JP5137823B2 - Reactive carboxylate compound, curable resin composition using the same, and use thereof - Google Patents

Description

  The present invention imparts reactivity to active energy rays to an epoxy resin having a high molecular orientation, and a carboxylate compound having properties excellent in heat resistance, toughness, and thermal conductivity in the cured product, and acid modification thereof Products, active energy ray resin compositions containing them, and uses thereof.

  In recent years, with the increase in circuit board density and progress in semiconductor device mounting methods, the use of lead-free solder, etc. protects higher heat resistance, toughness, chemical resistance, and even electronic devices that are vulnerable to heat Therefore, a film-forming material having high thermal conductivity is required.

  An example of these film forming materials is solder resist ink. The purpose of this is to avoid adhesion of solder to parts other than the target part when soldering parts to the printed wiring circuit board and to protect the circuit on the printed wiring circuit board. And various properties such as chemical resistance are required. At present, epoxy acrylate solder resist ink is the mainstream.

  These epoxy acrylate solder resist inks acrylate the epoxy resin to provide reactivity, or when patterning by alkaline water development is required, acid-modify after acrylate formation, and these are UV curable solder resist inks It is common to use as. Alkali water development type solder resists are generally used due to demands for improving the accuracy of circuit pattern density due to recent downsizing, high functionality, resource saving, and cost reduction of electronic devices. As these examples, a composition using a phenol novolac type epoxy resin or a resin obtained by reacting an acid anhydride with a reaction product of a cresol type epoxy resin and an unsaturated monobasic acid is widely used. (Japanese Patent Publication No. 7-67008, Japanese Patent Publication No. 7-17737, Japanese Patent No. 2598346).

  Further, an epoxy acrylate compound derived from an epoxy acrylate having a biphenyl skeleton, an acid-modified epoxy acrylate derived from its acid anhydride, and its use are also known (Japanese Patent Laid-Open No. 11-140144).

In recent years, the problem of heat dissipation has been raised with the progress of high-density circuit boards and semiconductor device mounting methods. For example, it is described that an epoxy resin having a mesogenic group in a molecule in an epoxy resin or the like exhibits high thermal conductivity in the cured product (Japanese Patent Laid-Open No. 2003-268070).
However, these epoxy resins having a mesogenic group generally have a disadvantage that they have a complicated molecular structure and are difficult to produce, and are difficult to provide at low cost and in large quantities.

  Furthermore, it is known that a higher thermal conductivity is generally imparted by blending an inorganic material having a high thermal conductivity into the composition (Japanese Patent Laid-Open No. 10-242637). However, even if these inorganic materials are blended in a resin material that is inferior in heat dissipation, the effect is limited.

  An epoxy resin having a bisphenol F structure and an epoxy resin having a biphenol structure are already known (Japanese Patent Laid-Open No. 9-227653). However, these do not disclose anything about imparting reactivity to active energy rays. Furthermore, no mention is made of showing excellent thermal conductivity by the ratio of the structure derived from the bisphenol F type and the biphenol structure.

  An object of the present invention is to provide a material that not only excels in basic performances such as toughness, heat resistance, and electrical characteristics, but also has improved heat dissipation, that is, thermal conductivity.

  In light of these circumstances, the present inventors have conducted intensive research, and as a result, they are easy to manufacture and can react with an epoxy resin that can easily realize a state in which molecules are oriented, and can be cured with active energy rays. It has been found that a cured product imparted with high thermal conductivity can be obtained by introducing a group.

  That is, the present invention

Both of the structural units represented by the above formulas (I) and (II) have an average value of the total number of repetitions of the formulas (I) and (II) of 1.1 to 20, and the formula (I) The epoxy resin (a), wherein the value represented by the number of repetitions of ÷ the number of repetitions of formula (II) is 0.5 to 50, and one or more polymerizable ethylenically unsaturated groups in the molecule And a reactive carboxylate compound (A) obtained by reacting a compound (b) having at least one carboxyl group.
Furthermore, the average value of the sum of the number of repetitions of formula (I) and formula (II) is 1.3 to 5, and the value represented by the number of repetitions of formula (I) ÷ the number of repetitions of formula (II) is 0. It relates to the reactive carboxylate compound (A) according to claim 1, which is 5 or more and 10 or less and both ends are epoxy groups.
Furthermore, it is related with the reactive polycarboxylic acid compound (B) obtained by making a polybasic acid anhydride (c) react with the said carboxylate compound (A).
Furthermore, the present invention relates to an active energy ray-curable resin composition comprising the carboxylate compound (A) or the reactive polycarboxylic acid compound (B).
Furthermore, the present invention relates to an active energy ray-curable resin composition comprising the carboxylate compound (A) or the reactive polycarboxylic acid compound (B) and another reactive compound (C).
Furthermore, in the said active energy ray curable resin composition, it is related with the active energy ray curable resin composition whose other reactive compound (C) is radical reaction type acrylates.
Furthermore, the present invention relates to an active energy ray-curable resin composition comprising a thermal conductive inorganic filler in the active energy ray-curable resin composition.
Furthermore, it is related with the said active energy ray hardening-type resin composition which is a molding material.
Furthermore, it is related with the said active energy ray hardening-type resin composition which is a film forming material.
Furthermore, it is related with the said active energy ray hardening-type resin composition which is a resist material.
Furthermore, it is related with the said active energy ray hardening-type resin composition which is a heat conductive material.
Furthermore, it is related with the hardened | cured material of an active energy ray curable resin composition.
Furthermore, it is related with the multilayer material which has a layer of hardened | cured material.

  By using the reactive carboxylate compound of the present invention, a cured product having high thermal conductivity can be obtained. Furthermore, higher heat dissipation is demonstrated by using together the heat conductive inorganic filler excellent in heat dissipation. Thereby, it can use suitably for uses, such as a film formation material in which especially heat dissipation is calculated | required, especially a soldering resist.

  The epoxy resin (a) having both the structural units represented by the above formulas (I) and (II) used in the present invention is a phenol compound represented by the following formula (2) or the following formula (3) as an epihalohydrin. The low molecular weight epoxy resin (a ′) obtained by reacting in the presence of an alkali metal hydroxide is further reacted with a phenol compound represented by formula (2) or formula (3), and crystals are formed in a solvent. It can be obtained by precipitation. In the present invention, the epoxy resin (a) having both the structural units represented by the formulas (I) and (II) has both the structural units represented by the following formulas (I ′) and (II ′). Those are preferred.

  The position of substitution of the hydroxyl group of the phenolic compound of formula (2) to the aromatic ring is not particularly limited, but considering the effects of the present invention on toughness, heat resistance, electrical properties, and heat dissipation, 4, The case where it is 4′-form and / or the case where it is 2,2′-form is preferred, the case where it is 4,4′-form or the case where it is 2,2′-form is more preferred, and 4,4′-form. More preferably, it is a body. The melting points of these phenolic compounds are crystals of around 163 ° C. and 118 ° C., respectively, and the 4,4′-form is considered to have a higher melting point, that is, higher crystallinity. This is considered to have a positive effect on the crystallinity when an epoxy resin is used, and an epoxy resin composed of a 4,4′-phenol compound is expected to have higher crystallinity, that is, thermal conductivity. it can. The phenolic compound of the formula (2) is commercially available as p, p′-BPF and o, o′-BPF (all manufactured by Honshu Chemical Co., Ltd.).

  As a method for producing an epoxy resin having both the structural units represented by the formulas (I) and (II), (i): a reaction product of a compound of formula (2) and an epihalohydrin is chained with a compound of formula (3). (Ii): Any of the methods of chain extending the reaction product of the compound of formula (3) and epihalohydrin with the compound of formula (2) can be adopted. In the present invention, the method of (i) preferable. The method (i) will be described below. The method (ii) is obtained by replacing the phenol compound of the formula (2) and the phenol compound of the formula (3) in the method (i). The structural units represented by the formulas (I) and (II) may be connected at random or may be connected by constituting a block for each structural unit.

  In the epoxy resin having both the structural units represented by the formulas (I) and (II), the value represented by the number of repetitions of the formula (I) ÷ the number of repetitions of the formula (II) is 0.5 or more and 50 or less Moreover, the effect regarding the heat conduction is exhibited, preferably 0.5 or more and 10 or less, more preferably 1.2 or more and less than 5. When this value is large, the characteristic of having two phenolic compounds in the structural unit of the epoxy resin is thin, and when this value is small, the resin skeleton becomes too rigid to obtain an epoxy resin.

  Epichlorohydrin or epibromohydrin can be used as the epihalohydrin in the method for producing an epoxy resin having both the structural units represented by the formulas (I) and (II). The amount of epihalohydrin is usually 2 to 15 mol, preferably 3 to 12 mol, per 1 mol of the hydroxyl group of the compound of formula (2).

  Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and the like. Solid or an aqueous solution thereof may be used. When an aqueous solution is used, it is continuously added to the reaction system and simultaneously under reduced pressure. Alternatively, a method may be employed in which normal pressure sewage and epihalohydrin are distilled and further separated, water is removed, and epihalohydrin is continuously returned to the reaction system. The usage-amount of an alkali metal hydroxide is 0.9-1.2 mol normally with respect to 1 equivalent of hydroxyl groups of the compound of Formula (2), Preferably it is 0.95-1.15 mol. The reaction temperature is usually 20 to 110 ° C, preferably 25 to 100 ° C. The reaction time is usually 0.5 to 15 hours, preferably 1 to 10 hours.

  Addition of alcohols such as methanol, ethanol, propanol and butanol, or aprotic polar solvents such as dimethyl sulfoxide and dimethyl sulfone is preferable for promoting the reaction.

  When using alcohol, the amount of its use is 3-30 weight% normally with respect to the quantity of epihalohydrin, Preferably it is 5-20 weight%. When an aprotic polar solvent is used, the amount used is usually 10 to 150% by weight, preferably 15 to 120% by weight, based on the amount of epihalohydrin.

  In addition, the reaction between the epihalohydrin and the compound of the formula (2) was added to the mixture of both as a quaternary ammonium salt catalyst such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride and the like at 0.5 to 30 ° C. Hydrogen halide solid or aqueous solution of halohydrin ether compound of the formula (2) obtained by reacting for ˜8 hours is added and reacted at 20-100 ° C. for 1-10 hours for dehydrohalogenation (ring closure) ).

  Subsequently, excess epihalohydrin, a solvent, etc. are removed under the heat-reduced pressure after washing these epoxidation reaction products with water or without washing with water. Furthermore, in order to make an epoxy resin with less hydrolyzable halogen, the recovered epoxy resin is dissolved in toluene, methyl isobutyl ketone, etc., and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to perform ring closure. Can also be ensured. In this case, the usage-amount of an alkali metal hydroxide is 0.01-0.3 mol normally with respect to 1 mol of hydroxyl groups of a compound of Formula (2), Preferably it is 0.05-0.2 mol. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is removed under heating and reduced pressure to obtain a low molecular weight epoxy resin (a ′). The epoxy equivalent of the epoxy resin (a ′) is usually 160 to 200 g / eq.

  Next, low molecular weight epoxy resin (a ′) and 4,4′-biphenol represented by the above formula (3) are subjected to an addition reaction to increase the molecular weight. The charging ratio of the low molecular weight epoxy resin (a ′) and 4,4′-biphenol is usually 0.05 to 0.001 of the hydroxyl group of the compound of the formula (3) with respect to 1 mol of the epoxy group of the epoxy resin (a ′). The ratio is 0.95 mol, preferably 0.1 to 0.9 mol.

  Although the addition reaction can be carried out without a catalyst, it is preferable to use a catalyst for promoting the reaction. Catalysts that can be used include triphenylphosphine, tetramethylammonium chloride, sodium hydroxide, potassium hydroxide, benzyltriphenylphosphonium chloride, butyltriphenylphosphonium, ethyltriphenylphosphonium iodide, ethyltriphenylphosphine. Examples include phonium bromide. The amount of the catalyst used is 0.001 to 1% by weight, preferably 0.01 to 0.5% by weight, based on the total weight of the reaction.

  In the addition reaction, it is preferable to use a solvent for controlling the reaction temperature. Examples of the solvent that can be used include cyclopentanone, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, toluene, N-methylpyrrolidone, N, N-dimethyl sulfoxide, N, N-dimethylformamide, and the like. The amount of the solvent used is usually 5 to 150% by weight, preferably 10 to 100% by weight, based on the total weight of the low molecular weight epoxy resin (a ′) and the compound of formula (3).

  The reaction temperature is usually 60 to 180 ° C, preferably 70 to 160 ° C. The progress of the reaction can be followed by GPC (gel permeation chromatography) or the like, and is performed until the compound of formula (3) is not completely detected. The reaction time is usually 0.5 to 15 hours, preferably 1 to 10 hours. The epoxy resin (a) can be obtained by distilling off the solvent used as necessary from the reaction mixture thus obtained, but a crystalline powder can be obtained as follows depending on the use of the epoxy resin. .

  That is, after completion of the reaction, an epoxy resin crystal is precipitated by adding a poor solvent and cooling. Examples of the poor solvent include methyl isobutyl ketone, methyl ethyl ketone, acetone, toluene, methanol, ethanol, water and the like. The amount of the poor solvent to be added is usually 50 to 400% by weight, preferably 100 to 300% by weight, based on the total weight of the low molecular weight epoxy resin (a ′) and the compound of the formula (3). After the crystals are precipitated, the crystalline epoxy resin (a) can be obtained by filtering and drying. Further, the resinous epoxy resin (a) can be heated to the melting point or higher and gradually cooled to obtain a crystalline resin mass.

  In addition, when the addition reaction is carried out without solvent, after completion of the reaction, the product is dissolved in a good solvent such as N-methylpyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, and then methanol, ethanol, isopropanol, acetone The epoxy resin of the present invention can be obtained in good yield by adding a water-soluble poor solvent such as methyl ethyl ketone and further adding water. In this case, the amount of the good solvent used is usually 5 to 200% by weight, preferably 10 to 150% by weight, based on the total weight of the low molecular weight epoxy resin (a ′) and the compound of formula (3). The use amount of the water-soluble poor solvent is usually 5 to 200% by weight, preferably 10 to 150% by weight, based on the theoretical yield of the epoxy resin. The amount of water used is usually 50 to 400% by weight, preferably 100 to 300% by weight, based on the total weight of the low molecular weight epoxy resin (a ′) and the compound of formula (3).

  The epoxy resin (a) thus obtained is usually a crystal having a melting point of 70 to 180 ° C., and the epoxy equivalent is usually 200 to 2000 g / eq, preferably 250 to 1500 g / eq. When the epoxy resin (a) is measured by DSC (differential thermal analyzer), endothermic peaks are often observed at two or more locations. This phenomenon indicates that the epoxy resin (a) has liquid crystallinity. Furthermore, it is possible to specify the temperature region in which the epoxy resin (a) exhibits optical anisotropy by observing while raising the temperature using a polarizing microscope. Generally, the temperature range in which the epoxy resin (a) exhibits optical anisotropy is 100 to 200 ° C. In addition, although the sum total of the repeating number of the formula (I) and the formula (II) of the obtained epoxy resin normally represents 1.1-20 in an average value, Preferably it is 1.3-5, Especially preferably, 1. 5-3. The sum of the number of repetitions of formula (I) and formula (II) can be estimated for the obtained resin by GPC, NMR measurement or calculation from epoxy equivalent. The value of the number of repetitions of formula (I) / the number of repetitions of formula (II) is determined from the charged amount. This value can also be calculated from the ratio of hydrogen atom on the aromatic ring to the methylene of bisphenol by NMR.

  The obtained epoxy resin (a) can be used in the crystalline state in the preparation of the epoxy resin composition, but it should also be used in a resin state obtained by heating once to the melting point or higher to make it molten and then supercooling. I can do it. In the case of a resin state, the softening point is usually 45 to 100 ° C.

  The epoxy resin (a) thus obtained is reacted with a compound (b) having both a polymerizable ethylenically unsaturated group and one or more carboxyl groups (hereinafter simply referred to as a carboxylic acid compound (b)), thereby producing the present invention. The reactive carboxylate compound (A) can be obtained.

  The carboxylic acid compound (b) is reacted in order to impart reactivity to active energy rays. Specific examples include (meth) acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. In the above, examples of the acrylic acid include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride and 1 molecule. Half-esters that are (meth) acrylate derivatives having one hydroxyl group and equimolar reactants, half-esters that are equimolar reactants of saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives, etc. And monocarboxylic acid compounds containing one carboxyl group in one molecule.

  In addition, (meth) acrylate derivatives having a plurality of hydroxyl groups in one molecule and half-esters which are equimolar reactants, glycidyl (meth) acrylate derivatives having a saturated or unsaturated dibasic acid and a plurality of epoxy groups. Examples thereof include polycarboxylic acid compounds having a plurality of carboxyl groups in one molecule such as half-esters which are molar reactants.

  Of these, considering the stability of the reaction between the epoxy resin (a) and the carboxylic acid compound (b), (b) is preferably a monocarboxylic acid, even when the monocarboxylic acid and the polycarboxylic acid are used in combination. The ratio represented by the molar amount of monocarboxylic acid / the molar amount of polycarboxylic acid is preferably 15 or more.

  Most preferably, (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid is used from the viewpoint of sensitivity when an active energy ray-curable resin composition is used.

  The charging ratio of the epoxy resin (a) and the carboxylic acid compound (b) in this reaction should be appropriately changed according to the application. That is, when all the epoxy groups are carboxylated, unreacted epoxy groups do not remain, so that the storage stability as a reactive carboxylate compound is high. In this case, only the reactivity due to the introduced double bond is used.

  On the other hand, by reducing the charged amount of the carboxylic acid compound (b) and leaving an unreacted residual epoxy group, the reactivity due to the introduced unsaturated bond and the reaction due to the remaining epoxy group, for example, the polymerization reaction by the photocation catalyst, It is also possible to use the thermal polymerization reaction in combination. In this case, however, attention should be paid to the storage of the reactive carboxylate compound and the examination of the production conditions.

  When producing the reactive carboxylate compound (A) that does not leave an epoxy group, the carboxylic acid compound (b) is preferably 90 to 120 equivalent%, and 95 to 105 equivalent, based on 1 equivalent of the epoxy resin (a). % Is more preferable. Within this range, it is possible to manufacture under relatively stable conditions. When the amount of the carboxylic acid compound charged is larger than this, an excess of the carboxylic acid compound (b) remains, which is not preferable.

  Moreover, when leaving an epoxy group, it is preferable that a carboxylic acid compound (b) is 20-90 equivalent% with respect to 1 equivalent of epoxy resins (a), and it is more preferable that it is 30-80 equivalent%. When deviating from this range, the effect of the composite curing is reduced. Of course, in this case, sufficient attention must be paid to gelation during the reaction and stability with time of the reactive carboxylate compound (A).

  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. In addition, in the case of producing using a solvent in the carboxylation reaction that is the previous step, it may be subjected directly to the acid addition reaction that is the next step without removing the solvent, provided that both reactions are inert. it can.

Specifically, for example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and mixtures thereof, petroleum ether, white Examples include gasoline and solvent naphtha.
Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, Mono- or polyalkylene glycol monoalkyl ether monoacetates such as triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, adipine Polyesters of polycarboxylic acids such as dialkyl acids Kind, and the like.
Examples of ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, 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. Glycol ethers, and cyclic ethers such as tetrahydrofuran.
Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

  In addition, it can carry out in other organic compound alone, such as other reactive compounds (C). In this case, when used as a curable composition, it can be used directly as a composition, which is preferable.

  The amount of the solvent used in the reaction of the epoxy resin (a) and the carboxylic acid compound (b) or the other reactive compound (C) includes (a), (b), the solvent or (C), the catalyst, etc. The total amount is preferably 60% by weight or less, and more preferably 20 to 50% by weight.

  During the reaction, a catalyst can be used to promote the reaction, and the amount of the catalyst used is a reaction with the addition of the reactants, that is, the epoxy compound (a), the carboxylic acid compound (b), and optionally a solvent or the like. It is 0.1 to 10 weight% with respect to the total amount of a thing. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used in the present invention include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, and octane. Known general basic catalysts such as chromium acid and zirconium octoate are exemplified.

  In addition, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4hydroxytoluene and the like are used as thermal polymerization inhibitors that can be used in the present invention. preferable.

  The end point of this reaction is the time when the acid value of the sample is 1 mgKOH / g or less, preferably 0.5 mgKOH / g or less, while sampling appropriately.

  The reactive polycarboxylic acid compound (B) of the present invention can be obtained by subjecting the obtained reactive carboxylate compound (A) of the present invention to an addition reaction of the polybasic acid anhydride (c). The acid addition step is performed for the purpose of introducing a carboxyl group through an ester bond by addition reaction of the polybasic acid anhydride (c) to the hydroxyl group generated by the carboxylation reaction.

  As specific examples of the polybasic acid anhydride (c) that can be used in the present invention, any compound having an acid anhydride structure in the molecule can be used. For example, alkaline aqueous solution developability, heat resistance, Excellent succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride Alternatively, maleic anhydride is preferred.

  The addition amount of the polybasic acid anhydride (c) can be appropriately changed according to the use. However, when the reactive polycarboxylic acid compound (B) of the present invention is to be used as an alkali development resist, the solid content acid value (JIS K5601) of the finally obtained reactive polycarboxylic acid compound (B). 2-1: Based on 1999) It is preferable to charge polybasic acid anhydride (c) having a calculated value of 40 to 120 mg · KOH / g, more preferably 60 to 110 mg · KOH / g. If the solid content acid value at this time is smaller than this range, the alkaline aqueous solution developability of the active energy ray-curable resin composition of the present invention is remarkably lowered, and in the worst case, development may not be possible. When an acid value exceeds this, an acid anhydride becomes excess with respect to a reaction point, and an unreacted polybasic acid anhydride (c) remains. Alternatively, the developability becomes too high and patterning may not be possible.

  During the reaction, it is preferable to use a catalyst to promote the reaction. The amount of the catalyst used is the reactive carboxylate compound (A) of the present invention, the polybasic acid anhydride (c), and optionally a solvent or the like. Is 0.1 to 10% by weight based on the total amount of the reaction product added. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used in the present invention include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, and octane. Examples include chromium acid and zirconium octoate.

  The acid addition reaction can be performed 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 acid addition reaction. In addition, in the case of producing using a solvent in the carboxylation reaction that is the previous step, it may be subjected directly to the acid addition reaction that is the next step without removing the solvent, provided that both reactions are inert. it can.

  Specific examples include the same solvents that can be used in the carboxylation reaction.

  In addition, it can carry out in other organic compound alone, such as other reactive compounds (C). In this case, when used as an active energy ray-curable resin composition, it can be used directly as a composition, which is preferable.

  The amount of the solvent used in the reaction of the carboxylate compound (A) and the polybasic acid anhydride (c) or the other reactive compound (C) is (A), (c), solvent or (C), catalyst It is preferable that it is 60 weight% or less in the total amount which combined etc., More preferably, it is 20 to 50 weight%.

  Further, as the thermal polymerization inhibitor and the like that can be used in the acid addition reaction, it is preferable to use the same ones as exemplified in the carboxylation reaction.

  In this reaction, the end point is determined when the acid value of the reaction product is within a range of plus or minus 10% of the set acid value while appropriately sampling.

  The other reactive compound (C) contained in the active energy ray-curable resin composition of the present invention is a generic name for those reactive with active energy rays, like the reactive carboxylate compound (A) of the present invention. is there. These are preferably used for imparting physical properties before and after curing according to the purpose of use.

  Specific examples of other reactive compounds (C) that can be used include so-called reactive oligomers such as radical-reactive acrylates, cation-reactive other epoxy compounds, and vinyl compounds sensitive to both. It is done.

  Examples of radical reaction type acrylates that can be used include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, other epoxy acrylates, polyester acrylates, urethane acrylates, and the like.

  Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, alkyl (meth) acrylates such as lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene Alkylene glycol mono (meth) acrylates such as glycol (meth) acrylate monomethyl ether, aromatic (meth) acrylates such as benzyl (meth) acrylate, phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) Examples thereof include cycloaliphatic (meth) acrylates such as acrylate, and heterocyclic-containing (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate.

  Polyfunctional (meth) acrylates include butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate and other alkylene diol (meth) acrylates Glycol di (meth) acrylate, diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, alkylene glycol di (meth) acrylate such as polypropylene glycol di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, Aromatic (meth) acrylates such as bisphenol di (meth) acrylate, cycloaliphatic (meth) acrylates such as hydrogenated bisphenol ethylene oxide (meth) acrylate , Heterocycle-containing (meth) acrylates such as tris (meth) acryloyloxyethyl isocyanurate, other epoxy acrylates such as adipic acid epoxy di (meth) acrylate, dipentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, alkyl polyol (meth) acrylates such as triethylolpropane tri (meth) acrylate, ethylene such as dipentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) acrylate, triethylolpropane tri (meth) acrylate Di (meth) acrylates of ε-caprolactone adducts of hydroxybivalic acid neopent glycol, such as (meth) acrylates of oxide adducts or propylene oxide adducts Rate, polyol caprolactone modified (meth) acrylates of poly (meth) acrylate of a reaction product of dipentaerythritol and ε- caprolactone.

  Examples of vinyl compounds that can be used 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, methyl styrene, and ethyl styrene. Other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

  In addition, the cation reaction type other epoxy compounds are not particularly limited as long as they are generally compounds having an epoxy group. For example, normal epoxy compounds such as glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, or 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Carboxylates (such as “Syracure UVR-6110” manufactured by Union Carbide), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (“ELR-4206” manufactured by Union Carbide, etc.) ), Limonene dioxide (“Celoxide 3000” manufactured by Daicel Chemical Industries, Ltd.), allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate ("Syracure UVR-" manufactured by Union Carbide) 6128 "etc.), bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethyl Examples include so-called alicyclic epoxy compounds such as siloxane.

  Among these, as the other reactive compound (C), radical reaction type acrylates are most preferable. In the case of other cation-reactive epoxy compounds, carboxylic acid and epoxy react with each other, so that it is necessary to use a two-component mixed type.

  It is possible to obtain the active energy ray-curable resin composition of the present invention by mixing the carboxylate compound (A) or the reactive polycarboxylic acid compound (B) of the present invention with another reactive compound (C). it can. At this time, you may add another component suitably according to a use.

  The active energy ray-curable resin composition of the present invention contains 97 to 5% by weight of the carboxylate compound (A) or the reactive polycarboxylic acid compound (B) in the composition, preferably 87 to 10% by weight, and other reactions. 3 to 95% by weight of the active compound (C), more preferably 10 to 80% by weight. Other components may be included as necessary. In particular, when used as a composition containing an inorganic filler, the carboxylate compound (A) or the reactive polycarboxylic acid compound (B) is 10 to 40% by weight, the other reactive compound (C) is 5 to 50% by weight, It is preferable that 10 to 65% by weight of the inorganic filler and 75 to 20% by weight of other components such as an initiator and a volatile solvent that are used as necessary.

  The carboxylate compound (A) or the reactive polycarboxylic acid compound (B) in the active energy ray-curable resin composition of the present invention can be appropriately used depending on the application. For example, in the case of a so-called solvent development type in which a pattern is formed by a printing method or an unreacted site is washed away by a solvent or the like without developing even in the same solder resist application, a carboxylate compound (A) is used and alkaline water is used. In the case of developing by using a reactive polycarboxylic acid compound (B). In general, the reactive polycarboxylic acid compound (B) is often used for this application from the viewpoint that the alkaline water development type can easily form a fine pattern. Of course, there is no problem even if (A) and (B) are used in combination. When used in combination, the weight ratio of (A) :( B) can be in the range of 20:80 to 5:95.

  The active energy ray-curable resin composition of the present invention is easily cured by active energy rays. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays and laser rays, particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

  In the present invention, the molding material refers to a material in which an uncured composition is put into a mold or an object is molded by pressing the mold and then a curing reaction is caused by active energy rays, or a laser is applied to the uncured composition. It refers to a material that is used for applications in which it is irradiated with a focused light such as to cause a curing reaction to be molded.

  Specific applications include a sheet formed into a flat shape, a sealing material for protecting the element, a so-called nanoimprint material that performs fine molding by pressing a "mold" that has been micro-processed into an uncured composition, Furthermore, particularly suitable applications include peripheral sealing materials such as light-emitting diodes and photoelectric conversion elements, which have particularly severe thermal requirements.

  In the present invention, the film forming material is used for the purpose of coating the surface of a substrate. Specific applications include gravure inks, flexo inks, silk screen inks, offset inks and other ink materials, hard coats, top coats, overprint varnishes, clear coats and other coating materials, laminating, optical disk and other various adhesives. This corresponds to adhesive materials such as adhesives and adhesives, resist materials such as solder resists, etching resists, and resists for micromachines. Furthermore, after the film forming material is temporarily applied to the peelable substrate and formed into a film, it is bonded to the original target substrate to form a film, so-called dry film also corresponds to the film forming material. .

  Among these, the introduction of the carboxyl group of the reactive polycarboxylic acid compound (B) increases the adhesion to the substrate, and therefore, it is preferably used as an application for coating a plastic substrate or a metal substrate.

  Furthermore, taking advantage of the feature that the unreacted reactive polycarboxylic acid compound (B) is soluble in an alkaline aqueous solution, it is also preferable to use it as an alkaline water developable resist material composition.

  In the present invention, the resist material is formed by forming a coating layer of the composition of the present invention on a substrate, and then partially irradiating active energy rays such as ultraviolet rays, and the physical difference between irradiated and unirradiated parts. This refers to an active energy ray-sensitive composition that is intended to be drawn using. Specifically, the composition is used for the purpose of removing the irradiated part or the unirradiated part by dissolving the irradiated part or the non-irradiated part with, for example, a solvent or an alkaline solution.

  There are no particular restrictions on the method for forming the film, but an intaglio printing method such as gravure, a relief printing method such as flexo, a stencil printing method such as silk screen, a lithographic printing method such as offset, a roll coater, a knife coater, a die coater, Various coating methods such as curtain coater and spin coater can be arbitrarily adopted.

  In the present invention, the heat conducting material means that heat is quickly dissipated from a switching power source, power IC, CPU, lighting inverter, heater device, various electronic components such as a heating element such as a semiconductor element or a circuit board, or a heat absorbing body. Refers to a material used for the purpose of heat transfer or heat transfer.

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

  The multilayer material of the present invention refers to a material having at least two layers obtained by forming and curing a film of the active energy ray-curable resin composition of the present invention on a substrate.

  The cured product of the present invention is preferably used for applications requiring heat conductivity such as heat dissipation.

  In addition, for the purpose of adapting the active energy ray-curable resin composition of the present invention to various uses, other components may be added up to 70% by weight. Examples of other components include inorganic fillers, photopolymerization initiators, other additives, and coloring materials. Examples of other components that can be used are shown below.

  Among these, the characteristic of the active energy ray curable resin composition of this invention can be exhibited to the maximum by using the heat conductive inorganic filler which has high heat conductivity as an inorganic filler.

  The thermally conductive inorganic filler is used in combination in order to further enhance the ability of the reactive carboxylate compound (A) or the reactive polycarboxylic acid compound (B) having high thermal conductivity shown in the present invention. . For example, metal powders such as aluminum powder, copper powder, and silver powder may be mixed as long as the application may have electrical conductivity. In the case of applications requiring insulation, for example, solder resist applications, alumina, aluminum nitride, silica, magnesia, boron nitride and the like can be mentioned. Among these, those having a thermal conductivity of 10 W / m / K or more work particularly effectively in consideration of thermal conductivity. Specifically, alumina and aluminum nitride are preferable in view of thermal conductivity. The heat conductive inorganic filler is preferably used in an amount of about 10 to 65% by weight, more preferably 15 to 50% by weight, based on the total amount of the composition.

  Examples of the radical photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy 2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl-1- [4- ( Acetophenones such as methylthio) phenyl] -2-morpholino-propan-1-one; ant such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Quinones; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide Benzophenones such as 4,4′-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide A general radical type photoinitiator is mentioned.

  In addition, as the cationic initiator, Lewis acid diazonium salt, Lewis acid iodonium salt, Lewis acid sulfonium salt, Lewis acid phosphonium salt, other halides, triazine initiator, borate initiator, and others And a photoacid generator.

  Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate (Sun Shine SI-60L / SI-80L / SI-100L, etc., manufactured by Sanshin Chemical Industry Co., Ltd.) and the like. Examples of the Lewis acid iodonium salt include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate. Examples of the Lewis acid sulfonium salt include triphenylsulfonium hexafluorophosphonate (Cyracure UVI-6990 manufactured by Union Carbide). Etc.), triphenylsulfonium hexafluoroantimonate (available from Union Carbide: Cyracure UVI-) 974, etc.). Examples of the phosphonium salt of a Lewis acid, triphenyl phosphonium hexafluoroantimonate, and the like.

  As other halides, 2,2,2-trichloro- [1-4 ′-(dimethylethyl) phenyl] ethanone (manufactured by AKZO: Trigonal PI, etc.), 2.2-dichloro-1--4- (phenoxy) Phenyl) ethanone (manufactured by Sandoz: Sandray 1000), α, α, α-tribromomethylphenylsulfone (manufactured by Iron Chemical Co., Ltd .: BMPS, etc.), etc. Examples of triazine initiators include 2,4,6- Tris (trichloromethyl) -triazine, 2,4-trichloromethyl- (4′-methoxyphenyl) -6-triazine (such as Triazine A manufactured by Panchim), 2,4-trichloromethyl- (4′-methoxystyryl)- 6-triazine (manufactured by Panchi: Triazine PMS, etc.), 2,4-to Lichloromethyl- (pipronyl) -6-triazine (such as Triazine PP manufactured by Panchim), 2,4-trichloromethyl- (4′-methoxynaphthyl) -6-triazine (such as Triazine B manufactured by Panchim), 2 [2 ′ ( 5 "-methylfuryl) ethylidene] -4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd.), 2 (2'-furylethylidene) -4,6-bis (trichloromethyl)- Examples thereof include s-triazine (manufactured by Sanwa Chemical Co., Ltd.).

  Examples of the borate initiator include Nippon Senshoku Dye: NK-3876 and NK-3881, and other photoacid generators include 9-phenylacridine, 2,2′-bis (o-chlorophenyl). -4,4 ', 5,5'-tetraphenyl-1,2-biimidazole (manufactured by Kurokin Kasei Co., Ltd .: biimidazole), 2,2-azobis (2-amino-propane) dihydrochloride (Wako Pure Chemical) Manufactured by: V50, etc.), 2,2-azobis [2- (imidazolin-2-yl) propane] dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd .: VA044), [η-5-2-4- (cyclopentadecyl) (1,2,3,4,5,6, η)-(methylethyl) -benzene] iron (II) hexafluorophosphonate (manufactured by Ciba Specialty Chemicals: Irgacure 261, etc. Etc. The.

  In addition, an azo initiator such as azobisisobutyronitrile, a peroxide radical initiator sensitive to heat such as benzoyl peroxide, and the like may be used in combination. Further, both radical and cationic initiators may be used in combination. One type of initiator can be used alone, or two or more types can be used in combination.

  Other additives include thermosetting catalysts such as melamine, fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay, and thixotropy such as aerosil. Agents, phthalocyanine blue, phthalocyanine green, titanium oxide, silicone, fluorine-based leveling agents and antifoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether can be used.

  Examples of pigment materials include organic pigments such as phthalocyanine, azo, and quinacridone, inorganic pigments such as titanium oxide, carbon black, bengara, zinc oxide, barium sulfate, and talc, known general coloring, and extender pigments. can do.

  Other resins that are not reactive with active energy rays (so-called inert polymers), such as other epoxy resins, phenol 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. These are preferably used in the range of up to 40% by weight.

  In particular, when the reactive polycarboxylic acid compound (B) is to be used for solder resist applications, it is preferable to use a known general epoxy resin as a resin that does not show reactivity to active energy rays. This is because the carboxyl group derived from (B) remains even after being reacted and cured by active energy rays, and as a result, the cured product is inferior in water resistance and hydrolyzability. Therefore, by using an epoxy resin, the remaining carboxyl group is further carboxylated to form a stronger cross-linked structure. The preferable usage-amount of an epoxy resin is 0.5-3 equivalent with an epoxy group with respect to the carboxyl group contained in a composition, Preferably it is 1-1.5 equivalent.

  Depending on the purpose of use, a volatile solvent can be used in the entire composition for the purpose of adjusting the viscosity. In this case, the amount of the volatile solvent used is preferably in the range of 50% by weight, more preferably up to 40% by weight, based on the total amount of the composition. If the amount of solvent used is large, consideration must be given to processes such as drying.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. Moreover, unless otherwise indicated in an Example, a part shows a weight part.

Synthesis Example 1: Synthesis 1 of epoxy resin a
A phenolic compound represented by the above formula (2) (trade name p, p′-BPF, manufactured by Honshu Chemical Co., Ltd.) while purging nitrogen with a flask equipped with a thermometer, a condenser tube, a fractionating tube, and a stirrer. To 100 parts, 370 parts of epichlorohydrin and 26 parts of methanol were added and heated to 65-70 ° C. with stirring. After completely dissolved, 40.4 parts of flaky sodium hydroxide was added over 100 minutes under reflux conditions. Add in portions. Thereafter, the post reaction was further carried out at 70 ° C. for 1 hour. Subsequently, 150 parts of water was added and washed with water twice, and excess epichlorohydrin and the like were removed from the oil layer under heating and reduced pressure. 312 parts of methyl isobutyl ketone was added to the residue and dissolved, and 10 parts of 30% aqueous sodium hydroxide solution was added at 70 ° C. and reacted for 1 hour. After the reaction, the product was washed with water three times to remove generated salts and the like. Methyl isobutyl ketone was distilled off under reduced pressure by heating to obtain 150 parts of epoxy resin (a′-1). The epoxy equivalent of the obtained epoxy resin was 170 g / eq, the viscosity at 25 ° C. was 1000 mP · s, and the total chlorine content was 1200 ppm. Subsequently, 85 parts of this epoxy resin (a′-1) and 23 parts of the compound represented by the formula (3) were added and dissolved under stirring, and 0.08 part of benzyltriphenylphosphonium chloride was added. After reacting at 160 ° C. for 4 hours and 4,4′-biphenol completely disappeared in GPC, the reaction was further continued and reacted for a total of 6 hours, followed by cooling to 100 ° C. and adding 108 parts of dimethyl sulfoxide. Was completely dissolved. The mixture was further cooled to 60 ° C., and 108 parts of methanol was added with stirring. Next, the mixture was cooled to 30 ° C. and 208 parts of water was added to precipitate crystals. The crystals were filtered and dried to obtain 103 parts of a white powdery epoxy resin (a). The epoxy equivalent of this epoxy resin (a) was 443 g / eq (the total number of repetitions of the formulas (I) and (II) ≈2.09 (average value: calculated from the epoxy equivalent)). Further, the value of the number of repetitions of formula (I) ÷ the number of repetitions of formula (II) was 3.53. It was 111 degreeC when melting | fusing point of the obtained epoxy resin (a) was measured by DSC (differential thermal analyzer). In the DSC measurement results, two peak tops appeared and were 125 ° C. and 160 ° C. Furthermore, when the obtained epoxy resin (a) was observed at a heating rate of 1 ° C. per minute using a polarizing microscope, it was confirmed that the epoxy resin exhibited optical anisotropy at 140 to 160 ° C. .

Measurement of thermal conductivity The thermal conductivity of each of the resin of Synthesis Example 1 and a commercially available high molecular weight bisphenol F type resin (YDF-2001, manufactured by Tohto Kasei Co., Ltd.) was compared by a technique based on ASTM 1530.
As a result, Synthesis Example 1 was 0.41 (W / mK), and YDF-2001 was 0.19 (W / mK). The epoxy resin (a) exhibits high thermal conductivity, and the reactive carboxylate compound (A), the reactive polycarboxylic acid compound (C) and the active energy ray-curable resin composition of the present invention derived from the epoxy resin are also heat-sensitive. It is judged that the conductivity is excellent.

Example 1-1, Example 1-2: Preparation of carboxylate compound (A) 443 g of epoxy resin (a) prepared in Synthesis Example 1, one or more polymerizable ethylenically unsaturated groups and one or more in the molecule Acrylic acid (abbreviation: AA, Mw = 72) as the compound (b) having both of the carboxyl groups described in Table 1, the amount of triphenylphosphine 3 g as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent to a solid content of 80% 129 g of the solution, and allowed to react at 100 ° C. for 24 hours until the acid value of the solution reached 1 mg KOH / g or less, and the reactive carboxylate compound (A) solution of the present invention (Example 1-1, Example 1-2) was added. Obtained.

Comparative Example 1-1: Preparation of Carboxylate Compound of General Bisphenol F Type Epoxy Resin Instead of the epoxy resin (a) used in Example 1, a commercially available high molecular weight bisphenol F type resin (YDF-2001, manufactured by Toto Kasei Co., Ltd.) , Epoxy equivalent 471 g / eq) 471 g, and acrylic acid (abbreviation AA, Mw = 72) is represented as a compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in the molecule. 1, 3 g of triphenylphosphine as a catalyst and 136 g of propylene glycol monomethyl ether monoacetate as a solvent so as to have a solid content of 80%, reacted at 100 ° C. for 24 hours, and a general bisphenol F-type carboxylate compound solution (Comparative Example 1-1) was obtained.

Example 2-1 and Example 2-2: Preparation of reactive polycarboxylic acid compound (B) Polybasic acid anhydride (c) was added to 323 g of the carboxylate compound (A) solution obtained in Example 1-1. , Tetrahydrophthalic anhydride (abbreviated as THPA) listed in Table 2, and propylene glycol monomethyl ether monoacetate as a solvent so that the solid content is 65% by weight, heated to 100 ° C. and subjected to an acid addition reaction for 10 hours. The reactive polycarboxylic acid compound (B) solution (Example 2-1 and Example 2-2) was obtained.

Comparative Example 2-1 Preparation of General Bisphenol F-type Reactive Polycarboxylic Acid Compound 341 g of the bisphenol F-type carboxylate compound solution prepared in Comparative Synthesis Example 1-1 was carboxylated by the same method as in Example 2.

Examples 3-1 to 3-4, Comparative Example 3: Preparation of active energy ray-curable resin composition Carboxylate compounds prepared in Example 1-1 and Example 1-2, Example 2-1, Example 7 g each of the reactive polycarboxylic acid compound prepared in 2-2, the carboxylate compound prepared in Comparative Example 1-1, and the reactive polycarboxylic acid compound prepared in Comparative Example 2-1, other reactive compounds (C ) As dipentaerythritol hexaacrylate, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (commercial name: Irgacure) as a radical photopolymerization initiator as other additive components 907: 0.4 g of Ciba Specialty Chemicals, 0.05 g of 2,4-diethylthioxanthone (commercial name: Kayacure DETX-S: manufactured by Nippon Kayaku Co., Ltd.) It was mixed. The prepared active energy ray-curable resin composition was coated on a polyester film with a 150 micron applicator and dried in an oven at 80 ° C. for 30 minutes.
After completion of drying, 2000 mJ / cm ² of ultraviolet rays were irradiated to cause a curing reaction.
Each of the obtained cured products had a thickness of about 100 microns.

  The cured product (cured film) of the present invention (Examples 3-1 to 3-4) is superior in thermal conductivity of the reactive carboxylate compound (A) of the present invention to the reactive carboxylate compound of the comparative example. Since it is determined as described above, it is determined that the thermal conductivity is superior to the cured product of the comparative example.

Example 4-1 and Example 4-2: Measurement of effect of thermally conductive inorganic filler 7 g of the reactive polycarboxylic acid compound solution prepared in Example 2-1 and Comparative Example 2-1, other reactivity 2 g of dipentaerythritol hexaacrylate as the compound (C), 3 g of aluminum nitride or barium sulfate listed in Table 3 (average particle diameter 10 microns) as the thermally conductive inorganic filler, and 2-methyl-1-as the radical photopolymerization initiator [4- (Methylthio) phenyl] -2-morpholino-propan-1-one (commercial name Irgacure 907: manufactured by Ciba Specialty Chemicals) 0.1 g, 2,4-diethylthioxanthone 0.01 g (commercial name Kayacure DETX-S : Nippon Kayaku Co., Ltd.) and mixed with a three-roll mill.
The prepared active energy ray-curable resin composition was applied onto a polyester film with a 150-micron applicator and dried in an oven at 80 ° C. for 60 minutes. After completion of the drying, an ultraviolet ray of 8000 mJ / cm ² was irradiated to cause a curing reaction.
Each of the obtained cured products had a thickness of about 100 microns.

  It is judged that higher thermal conductivity can be exhibited by combining the reactive polycarboxylic acid compound (B) of the present invention and the thermally conductive inorganic filler.

Example 5: Evaluation as a resist material composition 7 g of the reactive polycarboxylic acid compound solution (A) of the present invention synthesized in Example 2-1, 2 g of dipentaerythritol hexaacrylate, and powdered barium sulfate (average) 3 g of particle size) 3 g, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one as a radical photopolymerization initiator (commercial name Irgacure 907: manufactured by Ciba Specialty Chemicals) 0.5 g, 2,4-diethylthioxanthone 0.1 g (commercial name Kayacure DETX-S: manufactured by Nippon Kayaku), 1,3,5-trisglycidyl isocyanuric acid 2 g, carbitol acetate 3 g as a solvent, This roll mill was kneaded to obtain a resist material composition.
The obtained composition was applied to an epoxy resin copper-clad laminate using a 100 mesh silk screen method, dried at 80 ° C. for 30 minutes, and the coating surface after drying was evaluated.
Further, a pattern mask was placed on the surface of the coating film, and irradiated with 500 mJ / cm ² of ultraviolet rays using a vertical exposure machine. After removing the mask, development was carried out by spraying a 1 wt% aqueous sodium carbonate solution for 1 minute. As a result, it was shown that the portion that was not exposed by the mask pattern flowed down with the developer, and only the irradiated portion remained and had developability.
After completion of development, the substrate is washed with water and heated in an oven at 150 ° C. for 1 hour, and the composition is derived from the carboxylic acid derived from the reactive polycarboxylic acid (B) and 1,3,5-trisglycidyl isocyanuric acid. A multilayer material in which a stronger cross-linked structure was formed by reacting the epoxy group was obtained.
The cured film thus obtained was evaluated by a pencil hardness test method (JIS K5600: 1999) and a cross-cut cellophane tape peel test (JIS K5600-5-6: 1999). Furthermore, after this coating film was immersed in a 260 ° C. solder bath for 1 minute, a cross-cut cellophane tape peeling test (JIS K5600-5-6: 1999) was performed to evaluate heat resistance.

Comparative Example 5: Evaluation as a resist material composition Instead of the reactive polycarboxylic acid compound of the present invention shown in Example 2-1 used in Example 5, the general bisphenol F type of Comparative Example 2-1 was used. A resist material composition was formed using a reactive polycarboxylic acid compound. The production method and evaluation method of the composition were performed according to Example 5. These results are shown in Table 4.

  From the above results, when the reactive polycarboxylic acid compound of the present invention is used as a solder resist ink, it has good resistance to solder and is good compared to the bisphenol-based material of Comparative Example 5. It became clear that it showed hardness and heat resistance.

Test Example 1: Evaluation of thermal conductivity The solvent was removed from the resin solution of the reactive carboxylate compound (A) of the present invention synthesized in Example 1-1 by drying under reduced pressure. Since the weight became constant, solvent removal was confirmed.
9.7 g of the resin excluding the solvent and 0.3 g of the polymerization initiator azobisisobutyronitrile were mixed well in an agate bowl. The mixture was formed into a disk shape having a diameter of 100 mm and a thickness of 4 mm using a tablet manufacturing machine. After forming, the metal mold was heated at 150 ° C. for 1 hour to react and further cure the reactive carboxylate compound.
After cooling, the thermal conductivity at 30 ° C. of a disk-shaped sample molded with an Unther Unimodel 2022 thermal conductivity measuring device was measured. The results are shown in Table 5 below.
The sample in this test example used thermosetting instead of active energy rays for the convenience of sample preparation. The chemical structure generated by the thermal reaction is the same as that caused by the curing reaction by the active energy ray, and is considered to show almost the same result as the cured product obtained by the active energy ray.

Comparative Test Example 1: Evaluation of Thermal Conductivity The reactive carboxylate compound (A) used in Test Example 1 was replaced with the general bisphenol F-type carboxylate compound solution obtained in Comparative Example 1-1, and Test Example 1 was conducted. The thermal conductivity was compared as well.

  From the above results, it became clear that the reactive carboxylate compound (A) of the present invention has a good thermal conductivity as compared with a general epoxy acrylate material.

Claims (11)

Both have structural units represented by the following formulas (I) and (II), the average value of the sum of the number of repetitions of formula (I) and formula (II) is 1.1 to 20, and the formula (I) The epoxy resin (a), wherein the value represented by the number of repetitions of ÷ the number of repetitions of formula (II) is 0.5 to 50, and one or more polymerizable ethylenically unsaturated groups in the molecule And a reactive carboxylate compound (A) obtained by reacting a compound (b) having at least one carboxyl group.

The average value of the sum of the number of repetitions of formula (I) and formula (II) is 1.3 to 5, and the value represented by the number of repetitions of formula (I) ÷ the number of repetitions of formula (II) is 0.5 or more. The reactive carboxylate compound (A) according to claim 1, which is 10 or less and both ends are epoxy groups. A reactive polycarboxylic acid compound (B) obtained by reacting the carboxylate compound (A) according to claim 1 with a polybasic acid anhydride (c). An active energy ray-curable resin composition comprising the carboxylate compound (A) according to claim 1 or the reactive polycarboxylic acid compound (B) according to claim 3. The active energy ray-curable resin composition according to claim 4, further comprising another reactive compound (C). The active energy ray-curable resin composition according to claim 5, wherein the other reactive compound (C) is a radical-reactive acrylate. An active energy ray-curable resin composition comprising a thermally conductive inorganic filler in the active energy ray-curable resin composition according to claim 5 or 6. The active energy ray-curable resin composition according to claim 4, which is a molding material. The active energy ray-curable resin composition according to claim 4, which is a film forming material. The active energy ray-curable resin composition according to claim 4, which is a resist material. The active energy ray-curable resin composition according to claim 4, which is a heat conductive material.