Modified epoxy resin, epoxy resin composition, cured product, prepreg, printed wiring board, and method for producing modified epoxy resin

Abstract

To provide: an unsaturated heterocycle-containing acyl group-modified epoxy resin excellent in heat resistance and low dielectric properties; an epoxy resin composition comprising the epoxy resin and a curing agent; a cured product of the composition; a prepreg and a printed wiring board that are formed using the epoxy resin composition; and a method for producing the epoxy resin.SOLUTION: The modified epoxy resin is represented by the formula (1) in the figure and has an epoxy equivalent weight of 300 to 10,000 g / eq. In the formula: X is a divalent group; Y is a hydrogen atom, a C5-20 unsaturated heterocycle-containing acyl group, or a glycidyl group; Z is a C5-20 unsaturated heterocycle-containing acyl group or a hydrogen atom, with the acyl groups constituting at least 5 mol%; and n represents the number of the repeating units.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a modified epoxy resin having excellent heat resistance and low dielectric properties, an epoxy resin composition containing the epoxy resin and a curing agent, a cured product thereof, a prepreg, and a printed wiring board, and a method for producing the modified epoxy resin. [Background technology]

[0002] Epoxy resins are widely used in the fields of paints, civil engineering, adhesion, electrical materials, etc., because of their excellent heat resistance, adhesiveness, chemical resistance, water resistance, mechanical strength, and electrical properties. Film-forming properties are imparted by increasing the molecular weight in various ways. Such highly molecular epoxy resins are called phenoxy resins. In particular, bisphenol A-type phenoxy resins are mainly used as base resins for paint varnishes and base resins for film molding, or are added to epoxy resin varnishes to adjust the flowability and improve the toughness and adhesiveness when cured. In addition, those having phosphorus atoms or bromine atoms in the skeleton are used as flame retardants to be blended with epoxy resin compositions and thermoplastic resins.

[0003] In recent years, information devices have been rapidly becoming smaller and more powerful, and as a result, materials used in the fields of semiconductors and electronic components are being required to have higher performance than ever before. In particular, epoxy resin compositions used as materials in electric and electronic components are being required to have low dielectric properties in line with the trend toward thinner substrates and higher functionality.

[0004] In response to this demand, a method has been proposed for improving the dielectric properties by converting the hydroxyl groups present in the side chains of the epoxy resin into esters using acetyl or benzoyl groups. Patent Document 1 discloses that an epoxy resin obtained by reacting a bifunctional epoxy resin with a diester compound and a cured product thereof have excellent dielectric properties, but there is still a problem in that the heat resistance is still insufficient. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2016-089165 A Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a modified epoxy resin having excellent heat resistance and low dielectric properties, a resin composition containing the modified epoxy resin and a curing agent, a cured product thereof having excellent heat resistance and low dielectric properties, and a prepreg or printed wiring board using the resin composition. [Means for solving the problem]

[0007] In order to solve the above problems, the present inventors have conducted extensive research into modified epoxy resins and have found that a cured product of a resin composition containing a modified epoxy resin having a specific structure has excellent heat resistance and low dielectric properties, thereby completing the present invention.

[0008] That is, the present invention relates to a modified epoxy resin represented by the following general formula (1) and having an epoxy equivalent of 300 to 10,000 g / eq. [ka] Here, X is a divalent group. Y is independently a hydrogen atom, an unsaturated heterocyclic ring-containing acyl group having 5 to 20 carbon atoms, or a glycidyl group. Z is independently a hydrogen atom or an unsaturated heterocyclic ring-containing acyl group having 5 to 20 carbon atoms, and 5 mol % or more of the acyl group is the above. n is the number of repetitions, and the average value is 1 or more and 50 or less.

[0009] Furthermore, Z preferably contains any one of the unsaturated heterocycle-containing acyl groups represented by the following formulae (2a) to (2f), and more preferably contains any one of the unsaturated heterocycle-containing acyl groups represented by the following formulae (3a) to (3c). [ka] R1 ~R 6 are independently a hydrocarbon group having 1 to 6 carbon atoms, n1 is an integer of 0 to 3, n2 is an integer of 0 to 5, n3 is an integer of 0 to 5, n4 is an integer of 0 to 4, n5 is an integer of 0 to 6, and n6 is an integer of 0 to 8. W is an oxygen atom or a sulfur atom. [ka]

[0010] The present invention also relates to an epoxy resin composition comprising a modified epoxy resin and a curing agent. The mole number of active hydrogen groups in the curing agent is preferably 0.2 to 1.5 moles per mole of epoxy groups in the total epoxy resin.

[0011] The curing agent incorporated in the above-mentioned epoxy resin composition is preferably at least one selected from the group consisting of phenolic resins, acid anhydride compounds, amine compounds, imidazole compounds, amide compounds, cyanate ester compounds, and active ester compounds.

[0012] The present invention also relates to a cured product obtained by curing the above-mentioned epoxy resin composition, and to a prepreg and a printed wiring board obtained by using the above-mentioned epoxy resin composition.

[0013] The present invention also relates to a method for producing the above-mentioned modified epoxy resin, which comprises reacting a bifunctional epoxy resin represented by the following general formula (4) with a compound represented by the following general formula (5). [ka] Where X 1 and X 2is a divalent group. G is a glycidyl group. Q is an unsaturated heterocycle-containing acyl group having 5 to 20 carbon atoms or a hydrogen atom, and 5 mol % or more of the acyl group is the above. m is the number of repetitions, the average value of which is 0 to 6. The compound represented by general formula (5) may be a mixture of two or more selected from a compound in which both Qs are the above acyl group, a compound in which one Q is the above acyl group, and a compound in which both Qs are hydrogen atoms. Effect of the Invention

[0014] The resin composition containing the modified epoxy resin of the present invention and a curing agent can provide a cured product with excellent heat resistance and low dielectric properties. In particular, the introduction of furyl groups is advantageous in terms of carbon neutrality, since it uses a raw material that can be obtained from a biomass raw material (corn). [Brief description of the drawings]

[0015] [Figure 1] 1 is a GPC chart of the modified epoxy resin of Example 1. [Diagram 2] 1 is an IR chart of the modified epoxy resin of Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The modified epoxy resin of the present invention can be advantageously obtained by the production method of the present invention. In this specification, the cured product obtained by curing the epoxy resin composition of the present invention may be referred to as the "cured product of the present invention," and the production method of the modified epoxy resin of the present invention may be referred to as the "production method of the present invention."

[0017] The modified epoxy resin of the present invention is represented by the following general formula (1) and has an epoxy equivalent (g / eq.) of 300 to 10,000. Within this range, the modified epoxy resin can participate in the curing reaction and be incorporated into a crosslinked structure. The epoxy equivalent is preferably 350 to 5,000, more preferably 380 to 3,000. [ka] Here, X is a divalent group. Y is independently a hydrogen atom, an unsaturated heterocyclic ring-containing acyl group having 5 to 20 carbon atoms, or a glycidyl group. Z is independently a hydrogen atom or an unsaturated heterocyclic ring-containing acyl group having 5 to 20 carbon atoms, and 5 mol % or more of the acyl group is the above. n is the number of repetitions, and the average value is 1 or more and 50 or less.

[0018] The weight average molecular weight (Mw) of the modified epoxy resin of the present invention is preferably 500 or more and 20,000 or less. If Mw is less than 500, the introduction of a structure that improves dielectric properties may be reduced. If Mw is more than 20,000, the impregnation into the substrate may be deteriorated. The upper limit is more preferably 10,000 or less. The Mw of the modified epoxy resin can be measured by the gel permeation chromatography method (GPC method) described in the examples.

[0019] In the general formula (1), the epoxy resin has a structure in which some or all of the hydrogen atoms in the hydroxyl groups of ordinary epoxy resins are substituted with unsaturated heterocyclic acyl groups having 5 to 20 carbon atoms. This structure results in low polarity, and the unsaturated heterocyclic skeleton, which is larger than the hydrogen atoms, suppresses micro-Brownian motion, resulting in excellent heat resistance. In addition, the epoxy resin has low moisture absorption and low dielectric properties (low dielectric tangent).

[0020] In general formula (1), X represents a divalent group. Preferably, X is a divalent hydrocarbon group or a hydrocarbon group which may have a group such as -O-, -CO-, -S-, -COO-, -SO-, -SO2- in the hydrocarbon chain. Examples of the divalent group include an aromatic skeleton representing a skeleton remaining after removing two hydroxyl groups from an aromatic diol compound, an aliphatic skeleton representing a skeleton remaining after removing two hydroxyl groups from an aliphatic diol compound, and an alicyclic skeleton representing a skeleton remaining after removing two hydroxyl groups from an alicyclic diol compound. These groups are derived from the residual skeleton obtained by removing two glycidyloxy groups from a difunctional epoxy resin (diglycidyl ether compound), the residual skeleton obtained by removing two ester structures from a diester compound, and the residual skeleton obtained by removing two hydroxyl groups from a difunctional phenol compound.

[0021] Specific examples of the aromatic skeleton having a structure in which two hydroxyl groups have been removed from an aromatic diol compound include bisphenol types which may be unsubstituted or have an alkyl group having 1 to 10 carbon atoms as a substituent, such as bisphenol A, bisphenolacetophenone, bisphenol AF, bisphenol AD, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, tetramethylbisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenoltrimethylcyclohexane, and bisphenolcyclohexane; and unsubstituted or carbon-substituted bisphenol types such as hydroquinone, resorcin, and catechol. Examples of the dihydroxyphenyl ether include benzene types such as dihydroxyphenyls which may have an alkyl group having 1 to 10 atoms as a substituent; naphthalene types such as dihydroxynaphthalenes which may have an unsubstituted or alkyl group having 1 to 10 carbon atoms as a substituent; biphenyl types such as dihydroxybiphenyls which may have an unsubstituted or alkyl group having 1 to 10 carbon atoms as a substituent; fluorene types such as bisphenolfluorenes and bisnaphtholfluorenes which may have an unsubstituted or alkyl group having 1 to 10 carbon atoms as a substituent, such as bisphenolfluorene and biscresolfluorene; thiodiphenol, dihydroxydiphenyl ether, and the like. In addition, in order to impart flame retardancy, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ), 10-(2,7-dihydroxynaphthyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-NQ), 10-(1,4-dihydroxy-2-naphthyl)-10H-9-oxa-10-phospha Examples of such phosphorus-containing phenols include unsubstituted or phosphorus-containing phenols which may have an alkyl group, an aryl group or an aralkyl group having 1 to 10 carbon atoms as a substituent, such as phenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphosphinyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol, and 1,5-cyclooctylenephosphinyl-1,4-phenyldiol.From the viewpoint of heat resistance, it is preferable to include bisphenol trimethylcyclohexane, bisphenol fluorene, biscresol fluorene, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ), and 10-(2,7-dihydroxynaphthyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-NQ).

[0022] Specific examples of the aliphatic skeleton include alkylene glycol skeletons such as ethylene glycol, propylene glycol, and butylene glycol.

[0023] Specific examples of the alicyclic skeleton include hydrogenated bisphenol skeletons such as hydrogenated bisphenol A, hydrogenated bisphenol F, and hydrogenated bisphenol acetophenone.

[0024] In the general formula (1), Y is independently a glycidyl group, a hydrogen atom, or an unsaturated heterocyclic ring-containing acyl group having 5 to 20 carbon atoms. When Y is a glycidyl group, an epoxy group is provided at the end, when Y is a hydrogen atom, a hydroxyl group is provided at the end, and when Y is the acyl group, an ester group is provided at the end. The acyl group is represented by R-CO-, where R is an unsaturated heterocyclic ring substituent having 4 to 19 carbon atoms. The glycidyl group is preferably 50 mol % or more of Y, more preferably 80 mol % or more, even more preferably 90 mol % or more, and particularly preferably 100 mol %.

[0025] In the acyl group (R-CO-), the unsaturated heterocyclic substituent having 4 to 19 carbon atoms represented by R is preferably an unsaturated heterocyclic substituent such as a furyl group having 4 carbon atoms (the following formula (2a), W = oxygen atom (O)), a thienyl group having 4 carbon atoms (the following formula (2a), W = sulfur atom (S)), a pyran skeleton substituent having 5 carbon atoms (the following formula (2b), W = O), a thiopyran skeleton substituent having 5 carbon atoms (the following formula (2c), W = S), a pyridyl group having 5 to 12 carbon atoms (the following formula (2d)), an azanaphthyl group (the following formula (2e)), or an azaanthracenyl group (the following formula (2f)). Among these, a furyl group (formula (3a) below), a thienyl group (formula (3b) below), and a pyridyl group (formula (3c) below) are preferred, and a furyl group (formula (3a) below) and a thienyl group (formula (3b) below) are particularly preferred. [ka] Here, R 1 ~R 6 are each independently a hydrocarbon group having 1 to 6 carbon atoms, n1 is an integer of 0 to 3, n2 is an integer of 0 to 5, n3 is an integer of 0 to 5, n4 is an integer of 0 to 4, n5 is an integer of 0 to 6, and n6 is an integer of 0 to 8. W is an oxygen atom or a sulfur atom. As the hydrocarbon group having 1 to 6 carbon atoms, a linear, branched or cyclic alkyl group or a phenyl group having 1 to 5 carbon atoms is preferable. As the alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a t-pentyl group, a methylbutyl group, a cyclopentyl group, and the like can be mentioned.

[0026] [ka]

[0027] In the general formula (1), Z is independently an unsaturated heterocyclic ring-containing acyl group having 5 to 20 carbon atoms or a hydrogen atom. At least 5 mol% of Z is the above acyl group, and the rest is a hydrogen atom. The content (mol%) of the acyl group in the total Z of the formula (1) is also referred to as the acylation rate. The acylation rate is preferably at least 10 mol%, more preferably at least 50 mol%, further preferably at least 70 mol%, and particularly preferably at least 90 mol%. The upper limit of the acylation rate is 100 mol%, but the reaction may be substantially at about 95 mol%. The above acyl group is the same as that exemplified for Y above, and the preferred acyl group is also the same. When all Z's (100 mol%) are acyl groups, the modified epoxy resin of the present invention does not contain secondary hydroxyl groups, and the dielectric properties and heat resistance can be further improved. On the other hand, for example, when finely adjusting the adhesion to metals, a suitable amount of secondary hydroxyl groups can be intentionally made to exist in the modified epoxy resin of the present invention by leaving a portion of Z as hydrogen atoms, within a range that does not significantly affect other physical properties including heat resistance. In addition, the fewer hydrogen atoms there are as Z, the more improved the solvent solubility and moisture resistance can be obtained. It is most preferable that the acyl group only has an unsaturated heterocyclic ring-containing acyl group having 5 to 20 carbon atoms, but other acyl groups may be present other than the unsaturated heterocyclic ring-containing acyl group having 5 to 20 carbon atoms as long as it does not have an adverse effect. In this case, the other acyl groups preferably account for less than 50 mol%, more preferably 20 mol% or less, and even more preferably 10 mol% or less of the total acyl groups.

[0028] In the general formula (1), n ​​is the number of repetitions and is an average value. The value ranges from 1 to 50. From the viewpoint of heat resistance, it is preferably from 1 to 30, more preferably from 1 to 20. The number n can be calculated from the number average molecular weight (Mn) obtained by the GPC method.

[0029] The modified epoxy resin of the present invention is a resin in which some or all of the secondary hydroxyl groups of a normal epoxy resin are acylated with an unsaturated heterocycle-containing acyl group having 5 to 20 carbon atoms, and can be obtained by various methods. A preferred production method is, for example, a production method in which a bifunctional epoxy resin represented by the following formula (4) is reacted with a diester compound of an unsaturated heterocycle-containing acyl group represented by the following formula (5). The epoxy resin modified with an unsaturated heterocycle-containing acyl group obtained by this production method is the modified epoxy resin of the present invention, and is represented by the same general formula (1).

[0030] [ka]

[0031] In formula (4), G is a glycidyl group, m is the number of repetitions, and its average value is from 0 to 6, preferably from 0 to 3, more preferably from 0 to 1, and further preferably from 0 to 0.3. In formula (5), Q is an unsaturated heterocyclic ring-containing acyl group having 5 to 20 carbon atoms or a hydrogen atom, and 5 mol % or more of Q is an unsaturated heterocyclic ring-containing acyl group having 5 to 20 carbon atoms, and the rest is a hydrogen atom. Here, the compound represented by formula (5) may be a mixture of two or more selected from a diester compound in which both Qs are the above-mentioned acyl group, a monoester compound in which one is the above-mentioned acyl group and the other is a hydrogen atom, and a diphenol compound in which both Qs are hydrogen atoms. The compound represented by formula (5) is called a diester compound. The diester compound may be a diester compound in which both Qs are the above-mentioned acyl group, or the main component (preferably 5 mol % or more, more preferably 50 mol % or more, even more preferably 70 mol % or more, particularly preferably 90 mol % or more) is the compound (mixture). That is, the molar ratio of acyl groups to hydrogen atoms (acyl groups / hydrogen atoms) is 100 / 0 to 5 / 95. X in formula (4) 1 and X in formula (5) 2 is selected to give X in equation (1). Also, X 1 and X 2 may be the same or different.

[0032] The bifunctional epoxy resin used in this production method is an epoxy resin represented by formula (4), for example, HO-X 1 Examples of the epoxy resin include an epoxy resin obtained by reacting a bifunctional phenol compound represented by -OH with epihalohydrin in the presence of an alkali metal compound. 1 is X in the above formula (4). 1 The epoxy equivalent (g / eq.) of the bifunctional epoxy resin represented by formula (4) is preferably 100 to 400, and the upper limit is more preferably 300 or less. The value m in formula (4) is preferably 0 to 1, and more preferably 0.3 or less.

[0033] Examples of epihalohydrin include epichlorohydrin and epibromohydrin. Examples of the alkali metal compound include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide; alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride, and potassium chloride; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; alkali metal salts of organic acids such as sodium acetate and sodium stearate; alkali metal epoxides, sodium hydride, and lithium hydride.

[0034] In the reaction between the bifunctional phenol compound and epihalohydrin to obtain the raw material epoxy resin, the alkali metal compound is preferably used in an amount of 0.80 to 1.20 times by mole, more preferably 0.85 to 1.05 times by mole, based on the functional group in the bifunctional phenol compound. If the amount is less than this, the amount of residual hydrolyzable chlorine may be large. The alkali metal compound is used in the form of an aqueous solution, an alcohol solution, or a solid.

[0035] In the epoxidation reaction, an excess amount of epihalohydrin is used relative to the bifunctional phenol compound. Usually, 1.5 to 15 times the molar amount of epihalohydrin is used relative to 1 mole of the functional group in the bifunctional phenol compound, preferably 2 to 10 times the molar amount, more preferably 5 to 8 times the molar amount. If the amount is more than this amount, the production efficiency decreases, and if it is less than this amount, the amount of high molecular weight epoxy resin produced increases, and it may become unsuitable as a raw material for the modified epoxy resin of the present invention.

[0036] The epoxidation reaction is usually carried out at a temperature of 120° C. or less. If the reaction temperature is high, the amount of so-called difficultly hydrolyzable chlorine increases, making it difficult to achieve high purification. The temperature is preferably 100° C. or less, and more preferably 85° C. or less.

[0037] When a bifunctional phenol compound is reacted with epihalohydrin, m usually becomes greater than 0. In order to make m 0, an epoxy resin produced by a known method can be highly purified by a technique such as distillation or crystallization, or a bifunctional phenol compound can be allylated and then epoxidized by oxidizing the olefin moiety.

[0038] The unsaturated heterocycle-containing compound (diester compound) represented by the above formula (5) is, for example, HO-X 2 The compound can be obtained by acylation of a bifunctional phenol compound represented by -OH with an acid anhydride of an unsaturated heterocyclic ring-containing organic acid, a halide of an unsaturated heterocyclic ring-containing organic acid, or a condensation reaction with an unsaturated heterocyclic ring-containing organic acid.

[0039] By using a bifunctional epoxy resin in which m in formula (4) is 0 as the raw material, the modified epoxy resin of the present invention does not contain secondary hydroxyl groups, and the dielectric properties and heat resistance can be further improved. In addition, for example, when finely adjusting the adhesion to metal, by using a bifunctional epoxy resin with an appropriate m number, it is possible to intentionally make an appropriate amount of secondary hydroxyl groups present in the modified epoxy resin within a range that does not significantly affect other physical properties including heat resistance.

[0040] The amount of the bifunctional epoxy resin and the unsaturated heterocycle-containing compound (diester compound) used is preferably 0.2 to 0.95 equivalents of the ester group (acyloxy group) or hydroxyl group in the unsaturated heterocycle-containing compound per equivalent of the epoxy group, more preferably 0.25 to 0.9 equivalents, and even more preferably 0.3 to 0.85 equivalents. The smaller the equivalent ratio, the smaller the epoxy equivalent of the modified epoxy resin obtained, and the heat resistance and dielectric properties of the cured product are improved. On the other hand, the higher the equivalent ratio, the more film-forming properties can be imparted to the modified epoxy resin. Within this range, excellent physical properties can be expressed, and the physical properties can be finely adjusted by varying the equivalent ratio. In addition, it is also possible to replace a part of the unsaturated heterocycle-containing compound with a bifunctional phenol compound. This allows the modified epoxy resin to have an appropriate amount of secondary hydroxyl groups, allowing fine adjustment of the physical properties. The molar ratio (acyloxy group / hydroxyl group) of the ester group (acyloxy group) and the hydroxyl group in the unsaturated heterocycle-containing compound is 100 / 0 to 5 / 95, and this makes it possible to satisfy the content of 5 mol% or more of the acyl group in the total Z of formula (1). In addition, when a phenol compound is mixed, the hydroxyl group is also included. In this production method, the molecular weight of the modified epoxy resin of the present invention is increased and a portion of the hydroxyl groups of the epoxy resin is esterified.

[0041] In the production method of the present invention, a catalyst may be used, and the catalyst may be any compound having catalytic ability to promote the reaction between an epoxy group and an ester bond. For example, tertiary amines, cyclic amines, imidazoles, organic phosphorus compounds, quaternary ammonium salts, etc. may be mentioned. These catalysts may be used alone or in combination of two or more kinds.

[0042] Examples of tertiary amines include, but are not limited to, triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and the like.

[0043] Examples of cyclic amines include, but are not limited to, 1,4-diazabicyclo[2,2,2]octane (DABCO), 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1,5-diazabicyclo[4,3,0]nonene-5 (DBN), N-methylmorpholine, pyridine, and 4-dimethylaminopyridine (DMAP).

[0044] Examples of imidazoles include, but are not limited to, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-phenylimidazole.

[0045] Examples of the organic phosphorus compound include phosphines such as tri-n-propylphosphine, tri-n-butylphosphine, diphenylmethylphosphine, triphenylphosphine, tris(p-tolyl)phosphine, tricyclohexylphosphine, tri(t-butyl)phosphine, tris(p-methoxyphenyl)phosphine, paramethylphosphine, 1,2-bis(dimethylphosphino)ethane, and 1,4-bis(diphenylphosphino)butane; tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, tetrabutylphosphonium hydroxide, and trimethylphosphonium iodide. Examples of phosphonium salts include, but are not limited to, trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, and triphenylbenzylphosphonium bromide.

[0046] Examples of quaternary ammonium salts include, but are not limited to, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride, and phenyltrimethylammonium chloride.

[0047] Among the catalysts listed above, 4-dimethylaminopyridine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]undecene-7, 1,5-diazabicyclo[4,3,0]nonene-5, 2-ethyl-4-methylimidazole, tris(p-tolyl)phosphine, tricyclohexylphosphine, tri(t-butyl)phosphine, and tris(p-methoxyphenyl)phosphine are preferred, and 4-dimethylaminopyridine, 1,8-diazabicyclo[5,4,0]undecene-7, 1,5-diazabicyclo[4,3,0]nonene-5, and 2-ethyl-4-methylimidazole are particularly preferred.

[0048] The amount of catalyst used is usually 0.001 to 1 mass% of the reaction solid content, but when these compounds are used as catalysts, the catalysts remain as residues in the resulting modified epoxy resin, which may deteriorate the insulating properties of the cured product or shorten the pot life of the composition, so the nitrogen content derived from the catalyst in the modified epoxy resin is preferably 0.5 mass% or less, more preferably 0.3 mass% or less. Also, the phosphorus content derived from the catalyst in the modified epoxy resin is preferably 0.5 mass% or less, more preferably 0.3 mass%.

[0049] In the production method, a reaction solvent may be used, and the solvent may be any solvent that dissolves the modified epoxy resin. Examples of the solvent include aromatic solvents, ketone solvents, amide solvents, glycol ether solvents, and ester solvents. These solvents may be used alone or in combination of two or more.

[0050] Examples of aromatic solvents include benzene, toluene, and xylene.

[0051] Examples of ketone solvents include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, acetylacetone, dioxane, diisobutyl ketone, isophorone, methylcyclohexanone, and acetophenone.

[0052] Examples of amide solvents include formamide, N-methylformamide, N,N-dimethylformamide (DMF), acetamide, N-methylacetamide, N,N-dimethylacetamide, 2-pyrrolidone, and N-methylpyrrolidone.

[0053] Examples of glycol ether-based solvents include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol mono-n-butyl ether; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol mono-n-butyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-butyl ether; ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; and polyethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and triethylene glycol dibutyl ether. ethylene glycol dialkyl ethers, propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, and propylene glycol dibutyl ether, polypropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, and tripropylene glycol dibutyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate,Examples of the polyethylene glycol monoalkyl ether acetates include triethylene glycol monobutyl ether acetate and other polyethylene glycol monoalkyl ether acetates, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate.

[0054] Examples of ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, benzyl acetate, ethyl propionate, ethyl butyrate, and butyl butyrate.

[0055] Other solvents include, for example, dimethylsulfoxide, sulfolane, dioxane, valerolactone, and γ-butyrolactone.

[0056] In the production method, the solid content during the reaction is preferably 35 to 100% by mass, more preferably 50 to 90% by mass, and even more preferably 70 to 90% by mass. If a highly viscous product is produced during the reaction, the reaction can be continued by adding additional solvent. After the reaction is completed, the solvent can be removed or further added as necessary.

[0057] The reaction temperature is within a range in which the catalyst used does not decompose. If the reaction temperature is too high, the catalyst may decompose and the reaction may stop, or the modified epoxy resin produced may deteriorate. If the reaction temperature is too low, the reaction may not proceed sufficiently to achieve the desired molecular weight. Therefore, the reaction temperature is preferably 50 to 230°C, more preferably 120 to 200°C. The reaction time is usually 1 to 12 hours, preferably 3 to 10 hours. When a low-boiling solvent such as acetone or methyl ethyl ketone is used, the reaction temperature can be ensured by carrying out the reaction under high pressure using an autoclave. When it is necessary to remove the heat of reaction, it is usually performed by evaporation, condensation, and reflux of the solvent used by the heat of reaction, indirect cooling, or a combination of these.

[0058] As a manufacturing method other than the above, for example, there is a method of reacting an epoxy resin represented by the following general formula (6) with an acylating agent (an acid component such as an acid anhydride of an organic acid, an organic acid halide, or an organic acid ester) to acylate the alcoholic hydroxyl group of the epoxy resin. Acylation may be performed not only by direct esterification but also by a method such as ester exchange. [ka] In formula (6), X and n are defined as in formula (1), and G is a glycidyl group.

[0059] The epoxy resin represented by formula (6) as the raw material can be obtained by a conventionally known method. Examples of the method include a method of reacting bifunctional phenolic compounds with epihalohydrin in the presence of an alkali metal compound (hereinafter referred to as the "one-step method") and a method of reacting bifunctional epoxy resins with bifunctional phenolic compounds in the presence of a catalyst (hereinafter referred to as the "two-step method"). The epoxy resin as the raw material may be obtained by any method, but in the case of a high molecular weight substance, it is easier to obtain it by the two-step method than by the one-step method, so it is preferable to use the two-step method. In both the one-step method and the two-step method, an epoxy resin in the desired range can be produced by appropriately adjusting the molar ratio of the raw materials.

[0060] Examples of bifunctional phenol compounds used in the production of the one-stage method and the two-stage method include bisphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, bisphenol C, bisphenolacetophenone, bisphenolfluorene, dihydroxybiphenyl ether, dihydroxybiphenyl thioether, etc., biphenols such as 4,4'-biphenol, 2,4'-biphenol, etc., 1,1-bi-2-naphthol, catechol, resorcin, hydroquinone, dihydroxynaphthalene, etc. Furthermore, a plurality of these bifunctional phenol compounds may be used in combination.

[0061] In addition, examples of bifunctional epoxy resins that are raw materials for the two-stage process include bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol acetophenone type epoxy resins, diphenyl sulfide type epoxy resins, diphenyl ether type epoxy resins, biphenol type epoxy resins, diphenyl dicyclopentadiene type epoxy resins, alkylene glycol type epoxy resins, naphthalene type epoxy resins, benzene type epoxy resins, and aliphatic cyclic epoxy resins. These epoxy resins may be substituted with substituents that do not have adverse effects, such as alkyl groups and aryl groups. A plurality of these epoxy resins may be used in combination.

[0062] As the acylating agent (acid component used for acylation), for example, the above-mentioned unsaturated heterocyclic ring-containing organic acids such as furan carboxylic acid, thiophene carboxylic acid, pyridine carboxylic acid, acid anhydrides of the organic acids, halides of the organic acids, esters of the organic acids, etc. can be used. Preferably, it is an acid anhydride containing an unsaturated heterocyclic ring. As the acid anhydride of an unsaturated heterocyclic ring-containing organic acid, for example, bis(2-furan carboxylic acid) anhydride, bis(2-thiophene carboxylic acid) anhydride, etc. can be mentioned. As the esters of an unsaturated heterocyclic ring-containing organic acid, for example, 2-ethyl furan carboxylate, 2-methyl thiophene, etc. can be mentioned. As the halides of an unsaturated heterocyclic ring-containing organic acid, for example, 2-furan carboxylic acid chloride, 2-thiophene carboxylic acid chloride, etc. can be mentioned. As the unsaturated heterocycle-containing compound used for esterification, a halide of an unsaturated heterocycle-containing organic acid such as 2-furancarboxylic acid chloride, or an acid anhydride of an unsaturated heterocycle-containing organic acid such as bis(2-furancarboxylic acid) anhydride is preferred, and an acid anhydride of an unsaturated heterocycle-containing organic acid such as bis(2-furancarboxylic acid) anhydride is particularly preferred in order to avoid contamination with halogens, which are undesirable in electrical material applications.

[0063] The charge ratio of an acid component such as an organic acid, an acid anhydride of an organic acid, an organic acid halide, or an ester of an organic acid used for esterifying the hydroxyl groups of an epoxy resin when reacting the epoxy resin with the acid component may be the same as the target esterification ratio, or when the reactivity is low, the acid component may be charged in excess relative to the hydroxyl groups, and after reacting until the target esterification ratio is reached, the unreacted acid component may be removed.

[0064] The organic acid, the acid anhydride of the organic acid, the halide of the organic acid, the ester of the organic acid, or the like is preferably reacted in an amount of 0.05 mol or more and less than 1.0 mol, more preferably 0.05 mol or more and 0.8 mol or less, and particularly preferably 0.05 mol or more and 0.6 mol or less, per mol of the alcoholic hydroxyl group equivalent of the epoxy resin.

[0065] The alcoholic hydroxyl group equivalent of the epoxy resin is limited to the alcoholic hydroxyl group generated by the ring-opening reaction of the epoxy group in any of the above-mentioned production methods, and does not include the alcoholic hydroxyl group already contained in the raw material epoxy resin.

[0066] When direct esterification is performed with an acid component, it can be performed while dehydrating using various esterification catalysts such as acid catalysts such as paratoluenesulfonic acid and phosphoric acid, and metal catalysts such as tetraisopropyl titanate, tetrabutyl titanate, dibutyltin oxide, dioctyltin oxide, zinc chloride, etc. In general, it is preferable to perform the esterification at 100 to 250°C under a nitrogen atmosphere, and more preferably at 130 to 230°C.

[0067] When an acid halide or an acid anhydride is used for esterification, the generated acid may be removed by any of the following methods, or a combination of these methods: a method of neutralizing with a basic compound and then filtering the salt, a method of neutralizing with a basic compound and then washing with water, a method of washing with water without neutralization, or a method of removing the acid by distillation, adsorption, etc. When an acid having a boiling point lower than that of the reaction solvent is to be removed, it is preferable to remove the acid by distillation.

[0068] When an epoxy resin is esterified by transesterification, it is usually desirable to carry out the esterification under a nitrogen atmosphere while dealcoholizing the resin using a known esterification catalyst, for example, dibutyltin oxide, dioctyltin oxide, stannoxane catalyst, tetraisopropyl titanate, tetrabutyl titanate, lead acetate, zinc acetate, antimony trioxide, or other organometallic catalyst, acid catalyst, for example, hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, or other basic catalyst, for example, lithium hydroxide, sodium hydroxide, or other basic catalyst.

[0069] The epoxy resin composition of the present invention is an epoxy resin composition containing at least the modified epoxy resin of the present invention and a curing agent. In addition, various additives such as an epoxy resin, an inorganic filler, a coupling agent, and an antioxidant, which will be described later, can be appropriately blended into the epoxy resin composition of the present invention as necessary. The epoxy resin composition of the present invention gives a cured product that satisfies various physical properties required for various applications.

[0070] In the present invention, a curing agent refers to a substance that contributes to the crosslinking reaction and / or chain extension reaction with a modified epoxy resin. In the present invention, even substances that are usually called "curing accelerators" are considered to be curing agents as long as they contribute to the crosslinking reaction and / or chain extension reaction of a modified epoxy resin.

[0071] The content of the curing agent in the epoxy resin composition of the present invention is preferably 0.2 to 1.5 moles of active hydrogen groups per mole of epoxy groups in the total epoxy resin (including the epoxy resin when the epoxy resin described below is used in combination). 0.3 to 1.4 moles is more preferable, 0.5 to 1.3 moles is even more preferable, and 0.8 to 1.2 moles is particularly preferable. Outside this range, curing tends to be incomplete and good cured physical properties may not be obtained. For example, when a phenolic resin or an amine compound is used, it is preferable to mix the active hydrogen groups in an approximately equimolar amount with respect to the epoxy groups. When an acid anhydride compound is used, it is preferable to mix 0.5 to 1.2 moles of acid anhydride groups per mole of epoxy groups, more preferably 0.6 to 1.0 moles.

[0072] The active hydrogen group in the present invention refers to a functional group having active hydrogen reactive with an epoxy group (including a functional group having latent active hydrogen that generates active hydrogen by hydrolysis or the like, and a functional group that exhibits an equivalent curing action). Specific examples include an acid anhydride group, a carboxyl group, an amino group, and a phenolic hydroxyl group. Regarding the active hydrogen group, 1 mole of a carboxyl group or a phenolic hydroxyl group is calculated as 1 mole, and an amino group (NH2) is calculated as 2 moles. In addition, when the active hydrogen group is not clear, the active hydrogen equivalent can be determined by measurement. For example, the active hydrogen equivalent of the curing agent used can be determined by reacting a monoepoxy resin such as phenyl glycidyl ether, whose epoxy equivalent is known, with a curing agent, whose active hydrogen equivalent is unknown, and measuring the amount of the consumed monoepoxy resin.

[0073] The curing agent used in the epoxy resin composition of the present invention is not particularly limited, and any agent generally known as an epoxy resin curing agent can be used. For example, phenolic resins, acid anhydride compounds, amine compounds, amide compounds, imidazole compounds, cyanate ester compounds, active ester compounds, etc. are listed. From the viewpoint of increasing heat resistance, preferred examples include phenolic resins, amide compounds, imidazole compounds, etc., and from the viewpoint of increasing water resistance, preferred examples include active ester compounds. These curing agents may be used alone or in combination of two or more types.

[0074] Examples of phenolic resins include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis(4-hydroxyepoxy)benzene, 1,3-bis(4-hydroxyepoxy)benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolac, bisphenol A novolac, o-cresol novolac, m-cresol novolac, p-cresol novolac, xylenol novolac, poly-p-hydroxystyrene, hydroquinone, resorcinol, catechol, t-butylcatechol, t- Butylhydroquinone, fluoroglycinol, pyrogallol, t-butylpyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated products or polyallylated products of the above dihydroxynaphthalenes, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, allylated pyrogallol, and the like.

[0075] Specific examples of acid anhydride curing agents include maleic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, methylnadic acid, copolymers of styrene monomer and maleic anhydride, copolymers of indenes and maleic anhydride, and the like.

[0076] Specific examples of the amine-based curing agent include aromatic amines such as diethylenetriamine, triethylenetetramine, metaxylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, polyetheramine, biguanide compounds, dicyandiamide, and anisidine, and amine compounds such as polyamidoamines which are condensates of acids such as dimer acid and polyamines.

[0077] Examples of the amide-based compounds include dicyandiamide and its derivatives, polyamide resins, and the like.

[0078] Examples of the imidazole compounds include 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolium] Examples of the imidazoles include 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins and the above imidazoles. Note that since imidazoles have catalytic activity, they can generally be classified as curing accelerators, which will be described later, but in the present invention, they are classified as curing agents.

[0079] The cyanate ester compound is not particularly limited as long as it has two or more cyanato groups (cyanate ester groups) in one molecule. For example, there are novolac-type cyanate ester curing agents such as phenol novolac type and alkylphenol novolac type, naphthol aralkyl type cyanate ester curing agents, biphenyl alkyl type cyanate ester curing agents, dicyclopentadiene type cyanate ester curing agents, bisphenol type cyanate ester curing agents such as bisphenol A type, bisphenol F type, bisphenol E type, tetramethyl bisphenol F type, and bisphenol S type, and prepolymers in which these are partially converted to triazine. Specific examples of cyanate ester-based hardeners include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate), bis(3-methyl-4-cyanate phenyl)methane, bis(3-ethyl-4-cyanate phenyl)methane, bis(4-cyanate phenyl)-1,1-ethane, 4,4-dicyanate-diphenyl, 2,2-bis(4-cyanate phenyl)-1,1,1,3,3,3-hexafluoropropane, 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenyl) Examples of the cyanate resin include bifunctional cyanate resins such as bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate-phenyl-1-(methylethylidene))benzene, bis(4-cyanate-phenyl)thioether, and bis(4-cyanate-phenyl)ether; cyanate esters of trivalent phenols such as tris(4-cyanate-phenyl)-1,1,1-ethane and bis(3,5-dimethyl-4-cyanate-phenyl)-4-cyanate-phenyl-1,1,1-ethane; polyfunctional cyanate resins derived from phenol novolac, cresol novolac, and dicyclopentadiene structure-containing phenolic resins; and prepolymers in which these cyanate resins are partially triazine-converted. These may be used alone or in combination.

[0080] The active ester compound is not particularly limited, but generally, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferably used. The active ester curing agent is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolac. One or more types of active ester curing agents can be used. Specific examples of the active ester curing agent include active ester curing agents containing a dicyclopentadienyldiphenol structure, active ester curing agents containing a naphthalene structure, active ester curing agents which are acetylated phenol novolac, and active ester curing agents which are benzoylated phenol novolac. Among these, active ester curing agents containing a dicyclopentadienyldiphenol structure are more preferred because they are excellent in improving peel strength. Commercially available products include Epicron HPC-8000-65T (manufactured by DIC Corporation).

[0081] Other curing agents that can be used in the epoxy resin composition of the present invention include, for example, acrylic ester resins, melamine resins, urea resins, cationic polymerization agents, organic phosphines, phosphonium salts, tetraphenylboron salts, hydrazide compounds, boron halide amine complexes, polymercaptan compounds, isocyanate compounds, polyisocyanate compounds, blocked isocyanate compounds, etc. These other curing agents may be used alone or in any combination and ratio of two or more.

[0082] The epoxy resin composition of the present invention may contain an epoxy resin in addition to the modified epoxy resin of the present invention. By using an epoxy resin, it is possible to compensate for insufficient physical properties and improve various physical properties. The epoxy resin is preferably one having two or more epoxy groups in the molecule, and more preferably an epoxy resin having three or more epoxy groups. For example, polyglycidyl ether compounds, polyglycidyl amine compounds, polyglycidyl ester compounds, alicyclic epoxy compounds, other epoxy resins, etc. may be mentioned. These epoxy resins may be used alone, or two or more types of epoxy resins of the same system may be used in combination, or epoxy resins of different systems may be used in combination.

[0083] Examples of the polyglycidyl ether compound include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, bisphenol Z type epoxy resins, bisphenol fluorene type epoxy resins, diphenyl sulfide type epoxy resins, diphenyl ether type epoxy resins, naphthalene type epoxy resins, hydroquinone type epoxy resins, resorcinol type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, alkyl novolac type epoxy resins, styrenated phenol novolac type epoxy resins, bisphenol novolac type epoxy resins, naphthol novolac type epoxy resins, phenol aralkyl type epoxy resins, β-naphthol aralkyl type epoxy resins, naphthalenediol aralkyl type epoxy resins, α-naphthol aralkyl type epoxy resins, biphenyl aralkyl phenol type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, dicyclopentadiene type epoxy resins, alkylene glycol type epoxy resins, and various epoxy resins such as alicyclic epoxy resins can be used.

[0084] Examples of polyglycidylamine compounds include diaminodiphenylmethane type epoxy resins, metaxylenediamine type epoxy resins, 1,3-bisaminomethylcyclohexane type epoxy resins, isocyanurate type epoxy resins, aniline type epoxy resins, hydantoin type epoxy resins, and aminophenol type epoxy resins.

[0085] Examples of the polyglycidyl ester compound include dimer acid type epoxy resins and trimellitic acid type epoxy resins.

[0086] Examples of the alicyclic epoxy compound include alicyclic epoxy resins such as Celloxide 2021 (manufactured by Daicel Corporation).

[0087] Other epoxy resins include, for example, urethane-modified epoxy resins, oxazolidone ring-containing epoxy resins, epoxy-modified polybutadiene rubber derivatives, carboxyl-terminated butadiene nitrile rubber (CTBN)-modified epoxy resins, polyvinylarene polyoxides (for example, divinylbenzene dioxide, trivinylnaphthalene trioxide, etc.), and the like.

[0088] When the modified epoxy resin of the present invention and an epoxy resin are used in combination in the epoxy resin composition of the present invention, the amount of the modified epoxy resin in the total components of the modified epoxy resin and the epoxy resin as solid contents is preferably 50 mass % or more, and more preferably 80 mass % or more.

[0089] The epoxy resin composition of the present invention may contain a solvent or a reactive diluent in order to appropriately adjust the viscosity of the epoxy resin composition when handling it for forming a coating film. In the epoxy resin composition of the present invention, the solvent or reactive diluent is used to ensure the handleability and workability in molding the epoxy resin composition, and there is no particular limit to the amount used. In the present invention, the term "solvent" and the above-mentioned term "solvent" are used separately depending on the form of use, but the same or different substances may be used independently.

[0090] Examples of solvents that may be contained in the epoxy resin composition of the present invention include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, etc., esters such as ethyl acetate, etc., ethers such as ethylene glycol monomethyl ether, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, etc., alcohols such as methanol, ethanol, etc., alkanes such as hexane, cyclohexane, etc., aromatics such as toluene, xylene, etc. The above-mentioned solvents may be used alone or in any combination and ratio of two or more.

[0091] Examples of reactive diluents include monofunctional glycidyl ethers such as allyl glycidyl ether, bifunctional glycidyl ethers such as propylene glycol diglycidyl ether, polyfunctional glycidyl ethers such as trimethylolpropane polyglycidyl ether, glycidyl esters, and glycidyl amines.

[0092] These solvents or reactive diluents are preferably used in an amount of 90% by mass or less as non-volatile matter, and the appropriate type and amount of use are appropriately selected depending on the application. For example, for printed wiring board applications, polar solvents with a boiling point of 160° C. or less, such as methyl ethyl ketone, acetone, and 1-methoxy-2-propanol, are preferably used in an amount of 40 to 80% by mass as non-volatile matter. For adhesive film applications, for example, ketones, acetates, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferably used in an amount of 30 to 60% by mass as non-volatile matter.

[0093] In the epoxy resin composition of the present invention, a curing accelerator or catalyst can be used as necessary. Examples of the curing accelerator or catalyst include imidazole compounds, tertiary amines, phosphorus compounds such as phosphines, metal compounds, Lewis acids, amine complex salts, etc. These may be used alone or in combination of two or more kinds.

[0094] The amount of the curing accelerator or catalyst may be appropriately selected depending on the purpose of use, but 0.01 to 15 parts by mass is used as necessary relative to 100 parts by mass of the epoxy resin component in the resin composition. It is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, even more preferably 0.1 to 5 parts by mass, and particularly preferably 0.1 to 1.0 parts by mass. By using the curing accelerator or catalyst, it is possible to lower the curing temperature and shorten the curing time.

[0095] In the epoxy resin composition of the present invention, various known flame retardants can be used to improve the flame retardancy of the cured product obtained, as long as the reliability is not reduced. Examples of flame retardants that can be used include halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organic metal salt-based flame retardants. From the viewpoint of the environment, flame retardants that do not contain halogens are preferred, and phosphorus-based flame retardants are particularly preferred. These flame retardants may be used alone, or two or more of the same type of flame retardants may be used in combination, or different types of flame retardants may be used in combination.

[0096] The epoxy resin composition of the present invention may contain components other than those listed above (sometimes referred to as "other components" in the present invention) for the purpose of further improving its functionality. Examples of such other components include fillers, thermoplastic resins, thermosetting resins, photocurable resins, ultraviolet protection agents, antioxidants, coupling agents, plasticizers, fluxes, thixotropy-imparting agents, smoothing agents, colorants, pigments, dispersants, emulsifiers, elasticity-reducing agents, release agents, antifoaming agents, ion-trapping agents, etc.

[0097] Examples of fillers include inorganic fillers such as fused silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, boehmite, talc, mica, clay, calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, barium sulfate, and carbon; fibrous fillers such as carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber, and ceramic fiber; and fine particle rubber.

[0098] Examples of thermoplastic resins include phenoxy resin, polyurethane resin, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, vinyl chloride resin, polyvinyl acetate resin, polymethyl methacrylate resin, polycarbonate resin, polyacetal resin, cyclic polyolefin resin, polyamide resin, thermoplastic polyimide resin, polyamideimide resin, polytetrafluoroethylene resin, polyetherimide resin, polyphenylene ether resin, modified polyphenylene ether resin, polyethersulfone resin, polysulfone resin, polyetheretherketone resin, polyphenylene sulfide resin, polyvinyl formal resin, etc. In terms of compatibility, phenoxy resin is preferred.

[0099] Examples of other components include organic pigments such as quinacridone, azo, and phthalocyanine pigments, inorganic pigments such as titanium oxide, metal foil pigments, and rust-preventive pigments, ultraviolet absorbers such as hindered amine, benzotriazole, and benzophenone, antioxidants such as hindered phenol, phosphorus, sulfur, and hydrazide, release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, and additives such as leveling agents, rheology control agents, pigment dispersants, anti-cision agents, and antifoaming agents. The amount of these other components to be blended is preferably in the range of 0.01 to 20% by mass based on the total solid content in the resin composition.

[0100] The epoxy resin composition of the present invention is obtained by uniformly mixing the above-mentioned components. The epoxy resin composition of the present invention, which contains the modified epoxy resin, the curing agent, and further various components as necessary, can be easily cured by a method similar to that known in the art. This cured product has an excellent balance of low moisture absorption, dielectric properties, heat resistance, adhesion, etc., and exhibits good cured physical properties. The term "curing" as used herein means that the epoxy resin composition is intentionally cured by heat and / or light, etc., and the degree of curing may be controlled depending on the desired physical properties and applications. The degree of progress may be completely cured or semi-cured, and is not particularly limited, but the reaction rate of the curing reaction between the epoxy group and the curing agent is usually 5 to 95%.

[0101] The epoxy resin composition of the present invention can be cured in the same manner as known epoxy resin compositions to obtain a cured product. The same methods as known epoxy resin compositions can be used to obtain a cured product, and methods such as casting, injection, potting, dipping, drip coating, transfer molding, compression molding, and lamination in the form of a resin sheet, resin-coated copper foil, prepreg, etc., and curing under heat and pressure to obtain a laminate are preferably used. The curing temperature is usually in the range of 80 to 300°C, and the curing time is about 10 to 360 minutes. This heating is preferably performed in two stages, namely, primary heating at 80 to 180°C for 10 to 90 minutes and secondary heating at 120 to 200°C for 60 to 150 minutes. In addition, in a compounding system in which the glass transition temperature (Tg) exceeds the secondary heating temperature, it is preferable to further perform tertiary heating at 150 to 280°C for 60 to 120 minutes. By performing such secondary and tertiary heating, poor curing can be reduced. When producing a semi-cured resin product such as a resin sheet, a copper foil with a resin, or a prepreg, the curing reaction of the epoxy resin composition is usually allowed to proceed to an extent that the shape can be maintained by heating, etc. When the epoxy resin composition contains a solvent, most of the solvent is usually removed by techniques such as heating, reducing pressure, and air drying, but 5% by mass or less of the solvent may remain in the semi-cured resin product.

[0102] The prepreg obtained by using the epoxy resin composition of the present invention will be described. As the sheet-like substrate, woven or nonwoven fabrics of inorganic fibers such as glass, or organic fibers such as polyester, polyamine, polyacrylic, polyimide, Kevlar (registered trademark), cellulose, etc. can be used, but are not limited thereto. The method for producing a prepreg from the epoxy resin composition of the present invention and the sheet-like substrate is not particularly limited, and for example, the above-mentioned sheet-like substrate is immersed in an epoxy resin varnish in which the viscosity of the above-mentioned epoxy resin composition is adjusted with a solvent, and then heated and dried to semi-cure (B-stage) the resin component, and can be obtained by, for example, heating and drying at 100 to 200°C for 1 to 40 minutes. Here, the amount of resin in the prepreg is preferably 30 to 80 mass% of the resin content.

[0103] A method for manufacturing a laminate using a prepreg or an insulating adhesive sheet will be described. When forming a laminate using a prepreg, one or more prepregs are laminated, metal foil is placed on one or both sides to form a laminate, and this laminate is heated and pressed to laminate and integrate it. Here, as the metal foil, a single metal foil, an alloy metal foil, or a composite metal foil of copper, aluminum, brass, nickel, etc. can be used. The conditions for heating and pressing the laminate may be appropriately adjusted so that the resin composition is cured, but if the pressure is too low, air bubbles may remain inside the obtained laminate, which may deteriorate the electrical properties, so it is desirable to pressurize under conditions that satisfy the moldability. For example, the temperature is 160 to 220°C, and the pressure is 49 to 490 N / cm. 2 (5~50kgf / cm 2 ) and the heating time can be set to 40 to 240 minutes. In addition, molding is preferably performed in a nitrogen atmosphere.

[0104] Furthermore, a multilayer board can be produced by using the laminate obtained in this way as an inner layer material. In this case, a circuit is first formed on the laminate by an additive method, a subtractive method, or the like, and the surface of the formed circuit is blackened by treating it with an acid solution to obtain an inner layer material. An insulating layer is formed on one or both circuit-forming surfaces of this inner layer material using a prepreg or an insulating adhesive sheet, and a conductor layer is formed on the surface of the insulating layer to produce a multilayer board.

[0105] When forming an insulating layer using an insulating adhesive sheet, an insulating adhesive sheet is placed on the circuit-forming surface of a plurality of inner layer materials to form a laminate. Alternatively, an insulating adhesive sheet is placed between the circuit-forming surface of the inner layer material and a metal foil to form a laminate. Then, this laminate is heated and pressurized to be integrally molded, thereby forming the cured product of the insulating adhesive sheet as an insulating layer and forming a multi-layered inner layer material. Alternatively, the inner layer material and the metal foil as a conductor layer form the cured product of the insulating adhesive sheet as an insulating layer. Here, the metal foil can be the same as that used in the laminate used as the inner layer material. The hot and press molding can be carried out under the same conditions as those for molding the inner layer material. When forming an insulating layer by applying a resin composition to a laminate, the resin composition is applied to the circuit forming surface of the outermost layer of the inner layer material, preferably to a thickness of 5 to 100 μm, and then heated and dried at 100 to 200° C. for 1 to 90 minutes to form a sheet. It is generally formed by a method called a casting method. It is preferable to form the thickness after drying to 5 to 80 μm. A printed wiring board can be formed by further forming via holes and circuits on the surface of the multilayer laminate thus formed by an additive method or a subtractive method. Furthermore, by repeating the above-mentioned process using this printed wiring board as an inner layer material, a multi-layer laminate can be formed.

[0106] When forming an insulating layer using prepreg, one or more prepreg sheets are placed on the circuit forming surface of the inner layer material, and a metal foil is placed on the outside of the prepreg to form a laminate. This laminate is then heated and pressurized to form an integral mold, whereby the cured prepreg is formed as an insulating layer, and the metal foil on the outside is formed as a conductor layer. Here, the metal foil may be the same as that used for the laminate used as the inner layer material. The hot press molding may be performed under the same conditions as those for molding the inner layer material. The surface of the multilayer laminate thus molded may be further subjected to via hole formation or circuit formation by an additive method or a subtractive method to mold a printed wiring board. Furthermore, by repeating the above process using this printed wiring board as an inner layer material, a multi-layer board with even more layers can be formed.

[0107] The cured product obtained from the epoxy resin composition of the present invention and the laminate suitable for use in electric and electronic circuits have excellent flame retardancy and heat resistance. EXAMPLES

[0108] The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, parts means "parts by mass" and % means "% by mass". Analytical and measuring methods are shown below. Furthermore, the unit of various equivalents is "g / eq.".

[0109] (1) Epoxy equivalent: Measurements were performed in accordance with JIS K7236 and expressed in units of "g / eq.". Specifically, a potentiometric titrator (HIRANUMA SANGYO CO., LTD., COM-1600ST) was used, chloroform was used as the solvent, tetraethylammonium bromide acetate solution was added, and a 0.1 mol / L perchloric acid-acetic acid solution was used. For products containing solvent, the value was calculated as a solids content equivalent from the non-volatile content.

[0110] (2) Weight average molecular weight (Mw) and number average molecular weight (Mn): It was determined by GPC measurement. Specifically, a main body HLC8320GPC (manufactured by Tosoh Corporation) equipped with columns (TSKgel SuperH-H, SuperH2000, SuperHM-H, SuperHM-H, all manufactured by Tosoh Corporation) in series was used, and the column temperature was set to 40°C. The eluent was tetrahydrofuran (THF), the flow rate was 1.0 mL / min, and the detector was a differential refractive index detector. The measurement sample was prepared by dissolving 0.1 g of solid content in 10 mL of THF and filtering through a 0.45 μm microfilter, and the injection amount was 50 μL. Mw was calculated by conversion from a calibration curve obtained from standard polystyrene (manufactured by Tosoh Corporation, PStQuick A, PStQuick B, PStQuick C). The data was processed using GPC8020 model II version 6.00 (manufactured by Tosoh Corporation).

[0111] (3)IR (infrared absorption spectrum): A Fourier transform infrared spectrophotometer (Perkin Elmer Precisely, Spectrum One FT-IR Spectrometer 1760X) was used, and sodium chloride was used as the cell. The sample dissolved in chloroform was applied to the cell, dried, and then measured at a wave number of 500 to 4000 cm. -1 The transmittance was measured.

[0112] (4) Heat resistance: The measurement was performed in accordance with the IPC-TM-650 2.4.25.c standard. Specifically, a sample with a thickness of 4 mm and a diameter of 3 mm was measured in two cycles in the range of 20 to 200°C at a temperature increase rate of 10°C / min using a differential scanning calorimeter EXSTAR6000 DSC6200 (manufactured by Hitachi High-Tech Science Corporation), and the glass transition temperature was expressed as the midpoint glass transition temperature (Tmg) of the measurement chart obtained by the second scan.

[0113] (5)Dielectric properties: Measurement was performed in accordance with IPC-TM-650 2.5.5.9. Specifically, the dielectric loss tangent at a frequency of 1 GHz was determined by the capacitance method using a material analyzer (manufactured by AGILENT Technologies).

[0114] The abbreviations used in the examples and comparative examples are as follows.

[0115] [Bifunctional epoxy resin] A1: Tetramethylbiphenol type epoxy resin (Mitsubishi Chemical Corporation, YX4000, epoxy equivalent 185, m≒0.05) [ka] Here, m has the same meaning as m in formula (4).

[0116] [Diester compounds] B1: 2-furancarboxylic acid, 4,4'-(3,3,5-trimethylcyclohexylidene)-di-4,1-phenylene ester (Honshu Chemical Industry Co., Ltd., BH-1, active ester group equivalent 249) [ka] B2: 2-furan carboxylic acid, 4,4'-biphenyl ester (Honshu Chemical Industry Co., Ltd., BH-2, active ester group equivalent: 187) [ka] B3: 1,1-bis(4-(2-thiophenecarboxyphenyl))-3,3,5-trimethylcyclohexane (active ester group equivalent: 265) obtained in Synthesis Example 1 [ka] B4: 1,1-bis(4-(2-quinolinecarboxyphenyl))-3,3,5-trimethylcyclohexane (active ester group equivalent: 310) obtained in Synthesis Example 3 [ka] B5: 1,1-bis(4-acetoxyphenyl)-3,3,5-trimethylcyclohexane (active ester group equivalent: 197) obtained in Synthesis Example 4 [ka] B6: 4,4-diacetoxybiphenyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., active ester equivalent = 135) [ka]

[0117] C1: 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (Honshu Chemical Industry Co., Ltd., BisP-HTG, hydroxyl equivalent 155) [ka]

[0118] [catalyst] D1: 4-Dimethylaminopyridine (Tokyo Chemical Industry Co., Ltd.)

[0119] [Solvents] S1: Cyclohexanone

[0120] [Acid anhydride] E1: Thiophene-2-carboxylic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) E2: Acetic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) E3: 2-quinolinecarboxylic anhydride obtained in Synthesis Example 2

[0121] [Hardening agent] H1: Active ester curing agent obtained in Synthesis Example 6 (active ester equivalent: 246)

[0122] Synthesis Example 1 A glass reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet, a cooling tube, and a dropping device was charged with 50 parts of C1, 154 parts of E1, and 150 parts of pyridine at room temperature, and the mixture was heated to 60°C while stirring under nitrogen gas flow, and reacted for 2 hours. The mixture was then dried under reduced pressure at 130°C and 1.3 kPa (10 torr) for 2 hours to remove pyridine. The mixture was then washed with a large amount of water to obtain 70 parts of 1,1-bis(4-(2-thiophenecarboxyphenyl))-3,3,5-trimethylcyclohexane (B3).

[0123] Synthesis Example 2 In a glass reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction device, a cooling tube, and a dropping device, 195 parts of sodium quinaldate (Tokyo Chemical Industry Co., Ltd.), 192 parts of quinaldoyl chloride (Sigma-Aldrich Co., Ltd.), and 300 parts of nitroethane (Fujifilm Wako Pure Chemical Industries, Ltd.) were charged at room temperature, and the mixture was heated to 110°C while stirring under nitrogen gas flow, and reacted for 3 hours. After that, the mixture was dried under reduced pressure at 120°C and 1.3 kPa (10 torr) for 2 hours, and 292 parts of 2-quinolinecarboxylic anhydride (E3) was obtained.

[0124] Synthesis Example 3 In a glass reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet, a cooling tube, and a dropping device, 100 parts of C1, 106 parts of E3, 102 parts of pyridine, and 100 parts of toluene were charged at room temperature, and the mixture was heated to 60°C while stirring under nitrogen gas flow, and reacted for 2 hours. After that, the mixture was dried under reduced pressure at 115°C and 1.3 kPa (10 torr) for 2 hours, and 200 parts of 1,1-bis(4-(2-quinolinecarboxyphenyl))-3,3,5-trimethylcyclohexane (B2) was obtained.

[0125] Synthesis Example 4 In a glass reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet, a cooling tube, and a dropping device, 100 parts of C1, 131 parts of E2, and 102 parts of pyridine were charged at room temperature, and the mixture was heated to 60°C while being stirred under nitrogen gas flow, and reacted for 2 hours. After that, the mixture was dried under reduced pressure at 115°C and 1.3 kPa (10 torr) for 2 hours, and 110 parts of 1,1-bis(4-acetoxyphenyl)-3,3,5-trimethylcyclohexane (B5) was obtained.

[0126] Synthesis Example 5 500 parts of 2,6-xylenol and 7.3 parts of 47% BF3 ether complex were charged into a reaction apparatus consisting of a glass separable flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, a dropping funnel, and a cooling tube, and heated to 100 ° C. while stirring. While maintaining the same temperature, 67.6 parts of dicyclopentadiene (0.12 times the moles relative to 2,6-xylenol) were dropped over 1 hour. Further, the reaction was carried out at a temperature of 115 to 125 ° C. for 4 hours, and 11 parts of calcium hydroxide were added. Further, 19 parts of a 10% aqueous oxalic acid solution were added. After that, the mixture was heated to 160 ° C. for dehydration, and then heated to 200 ° C. under a reduced pressure of 5 mmHg to evaporate and remove the unreacted raw materials. 1320 parts of methyl isobutyl ketone (MIBK) were added to dissolve the product, and 400 parts of 80 ° C. hot water was added to wash it, and the lower layer water tank was separated and removed. Thereafter, the mixture was heated to 160° C. under a reduced pressure of 5 mmHg to evaporate and remove the MIBK, yielding 164 parts of a reddish-brown aromatic hydroxy compound (PH1).

[0127] Synthesis Example 6 In a reaction apparatus equipped with a stirrer, a thermometer, a nitrogen inlet, a dropping funnel, and a cooling tube, 100 parts of PH1 obtained in Synthesis Example 5, 24.6 parts of 1-naphthol (PH4), 1.7 parts of tetra n-butylammonium bromide (TBAB), 69.8 parts of isophthalic acid chloride, and 457 parts of toluene (TL) were charged, and the temperature was raised to 50 ° C. to dissolve. While controlling the temperature in the system to 60 ° C. or less, 137.1 parts of 20% aqueous sodium hydroxide solution (20% NaOH) was dropped over 3 hours, and then stirring was continued at the same temperature for another 4 hours. The reaction mixture was left to stand and separated, and the water tank was removed. This operation was repeated until the pH of the water tank reached 7. Thereafter, water was removed by reflux dehydration to obtain an active ester resin (H1) in a toluene solution state with a non-volatile content of 65%. The active ester equivalent calculated from the amount of raw materials charged was 246. [ka] where k is the number of iterations, which is 7.1 on average.

[0128] Example 1 A glass reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet, cooling tube, and dropping device was charged with 100 parts of A1, 113.3 parts of B1, and 24 parts of S1 as a reaction solvent at room temperature, and heated to 130°C while stirring under nitrogen gas flow. After adding 0.2 parts of D1 as a catalyst, the temperature was raised to 145°C and the reaction was carried out at the same temperature for 5 hours to obtain a modified epoxy resin (R1). The epoxy equivalent was 2690.

[0129] Examples 2 to 6, Comparative Examples 1 to 4 Modified epoxy resins were obtained by the same procedure as in Example 1, according to the amounts (parts) of each raw material shown in Table 1. The "molar ratio" in the table indicates the molar ratio (equivalent ratio) of the acyl group of the diester compound to the epoxy group of the bifunctional epoxy resin.

[0130] [Table 1]

[0131] Example 7 15 parts (solid content value) of the modified epoxy resin (R1) obtained in Example 1, 1.4 parts (solid content value) of the curing agent (H1), and 0.15 parts of the curing catalyst (D1) were mixed, and further diluted with methyl ethyl ketone to a non-volatile content of 50% to obtain a resin composition. These were then applied to an iron plate so that the film thickness after drying was 150 μm, and dried at 130 ° C. for 15 minutes using a dryer. The obtained dried powder was pressed for 80 minutes under conditions of a vacuum degree of 0.5 kPa, a heating temperature of 220 ° C., and a pressing pressure of 2 MPa to obtain a cured product with a thickness of 1 mm. A spacer of 1 mm was used to adjust the thickness. The values ​​in the table indicate solid content values.

[0132] Examples 8 to 12, Comparative Examples 5 to 8 The same procedures as in Example 7 were carried out using the blending amounts shown in Tables 2 and 3 to obtain cured products. The heat resistance and dielectric properties of the resulting cured products were measured, and the results are shown in Tables 2 and 3.

[0133] [Table 2]

[0134] [Table 3]

[0135] It can be seen from Tables 2 and 3 that the cured product made of the epoxy resin composition using the modified epoxy resin of the present invention has excellent heat resistance and dielectric properties. [Industrial Applicability]

[0136] The modified epoxy resin and resin composition of the present invention are applicable to various fields such as adhesives, paints, civil engineering building materials, insulating materials for electric and electronic parts, and are particularly useful in the electric and electronic fields as insulating casting, lamination materials, sealing materials, etc. The epoxy resin of the present invention and a resin composition containing the same can be suitably used for laminates for electric and electronic circuits such as multilayer printed wiring boards and capacitors, adhesives such as film adhesives and liquid adhesives, semiconductor sealing materials, underfill materials, interchip fill materials for 3D-LSI, insulating sheets, prepregs, heat dissipation substrates, etc.

Claims

1. A modified epoxy resin represented by the following general formula (1) and having an epoxy equivalent of 300 to 10,000 g / eq. 【Chemistry 1】 Here, X is a divalent group. Y is independently a hydrogen atom, an unsaturated heterocyclic ring-containing acyl group having 5 to 20 carbon atoms, or a glycidyl group. Z is independently a hydrogen atom or an unsaturated heterocyclic ring-containing acyl group having 5 to 20 carbon atoms, and 5 mol % or more of the acyl group is the above-mentioned. n is the number of repetitions, and the average value is 1 or more and 50 or less.

2. 2. The modified epoxy resin according to claim 1, wherein the unsaturated heterocyclic ring-containing acyl group having 5 to 20 carbon atoms is any one of the unsaturated heterocyclic ring-containing acyl groups represented by the following formulas (2a) to (2f): 【Chemistry 2】 Here, R １ ~R ６ are independently a hydrocarbon group having 1 to 6 carbon atoms, n1 is an integer from 0 to 3, n2 is an integer from 0 to 5, n3 is an integer from 0 to 5, n4 is an integer from 0 to 4, n5 is an integer from 0 to 6, and n6 is an integer from 0 to 8. W is an oxygen atom or a sulfur atom.

3. The modified epoxy resin according to claim 1, wherein the Z comprises any one of the unsaturated heterocycle-containing acyl groups represented by the following formulas (3a) to (3c): 【Chemistry 3】

4. An epoxy resin composition comprising the modified epoxy resin according to claim 1 and a curing agent.

5. 5. The epoxy resin composition according to claim 4, wherein the curing agent is at least one selected from the group consisting of phenolic resins, acid anhydride compounds, amine compounds, imidazole compounds, amide compounds, cyanate ester compounds, and active ester compounds.

6. 5. The epoxy resin composition according to claim 4, wherein the molar ratio of active hydrogen groups in the curing agent is 0.2 to 1.5 mol per mol of epoxy groups in the total epoxy resins.

7. A cured product obtained by curing the epoxy resin composition according to any one of claims 4 to 6.

8. A prepreg using the epoxy resin composition according to any one of claims 4 to 6.

9. A printed wiring board, comprising the epoxy resin composition according to any one of claims 4 to 6.

10. A method for producing the modified epoxy resin according to claim 1, comprising reacting a bifunctional epoxy resin represented by the following general formula (4) with a compound represented by the following general formula (5): 【Chemistry 4】 Here, X １ and X ２ is a divalent group. G is a glycidyl group. Q is an unsaturated heterocycle-containing acyl group having 5 to 20 carbon atoms or a hydrogen atom, and 5 mol % or more of the acyl group is the above. m is the number of repetitions, the average value of which is 0 to 6. The compound represented by general formula (5) may be a mixture of two or more selected from a compound in which both Qs are the above acyl group, a compound in which one Q is the above acyl group, and a compound in which both Qs are hydrogen atoms.

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