy resin (d) was prepared using the epoxy resin (d-1) obtained in Production Example 2, an epoxy resin represented by the following formula (d''-1) (FAE-2500, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 216 g / eq., softening point 86°C), and an epoxy resin represented by the following formula (d''-2) (EPPN-503, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 185 g / eq., softening point 94°C). The carboxylic acid compound (e) was acrylic acid (AA) or methacrylic acid (MAA) in the amounts shown in Table 1. The compound (f) was dimethylolpropionic acid (hereinafter abbreviated as "DMPA") in the amounts shown in Table 1. 3 g of triphenylphosphine was used as a catalyst, 1.5 g of methoquinone as a polymerization inhibitor, and propylene glycol monomethyl ether monoacetate as a solvent were added to a solids content of 80% by mass. The mixture was reacted at 100°C for 24 hours to obtain reactive epoxy acrylate resin (A) and (A') solutions.

[0116] [ka]

[0117] [Table 1]

[0118] [Example 2 and Comparative Example 2] Preparation and evaluation of hard coat compositions of reactive epoxy carboxylate resins (A) and (A') 20 g of the reactive carboxylate compounds (A) and (A') synthesized in Example 1 and Comparative Example 1, 6.0 g of dipentaerythritol hexaacrylate, which is a radical curing monomer (C), and 1.5 g of Irgacure 184 as a UV-reactive initiator were heated and dissolved. This was then applied to a polycarbonate plate using a hand applicator to a dry film thickness of 20 microns, and the solvent was dried in an electric oven for 30 minutes at 80°C. After drying, the coating was cured by irradiating it with ultraviolet light at a dose of 1000 mJ using a vertical ultraviolet exposure device (manufactured by Oak Manufacturing Co., Ltd.) equipped with a high-pressure mercury lamp, yielding a multilayer material. The hardness of the coating film of this multilayer material was measured according to JIS K5600-5-4:1999, and furthermore, the impact resistance test was carried out according to ISO6272-1:2002.

[0119] [Table 2]

[0120] As is clear from the above results, the hardness and impact resistance were improved in the Example compared to Comparative Examples 2-1 and 2-2.

[0121] [Example 3, Comparative Example 3] Synthesis of reactive polycarboxylic acid resins (B) and (B') To 200 g of the resulting reactive epoxy acrylate resin (A) or (A') solution, THPA (1,2,3,6-tetrahydrophthalic anhydride, manufactured by New Japan Chemical Co., Ltd.) and H-TMA (1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, manufactured by Mitsubishi Gas Chemical Co., Inc.) were added in the amounts (g) shown in Table 2, along with propylene glycol monomethyl ether monoacetate as a solvent to a solids content of 65%. The mixture was heated to 100°C and then subjected to an acid addition reaction to obtain reactive polycarboxylic acid resin (B) or (B') solutions. The solid acid values ​​(AV: mg KOH / g) of the resulting reactive polycarboxylic acid resins (B) and (B') are listed in Table 3. The solid acid values ​​(mg KOH / g) were measured as solutions and converted to values ​​based on the solids.

[0122] [Table 3]

[0123] Example 4: Preparation and evaluation of dry film resist material composition 50 g of the reactive polycarboxylic acid compounds (B) and (B') obtained in Example 3, 9.8 g of DPCA-20 (trade name: manufactured by Nippon Kayaku Co., Ltd.) as another reactive compound (C), 2.1 g of Irgacure 907 (manufactured by Ciba Specialty Chemicals) and 0.085 g of Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) as photopolymerization initiators, 10.3 g of YD-134 (manufactured by Nippon Kayaku Co., Ltd.) as a curing agent component, 0.1 g of triphenylphosphine as a thermal curing catalyst, and 19.1 g of propylene glycol monomethyl ether monoacetate as a concentration adjusting solvent were added, and the mixture was kneaded and uniformly dispersed using a bead mill to obtain a resist material resin composition.

[0124] Sensitivity evaluation, developability evaluation The resulting composition was uniformly applied to a polyethylene terephthalate film supporting film using a wire bar coater #20, and the coating was passed through a hot air oven at 70°C to form a 20µm thick resin layer. A polyethylene film protecting film was then attached to the resin layer to obtain a dry film. The resulting dry film was then attached to a polyimide printed circuit board (copper circuit thickness: 12µm, polyimide film thickness: 25µm) using a heated roll at 80°C, and the resin layer was attached to the entire surface of the board while peeling off the protective film.

[0125] Next, a UV exposure device (Oak Manufacturing Co., Ltd., Model HMW-680GW) was used to draw the circuit pattern on the mask and to estimate the sensitivity, and 500 mJ / cm was applied through Kodak Step Tablet No. 2. 2 The printed circuit board was irradiated with ultraviolet light for 60 minutes at 150°C. The film on the dry film was then peeled off and the peeling condition was confirmed. The resin in the unirradiated areas was then removed by spray development using a 1% aqueous solution of sodium carbonate. After rinsing and drying, the printed circuit board was subjected to a heat curing reaction in a hot air dryer at 150°C for 60 minutes to obtain a cured film.

[0126] Sensitivity was determined by how many density steps remained in the exposed area of ​​the step tablet after development. The larger the step number (value), the higher the sensitivity in the darker areas of the tablet (unit: step). The developability was evaluated based on the time it took for the patterned portion to be completely developed when developing the exposed portion that had passed through the pattern mask, that is, the break time (unit: seconds).

[0127] Dielectric properties The photosensitive resin composition obtained above was applied to a rolled copper foil (BHY-82F-HA-V2 (trade name), manufactured by JX Metals Corporation) having a thickness of 18 μm using an applicator, and then dried at a temperature of 80°C for 30 minutes to form a film-like photosensitive resin composition on the copper foil. The coating thickness of the photosensitive resin composition was adjusted so that the film-like photosensitive resin composition would have a thickness of 20 μm after drying. This film-like photosensitive resin composition was exposed to light at an exposure dose of 500 mJ / cm using a light source (Ultra-high pressure mercury lamp 500 W Multilight (trade name), manufactured by USHIO Corporation) capable of irradiating active energy rays including wavelengths of 405 nm (h-rays). 2 The resin film was then exposed to light at 1000 K, and then cured by heating at 150°C for 60 minutes in a nitrogen atmosphere. The copper foil was then removed by etching to obtain a cured film. The cured resin film was cut into 80 x 3 mm test pieces. The test pieces were left in an environment of 25°C and 20% humidity for one day, and then the relative permittivity and dielectric loss tangent at 10 GHz were measured using a cavity resonator dielectric constant measurement device (manufactured by AET Corporation). The measuring device used was an ADMSO10c1 vector network analyzer manufactured by AET, and the cavity resonator was a CP531 (10 GHz band resonator) manufactured by Kanto Electronics Application Development Co., Ltd. The results are shown in Table 1.

[0128] -Evaluation of insulation reliability The dry film prepared above was attached to a comb-shaped electrode (material: copper, pattern pitch: 18 μm, L / S=100 μm / 100 μm) formed on a substrate (polyimide film), and then 500 mJ / cm 2 The coating was exposed to light at 100°C and then heat-cured at 150°C for 1 hour to obtain a test specimen. After heating, the test specimen was placed in a chamber (ETAC PLAMOUBT HAST CHAMBER PM220, Kusumoto Chemicals Co., Ltd.) at 130°C and 85% humidity, and a DC voltage of 100V was applied between the electrodes using a migration tester (ETAC SIR-13mini, Kusumoto Chemicals Co., Ltd.) to measure the resistance between the electrodes. The insulation reliability was evaluated according to the following criteria. When the evaluation criteria are ○ or △, the insulation reliability is judged to be acceptable, the insulation retention is sufficient enough for practical use, and the insulation reliability is excellent.

[0129] (Insulation reliability criteria) ○: Resistance is 1×10 9 Ω or more, lasting for over 100 hours, with excellent insulation △: Resistance is 1×10 8 Ω or more, 1×10 9 Less than Ω for over 100 hours, providing excellent insulation ×: Resistance is 1×10 in less than 100 hours 8 If it drops below Ω, it is considered to be an insulation failure.

[0130] Glass transition temperature (Tg) evaluation The photosensitive resin compositions obtained in each of the Examples and Comparative Examples were applied to a rolled copper foil (BHY-82F-HA-V2 (trade name), manufactured by JX Metals Corporation) having a thickness of 18 μm using an applicator, and then dried at a temperature of 80°C for 30 minutes to form a film-like photosensitive resin composition on the copper foil. The applied thickness of the photosensitive resin composition was adjusted so that the film-like photosensitive resin composition would have a thickness of 20 μm after drying. This film-like photosensitive resin composition was exposed to light at an exposure dose of 500 mJ / cm using a light source (Ultra-high pressure mercury lamp 500 W Multilight (trade name), manufactured by USHIO Corporation) capable of irradiating active energy rays including wavelengths of 405 nm (h-rays). 2 The coating was then heated in a nitrogen atmosphere at 150° C. for 60 minutes to be cured, and the copper foil was then removed by etching to obtain a cured film. The dynamic viscoelasticity of the cured bismaleimide prepared as described above was measured using a dynamic viscoelasticity analyzer (DMA) (TA Instruments RSA-G2) (frequency 1 Hz, tensile mode, heating rate 5°C / min), and the glass transition temperature was determined from the maximum value of the loss tangent (tanδ). Furthermore, the tanδ peak waveform was examined from the perspective of compatibility, and the number of peaks was counted. The results are shown in Table 4.

[0131] Evaluation of thermal decomposition resistance The photosensitive resin compositions obtained in each of the Examples and Comparative Examples were applied to a rolled copper foil (BHY-82F-HA-V2 (trade name), manufactured by JX Metals Corporation) having a thickness of 18 μm using an applicator, and then dried at a temperature of 80°C for 30 minutes to form a film-like photosensitive resin composition on the copper foil. The applied thickness of the photosensitive resin composition was adjusted so that the film-like photosensitive resin composition would have a thickness of 20 μm after drying. This film-like photosensitive resin composition was exposed to light at an exposure dose of 500 mJ / cm using a light source (Ultra-high pressure mercury lamp 500 W Multilight (trade name), manufactured by USHIO Corporation) capable of irradiating active energy rays including wavelengths of 405 nm (h-rays). 2 The film was then exposed to light at 100°C, then cured by heating at 150°C for 60 minutes in a nitrogen atmosphere, after which the copper foil was removed by etching to obtain a cured film. The cured product was cut into 4 mm squares, and 1.0 to 5.0 mg was weighed and placed in a measuring pan. The 5% weight loss (Td5) was measured under conditions of an air flow rate of 100 mL / sec and a heating rate of 10°C / min. The measuring device used was a TGA / DSC1 (manufactured by METTLER TOLEDO).

[0132] [Table 4]

[0133] As described above, the cured product of the active energy ray-curable resin composition using the reactive polycarboxylic acid resin (B) of the present invention can be finely developed with high sensitivity in an alkaline environment, and also has excellent heat resistance and electrical properties, and good insulation reliability, and is therefore suitable for use as a molding material, a film-forming material, a resist material, and an interlayer insulating material.

Claims

1. A reactive epoxy acrylate resin (A) obtained by reacting a phenolic resin (c) obtained by reacting a compound represented by the following formula (a) with a compound represented by the following formula (b) with an epihalohydrin to give an epoxy resin (d), with a carboxylic acid compound (e) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and, if necessary, a compound (f) having both a hydroxyl group and a carboxy group in one molecule: 【Chemistry 1】 (In formula (a), each R independently represents a hydrocarbon group having 1 to 5 carbon atoms. The total number of carbon atoms in the R is 2 to 8. k is an integer of 1 to 4.)

2. a polycarboxylic acid resin (B) obtained by reacting a polybasic acid anhydride (g) with a reactive epoxy acrylate resin (A) obtained by reacting a phenolic resin (c) obtained by reacting a compound represented by the following formula (a) with a compound represented by the following formula (b) with an epoxy resin (d) obtained by reacting the phenolic resin (c) with an epihalohydrin; a carboxylic acid compound (e) having both a polymerizable ethylenically unsaturated group and a carboxy group in one molecule, and optionally a compound (f) having both a hydroxyl group and a carboxy group in one molecule; 【Chemistry 2】 (In formula (a), each R independently represents a hydrocarbon group having 1 to 5 carbon atoms. The total number of carbon atoms in the R is 2 to 8. k is an integer of 1 to 4.)

3. The epoxy acrylate resin (A) according to claim 1 and / or the polycarboxylic acid resin (B) according to claim 2, wherein the phenolic resin (c) is represented by the following general formula (c): 【Transformation 3】 (In formula (c), each of the multiple R's independently represents a hydrocarbon group having 1 to 5 carbon atoms. In each benzene ring substituted with R, the total number of carbon atoms of the multiple R's is 2 to 8. k is an integer of 1 to 4. n is the average number of repetitions, preferably 1 to 20.)

4. An active energy ray-curable resin composition comprising the epoxy acrylate resin (A) according to claim 1 and / or the polycarboxylic acid resin (B) according to claim 2.

5. 10. An active energy ray-curable resin composition comprising the epoxy acrylate resin (A) according to claim 1 and / or the polycarboxylic acid resin (B) according to claim 2, wherein the active energy ray-curable resin composition comprises a reactive compound (C) other than the epoxy acrylate resin (A) and the polycarboxylic acid resin (B).

6. An active energy ray-curable resin composition comprising the epoxy acrylate resin (A) according to claim 1 and / or the polycarboxylic acid resin (B) according to claim 2, further comprising a photopolymerization initiator.

7. An active energy ray-curable resin composition comprising the epoxy acrylate resin (A) according to claim 1 and / or the polycarboxylic acid resin (B) according to claim 2, further comprising a pigment.

8. An active energy ray-curable resin composition, which is a molding material, comprising the epoxy acrylate resin (A) according to claim 1 and / or the polycarboxylic acid resin (B) according to claim 2.

9. 10. An active energy ray-curable resin composition, which is a film-forming material, comprising the epoxy acrylate resin (A) according to claim 1 and / or the polycarboxylic acid resin (B) according to claim 2.

10. 10. An active energy ray-curable resin composition, which is a resist material composition, comprising the epoxy acrylate resin (A) according to claim 1 and / or the polycarboxylic acid resin (B) according to claim 2.

11. A cured product of an active energy ray-curable resin composition comprising the epoxy acrylate resin (A) according to claim 1 and / or the polycarboxylic acid resin (B) according to claim 2.

12. An article overcoated with a cured product of the active energy ray-curable resin composition according to claim 11.

13. A printed wiring board comprising at least one of a surface protective film and an interlayer insulating film formed from the photosensitive resin composition according to any one of claims 4 to 10.

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