Modified epoxy resin, resin composition, cured product, laminate for electrical and electronic circuits, and method for producing modified epoxy resin.

Abstract

Provided are: a modified epoxy resin excellent in terms of dielectric characteristics, solubility, and adhesiveness; a resin composition comprising the modified epoxy resin and a hardener; a cured object therefrom excellent in terms of dielectric characteristics and heat resistance; and a laminate for electrical / electronic circuits.　The modified epoxy resin is represented by general formula (1) and has an epoxy equivalent of 250-50,000 g / eq.　In formula (1), X is a divalent group; the Y moieties are independently a hydrogen atom, a C2-C20 acyl group, or a glycidyl group; Z is a C2-C20 acyl group or a hydrogen atom, 20-70 mol of the Z moieties being the acyl group; and n, indicating the average number of repetitions, is 1-500.

Description

[Technical Field]

[0001] The present invention relates to a modified epoxy resin having excellent dielectric properties, solubility, and adhesion; a resin composition containing the modified epoxy resin and a curing agent; a cured product thereof having excellent dielectric properties and heat resistance; and a laminate for electrical and electronic circuits made from the resin composition. [Background technology]

[0002] Epoxy resins are widely used in fields such as paints, civil engineering, adhesives, and electrical materials due to their excellent heat resistance, adhesive properties, chemical resistance, water resistance, mechanical strength, and electrical properties. Film-forming properties can be imparted by increasing the molecular weight through various methods. These high molecular weight epoxy resins are called phenoxy resins. In particular, bisphenol A type phenoxy resins are mainly used as base resins for paint varnishes and film molding, or added to epoxy resin varnishes to adjust fluidity, improve toughness and adhesiveness of cured products. Furthermore, those containing phosphorus or bromine atoms in their backbone are used as flame retardants blended into epoxy resin compositions and thermoplastic resins.

[0003] Epoxy resins used in electrical materials such as laminates for electrical and electronic circuits require not only dielectric properties but also solvent solubility, resin compatibility, and adhesion to copper foil. In recent years, the miniaturization and performance enhancement of information devices have progressed rapidly, and consequently, materials used in the fields of semiconductors and electronic components are required to have higher performance than before. In particular, excellent dielectric properties and heat resistance are required as substrates become thinner and more functional.

[0004] In response to such demands, a method has been proposed to improve dielectric properties by converting the hydroxyl groups present in the side chains of phenoxy resins into esters using acetyl or benzoyl groups. For example, Patent Document 1 discloses an epoxy resin composition in which an epoxy resin having a 2-acyl-1,3-propyleneglycoxy group with 1 to 3 carbon atoms in the acyl group in its molecular structure and a curing agent are essential components. Patent Document 2 discloses an epoxy resin composition in which a bisphenol-type epoxy resin having an acyl group with 1 to 3 carbon atoms in its molecular side chain and an organic solvent with a solubility parameter of 7.0 to 13.0 are essential components. Patent Document 3 discloses a phenoxy resin obtained by reacting a bifunctional epoxy resin with a diester compound and its cured product. However, it does not fully satisfy the required properties of the epoxy resin or phenoxy resin, including solubility and fluidity, as well as the dielectric properties and thermal conductivity of the cured product. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 8-333437 [Patent Document 2] Japanese Patent Application Publication No. 10-168287 [Patent Document 3] Japanese Patent Publication No. 2016-089165 [Overview of the project]

[0006] The object of the present invention is to provide a modified epoxy resin with excellent dielectric properties, solubility, and adhesion. Furthermore, the object is to provide a cured product with excellent dielectric properties and heat resistance by curing a resin composition containing this resin.

[0007] To solve the above problems, the inventors conducted diligent research and found that a modified epoxy resin having a specific structure exhibits excellent dielectric properties, solubility, and adhesion. Furthermore, they found that a cured product obtained by curing a resin composition containing this resin exhibits excellent dielectric properties and heat resistance, thus completing the present invention.

[0008] In other words, the present invention is a modified epoxy resin represented by the following general formula (1), having an epoxy equivalent of 250 to 50,000 g / eq. [ka] During the ceremony, X is a divalent group. Y is independently a hydrogen atom, an acyl group having 2 to 20 carbon atoms, or a glycidyl group. Z is an acyl group having 2 to 20 carbon atoms or a hydrogen atom, and 20 to 70 mol% is the aforementioned acyl group. n is the average number of repetitions, and is between 1 and 500.

[0009] In the modified epoxy resin of the present invention, it is desirable that 40 mol% or more of X are monocyclic or condensed polycyclic aromatic hydrocarbon groups having 6 to 20 carbon atoms, selected from the group consisting of benzene ring groups, naphthalene ring groups, anthracene ring groups, or phenanthrene ring groups. These monocyclic or condensed polycyclic aromatic hydrocarbon groups may have substituents. The modified epoxy resin of the present invention preferably has an epoxy equivalent content exceeding 5,000 g / eq.

[0010] Furthermore, the present invention relates to a resin composition comprising the above-mentioned modified epoxy resin and a curing agent. The above resin composition preferably contains 0.1 to 100 parts by mass of curing agent as solid content per 100 parts by mass of modified epoxy resin.

[0011] The above resin composition comprises the above-mentioned modified epoxy resin, another epoxy resin, and a curing agent, and the mass ratio of the solid content of the modified epoxy resin to the other epoxy resin can be 99 / 1 to 1 / 99. This resin composition preferably contains 0.1 to 100 parts by mass of curing agent as solid content, relative to 100 parts by mass of the total solid content of the modified epoxy resin and other epoxy resins.

[0012] The curing agent blended into the above resin composition is at least one selected from the group consisting of acrylic ester resins, melamine resins, urea resins, phenol resins, acid anhydride compounds, amine compounds, imidazole compounds, amide compounds, cationic polymerization initiators, organic phosphines, polyisocyanate compounds, blocked isocyanate compounds, carbodiimide compounds, and active ester-based curing agents.

[0013] The present invention also relates to a cured product obtained by curing the above resin composition. The present invention further relates to a laminate for electric and electronic circuits formed using the above resin composition.

[0014] The present invention also relates to a method for producing the modified epoxy resin described above, which comprises reacting a bifunctional epoxy resin represented by the following general formula (2) with a compound represented by the following general formula (3).

Chemical Formula

[0015] This is a method for producing the modified epoxy resin described above, which comprises reacting 0.3 to 0.8 moles of an acid anhydride represented by the following general formula (8) per 1 mole of alcoholic hydroxyl group equivalent of the epoxy resin represented by the following general formula (7).

Chemical Formula

[0016] According to the present invention, a modified epoxy resin with excellent dielectric properties, solubility, and adhesion can be provided. Furthermore, a resin composition using this modified epoxy resin can provide a cured product with excellent dielectric properties and heat resistance. For this reason, the modified epoxy resin and resin composition of the present invention are applicable to various fields such as adhesives, paints, civil engineering and construction materials, and insulating materials for electrical and electronic components, and are particularly useful as insulating casting materials, laminating materials, and encapsulating materials in the electrical and electronic field. The modified epoxy resin and resin composition containing the same of the present invention can be suitably used in multilayer printed circuit boards, laminates for electrical and electronic circuits such as capacitors, adhesives such as film adhesives and liquid adhesives, semiconductor encapsulating materials, underfill materials, interchip fill materials for 3D-LSIs, insulating sheets, prepregs, heat dissipation substrates, and the like. [Brief explanation of the drawing]

[0017] [Figure 1] This is the GPC chart for the modified epoxy resin of Example 1. [Figure 2] This is the IR chart for the modified epoxy resin of Example 1. [Modes for carrying out the invention]

[0018] The modified epoxy resin of the present invention is represented by general formula (1), has an epoxy equivalent weight (g / eq.) of 250 to 50,000, and has a structure in which 20 to 70 mol% of the hydrogen atoms in the hydroxyl group are substituted (modified) with acyl groups (Z). [ka] If the epoxy equivalent is within the above range, the modified epoxy resin can participate in the curing reaction and be incorporated into the cross-linked structure. The epoxy equivalent is preferably 300 to 40,000, more preferably 400 to 30,000, and even more preferably 500 to 20,000. For film applications, where film-forming properties are required, a higher epoxy equivalent is desirable, preferably 5,000 to 50,000, more preferably 10,000 to 50,000, and even more preferably 20,000 to 50,000. On the other hand, for substrate applications where the epoxy is impregnated into a substrate, good impregnation properties are required, so a lower epoxy equivalent is preferable, typically 300 to 10,000, more preferably 300 to 5,000, and even more preferably 300 to 3,000.

[0019] The weight-average molecular weight (Mw) of the modified epoxy resin of the present invention is preferably 1,000 or more and 200,000 or less. Here, if Mw is less than 1,000, there is a risk that the introduction of structures that improve the heat resistance of the cured product will be reduced, which is undesirable. If Mw is greater than 200,000, there is a risk of reduced compatibility and difficulty in handling the resin, which is undesirable. Furthermore, from the viewpoint of improving the film-forming properties of the modified epoxy resin, Mw is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more. From the viewpoint of improving compatibility and handling, Mw is more preferably 160,000 or less, even more preferably 120,000 or less, and particularly preferably 80,000 or less. For substrate applications where the resin is impregnated into a substrate, Mw may be 10,000 or less, more preferably 5,000 or less. The Mw of the modified epoxy resin can be measured by the gel permeation chromatography (GPC) method described in the examples.

[0020] The modified epoxy resin of the present invention has a structure in which some hydrogen atoms in the hydroxyl groups are replaced (modified) with acyl groups, resulting in low polarity, excellent dielectric properties, low hygroscopicity, good solvent solubility, and good resin compatibility.

[0021] In general formula (1), X is preferably a divalent group containing a monocyclic or condensed polycyclic aromatic hydrocarbon structure (Xa group) having 6 to 20 carbon atoms. X is independently either an Xa group or another divalent group (Xb group), but contains 40 mol% or more of the Xa group. These groups are derived from the residual skeleton obtained by removing two glycidyloxy groups from a bifunctional epoxy resin (diglycidyl ether compound), the residual skeleton obtained by removing two ester structures (acyloxy groups) from a diester compound, and the residual skeleton obtained by removing two hydroxyl groups from a bifunctional phenol compound.

[0022] The above Xa group is a monocyclic or condensed polycyclic aromatic hydrocarbon group having 6 to 20 carbon atoms, selected from the group consisting of a benzene ring group, a naphthalene ring group, anthracene ring group, or a phenanthrene ring group. Preferably, it is a benzene ring group or a naphthalene ring group.

[0023] These Xa groups may be unsubstituted, or they may have substituents such as a C1-C12 alkyl group, a C1-C12 alkoxy group, a C6-C12 aryl group, a C7-C13 aralkyl group, a C6-C12 aryloxy group, a C7-C13 aralkyloxy group, a C2-C12 alkenyl group, or a C2-C12 alkynyl group.

[0024] The alkyl group having 1 to 12 carbon atoms may be linear, branched, or cyclic. Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, methylcyclohexyl group, n-octyl group, cyclooctyl group, n-nonyl group, 3,3,5-trimethylcyclohexyl group, n-decyl group, cyclodecyl group, n-undecyl group, n-dodecyl group, cyclododecyl group, benzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, naphthylmethyl group, phenethyl group, and 2-phenylisopropyl group.

[0025] The alkoxy group having 1 to 12 carbon atoms can be linear, branched, or cyclic. Examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy, n-pentoxy, isopentoxy, neopentoxy, t-pentoxy, cyclopentoxy, n-hexyloxy, isohexyloxy, cyclohexyloxy, n-heptoxy, cycloheptoxy, and methyl hydroxy Examples include chlorohexyloxy group, n-octyloxy group, cyclooctyloxy group, n-nonyloxy group, 3,3,5-trimethylcyclohexyloxy group, n-decyloxy group, cyclodecyloxy group, n-undecyloxy group, n-dodecyloxy group, cyclododecyloxy group, benzyloxy group, methylbenzyloxy group, dimethylbenzyloxy group, trimethylbenzyloxy group, naphthylmethoxy group, phenethyloxy group, and 2-phenylisopropoxy group.

[0026] Examples of aryl groups having 6 to 12 carbon atoms include phenyl, o-tolyl, m-tolyl, p-tolyl, ethylphenyl, styryl, xylyl, n-propylphenyl, isopropylphenyl, mesityl, ethinylphenyl, naphthyl, and vinylnaphthyl groups.

[0027] Examples of aralkyl groups having 7 to 13 carbon atoms include benzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, phenethyl group, 1-phenylethyl group, 2-phenylisopropyl group, and naphthylmethyl group.

[0028] Examples of aryloxy groups having 6 to 12 carbon atoms include phenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, ethylphenoxy group, styryloxy group, xylyloxy group, n-propylphenoxy group, isopropylphenoxy group, mesityloxy group, ethinylphenoxy group, naphthyloxy group, vinylnaphthyloxy group, and the like.

[0029] Examples of aralkyloxy groups having 7 to 13 carbon atoms include benzyloxy group, methylbenzyloxy group, dimethylbenzyloxy group, trimethylbenzyloxy group, phenethyloxy group, 1-phenylethyloxy group, 2-phenylisopropyloxy group, and naphthylmethyloxy group.

[0030] Examples of alkenyl groups having 2 to 12 carbon atoms include vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, cyclohexenyl group, cyclohexadienyl group, cinnamyl group, naphthylvinyl group, and the like.

[0031] Examples of alkynyl groups having 2 to 12 carbon atoms include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1,3-butanedienyl group, phenylethynyl group, naphthylethynyl group, and others.

[0032] In the modified epoxy resin of the present invention, X in general formula (1) may be a divalent group other than an Xa group (Xb group). The content of Xb groups in X is less than 60 mol%, preferably 55 mol% or less, and more preferably 50 mol% or less. Examples of Xb groups include divalent hydrocarbon groups or hydrocarbon groups that may have groups such as -O-, -CO-, -S-, -COO-, -SO-, and -SO2- in their hydrocarbon chains. Examples of divalent groups include: an aromatic skeleton (Xb1) representing the remaining skeleton after removing two hydroxyl groups from an aromatic diol compound; an aliphatic skeleton (Xb2) representing the remaining skeleton after removing two hydroxyl groups from an aliphatic diol compound; an alicyclic skeleton (Xb3) representing the remaining skeleton after removing two hydroxyl groups from an alicyclic diol compound; an aromatic skeleton (Xb1) representing the remaining skeleton after removing two acyloxy groups from an aromatic diester compound; an aliphatic skeleton (Xb2) representing the remaining skeleton after removing two acyloxy groups from an aliphatic diester compound; and the remaining skeleton after removing two acyloxy groups from an alicyclic diester compound. Examples include an alicyclic skeleton (Xb3) representing the basic structure, an aromatic skeleton (Xb1) representing the remaining skeleton after removing two glycidyloxy groups from a diepoxy compound derived from an aromatic diol compound, an aliphatic skeleton (Xb2) representing the remaining skeleton after removing two glycidyloxy groups from a diepoxy compound derived from an aliphatic diol compound, an alicyclic skeleton (Xb3) representing the remaining skeleton after removing two glycidyloxy groups from a diepoxy compound derived from an alicyclic diol compound, and an alicyclic skeleton (Xb4) representing the remaining skeleton after removing two oxygen atoms from a cycloalkane diepoxy compound.

[0033] Examples of aromatic diol compounds, aromatic diester compounds, or aromatic diepoxy compounds that form the above aromatic skeleton (Xb1) include bisphenol types such as bisphenol A, bisphenolacetophenone, bisphenol AF, bisphenol AD, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenoltrimethylcyclohexane, bisphenolcyclohexane, dihydroxybenzophenone, dihydroxydiphenyl ether, phenolphthalein, phenolphthaleinanilide, and fluorescein, which are unsubstituted or may have alkyl groups having 1 to 10 carbon atoms as substituents; biphenyl types such as dihydroxybiphenyls, which are unsubstituted or may have alkyl groups having 1 to 10 carbon atoms as substituents; and bisphenol fluorene, which is unsubstituted or may have alkyl groups having 1 to 10 carbon atoms as substituents. Fluorene types such as fluorenes and bisnaphthol fluorenes, as well as 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-phosphaphenanthrene-10-oxide, diphenylphosph Examples include phosphorus-containing phenolic compounds such as phenylhydroquinone, diphenylphosphinyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol, and 1,5-cyclooctylenephosphinyl-1,4-phenyldiol, which may be unsubstituted or have alkyl, aryl, or aralkyl groups with 1 to 10 carbon atoms as substituents; diester compounds obtained by acyling these aromatic diol compounds; and diexo compounds derived from these aromatic diol compounds. Preferably, the compounds are unsubstituted or alkyl-substituted compounds having 1 to 10 carbon atoms of bisphenolacetophenone, bisphenol AF, bisphenoltrimethylcyclohexane, bisphenolcyclohexane, dihydroxybenzophenone, dihydroxydiphenyl ether, phenolphthalein, phenolphthalein anilide, and fluorescein; unsubstituted or alkyl-substituted compounds having 1 to 10 carbon atoms of dihydroxybiphenyl; unsubstituted or alkyl-substituted compounds having 1 to 10 carbon atoms of bisphenolfluorene; unsubstituted or alkyl-substituted compounds having 1 to 10 carbon atoms of bisnaphtholfluorene; unsubstituted or alkyl-substituted compounds having 1 to 10 carbon atoms of DOPO-HQ and DOPO-NQ; diester compounds obtained by acyling of preferred aromatic diol compounds; and diexo compounds derived from preferred aromatic diol compounds. Particularly preferred are bisphenolacetophenone, bisphenol AF, bisphenoltrimethylcyclohexane, bisphenolcyclohexane, dihydroxybenzophenone, dihydroxydiphenyl ether, phenolphthalein, dihydroxybiphenyl, bisphenol fluorene, biscresofluorene, bisnaphtholfluorene, DOPO-HQ, DOPO-NQ, diester compounds obtained by acyling of particularly preferred aromatic diol compounds, and diepoxy compounds derived from particularly preferred aromatic diol compounds.

[0034] Examples of aliphatic diol compounds, aliphatic diester compounds, or aliphatic diexo compounds that form the above-mentioned aliphatic skeleton (Xb2) include alkylene glycol skeletons such as ethylene glycol, propylene glycol, and butylene glycol, as well as diester compounds obtained by acyling these aliphatic diol compounds, and diexo compounds that use these aliphatic diol compounds as raw materials.

[0035] Examples of alicyclic diol compounds, alicyclic diester compounds, or alicyclic diexo compounds that form the above-mentioned alicyclic skeleton (Xb3) include hydrogenated bisphenol skeletons such as hydrogenated bisphenol A, hydrogenated bisphenol F, and hydrogenated bisphenolacetophenone, as well as diester compounds obtained by acyling these alicyclic diol compounds, and diexo compounds derived from these alicyclic diol compounds.

[0036] Examples of cycloalkane diepoxy compounds forming the alicyclic skeleton (Xb4) include diepoxy compounds of cyclohexylmethylcyclohexanecarboxylate, tetrahydroindene, and hydrogenated tricyclopentadiene. Preferably, the diepoxy compound of cyclohexylmethylcyclohexanecarboxylate is used.

[0037] In general formula (1), Y is independently a hydrogen atom, an acyl group having 2 to 20 carbon atoms, or a glycidyl group. When Y is a hydrogen atom, a hydroxyl group is given at the end; when it is an acyl group, an ester group is given at the end; and when it is a glycidyl group, an epoxy group is given at the end. The acyl group is represented as R-CO-, where R is a hydrocarbon group having 1 to 19 carbon atoms. The proportion of these end groups should be controlled according to the application. In the acyl group (R-CO-), the hydrocarbon group having 1 to 19 carbon atoms represented by R is preferably an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. The alkyl group having 1 to 12 carbon atoms may be linear, branched, or cyclic. Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, methylcyclohexyl group, n-octyl group, cyclooctyl group, n-nonyl group, 3,3,5-trimethylcyclohexyl group, n-decyl group, cyclodecyl group, n-undecyl group, n-dodecyl group, and cyclododecyl group. Examples of aryl groups having 6 to 12 carbon atoms include phenyl, tolyl, ethylphenyl, xylyl, n-propylphenyl, isopropylphenyl, mesityl, naphthyl, and methylnaphthyl groups. Examples of aralkyl groups having 7 to 13 carbon atoms include benzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, phenethyl group, 2-phenylisopropyl group, and naphthylmethyl group. Among these, acyl groups having a hydrocarbon group with 1 to 7 carbon atoms are more preferred, acetyl groups, propanoyl groups, butanoyl groups, benzoyl groups, and methylbenzoyl groups are even more preferred, and acetyl groups and benzoyl groups are particularly preferred.

[0038] In general formula (1), Z is an acyl group having 2 to 20 carbon atoms or a hydrogen atom. 20 to 70 mol% of Z is an acyl group, and the remainder is a hydrogen atom. 25 to 70 mol%, preferably 25 to 65 mol%, more preferably 25 to 60 mol%, and even more preferably 30 to 60 mol%, of Z is an acyl group. The above acyl group is the same as that exemplified by Y above, and the preferred acyl group is also the same.

[0039] In general formula (1), n ​​is the number of repetitions and is the average value. Its range is 1 to 500. From the viewpoint of fluidity and handling, it is preferably 1 to 400, more preferably 1 to 300. Preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more. The number of n can be calculated from the number-average molecular weight (Mn) obtained by the GPC method.

[0040] The modified epoxy resin of the present invention has some or all of its secondary hydroxyl groups acylated, and can be obtained by various methods. A preferred manufacturing method is, for example, the following method. (A); A method for producing a difunctional epoxy resin represented by general formula (2) and a diester compound and / or a difunctional phenol compound represented by general formula (3). Hereinafter, this may be referred to as production method (A). (B); A method of production in which an epoxy resin represented by general formula (7) (sometimes referred to as epoxy resin (a) to distinguish it from the modified epoxy resin of the present invention) is reacted with an acid component (acylating agent) such as an acid anhydride of an organic acid, a halogen of an organic acid, or an ester of an organic acid. Hereinafter, this may be referred to as production method (B). The modified epoxy resins obtained by manufacturing methods (A) and (B) are the modified epoxy resins of the present invention and are represented by the same general formula (1).

[0041] The above manufacturing method (A) is a method of reacting a bifunctional epoxy resin represented by general formula (2) with a compound represented by general formula (3). [ka] In the above general formula (2), G is a glycidyl group, m is the number of repetitions, and its average value is between 0 and 6, preferably between 0 and 3. In general formula (3), Q is an acyl group having 2 to 20 carbon atoms. In general formula (3), 5 mol% or more of Q, preferably 20 to 70 mol%, are acyl groups having 2 to 20 carbon atoms, and the remainder are hydrogen atoms. Here, the compound represented by general formula (3) may be a mixture of two or more compounds selected from diester compounds in which both Q are acyl groups, monoester compounds in which one is an acyl group and the other is a hydrogen atom, and diphenol compounds in which both are hydrogen atoms. Compounds represented by general formula (3) are called diester compounds.

[0042] X in general formulas (2) and (3) 1 , X 2 These are independently divalent groups, and X 1 and X 2 Preferably, 40 mol% or more of the total are monocyclic or condensed polycyclic aromatic hydrocarbon groups (Xa groups) having 6 to 20 carbon atoms, selected from the group consisting of benzene ring groups, naphthalene ring groups, anthracene ring groups, or phenanthrene ring groups, and these monocyclic or condensed polycyclic aromatic hydrocarbon groups may have substituents. X in general formula (2) 1 and X in general formula (3) 2is selected to provide X in general formula (1). Accordingly, X in general formula (2) 1 and X in general formula (3) 2 necessarily contains an Xa group in either of them. For example, X in general formula (2) 1 and X in general formula (3) 2 : when one of them contains an Xa group, the other may or may not contain an Xa group, and any moiety that is not the Xa group is another divalent group (Xb group) other than the Xa group.

[0043] The bifunctional epoxy resin used in production method (A) of the present invention is an epoxy resin represented by the above general formula (2), and examples thereof include epoxy resins obtained by reacting a bifunctional phenol compound represented by HO-X 1 -OH with epihalohydrin in the presence of an alkali metal compound. Here, X 1 is the same as X in the above general formula (2) 1 described above.

[0044] The epoxy equivalent (g / eq.) of the raw material epoxy resin represented by general formula (2) is preferably 100 to 400, more preferably 300 or less. The m value of general formula (2) is preferably 0 to 1, more preferably 0.3 or less.

[0045] Examples of epihalohydrin include epichlorohydrin, epibromohydrin, and the like. 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; and alkali metal phenoxide, sodium hydride, lithium hydride, and the like.

[0046] For the reaction between a difunctional phenol compound and epihalohydrin to obtain the raw epoxy resin, an alkali metal compound is used in an amount of 0.80 to 1.20 moles, preferably 0.85 to 1.05 moles, relative to the functional groups in the difunctional phenol compound. Using less than this amount is undesirable because it results in a large amount of residual hydrolyzable chlorine. The alkali metal compound can be used in aqueous solution, alcohol solution, or solid form.

[0047] In the epoxidation reaction, an excess amount of epihalohydrin is used relative to the difunctional phenol compound. Typically, 1.5 to 15 moles of epihalohydrin are used per mole of functional groups in the difunctional phenol compound, but preferably 2 to 10 moles, and more preferably 5 to 8 moles. Using more than this reduces production efficiency, while using less increases the amount of high molecular weight epoxy resin produced, making it unsuitable as a raw material.

[0048] The epoxidation reaction is usually carried out at a temperature of 120°C or lower. If the reaction temperature is too high, the amount of so-called poorly hydrolyzable chlorine increases, making it difficult to achieve high purity. Preferably, the temperature is 100°C or lower, and more preferably 85°C or lower.

[0049] When the above-mentioned bifunctional phenol compound reacts with an epihalohydrin, m is usually greater than 0. To make m 0, one can either highly purify the epoxy resin produced by known methods using techniques such as distillation and crystallization, or epoxidize the above-mentioned bifunctional phenol compound by allylation followed by oxidation of the olefin portion.

[0050] Furthermore, the diester compounds used in the production method (A) of the present invention are, for example, obtained by acyling a difunctional phenol compound in a condensation reaction with an acid anhydride of an organic acid, a halogenated organic acid, or an organic acid. Preferably, they are diester compounds obtained by acyling unsubstituted or alkyl-substituted versions of bisphenolacetophenone, bisphenol AF, bisphenoltrimethylcyclohexane, bisphenolcyclohexane, dihydroxybenzophenone, dihydroxydiphenyl ether, phenolphthalein, phenolphthalein anilide, and fluorescein, or unsubstituted or alkyl-substituted versions having 1 to 10 carbon atoms of dihydroxybiphenyl, or unsubstituted or alkyl-substituted versions having 1 to 10 carbon atoms of bisphenolfluorene, or alkyl-substituted versions having 1 to 10 carbon atoms of bisnaphtholfluorene, or unsubstituted or alkyl-substituted versions having 1 to 10 carbon atoms of DOPO-HQ, DOPO-NQ. Particularly preferred are diester compounds obtained by acyling bisphenolacetophenone, bisphenol AF, bisphenoltrimethylcyclohexane, bisphenolcyclohexane, dihydroxybenzophenone, dihydroxydiphenyl ether, phenolphthalein, dihydroxybiphenyl, bisphenol fluorene, biscresofluorene, bisnaphtholfluorene, DOPO-HQ, and DOPO-NQ.

[0051] The amounts of the above-mentioned bifunctional epoxy resin and diester compound used should be appropriately adjusted depending on the epoxy equivalent of the target modified epoxy resin, but a ratio of 0.3 to 1.0 equivalents of ester groups per equivalent of epoxy groups is preferred. This equivalent ratio facilitates the development of high molecular weight while maintaining epoxy groups at the molecular ends. It is also possible to replace some of the diester compound with the above-mentioned bifunctional phenol compound. In manufacturing method (A), polymerization and esterification reactions of secondary hydroxyl groups occur, increasing Mw and producing a modified epoxy resin.

[0052] In manufacturing method (A), a catalyst may be used, and any compound that has catalytic activity to promote the reaction between epoxy groups and ester groups may be used as the catalyst. Examples include tertiary amines, cyclic amines, imidazoles, organophosphorus compounds, and quaternary ammonium salts. These catalysts may be used individually or in combination of two or more.

[0053] Examples of tertiary amines include, but are not limited to, triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine, and 2,4,6-tris(dimethylaminomethyl)phenol.

[0054] 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 N,N-dimethylaminopyridine (DMAP).

[0055] 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.

[0056] Examples of organophosphorus compounds 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, as well as tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, tetrabutylphosphonium hydroxide, and Examples of phosphonium salts include, but are not limited to, methylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, and triphenylbenzylphosphonium bromide.

[0057] 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.

[0058] Among the catalysts listed above, 4-(dimethylamino)pyridine, 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 in particular, 4-(dimethylamino)pyridine, 1,8-diazabicyclo[5,4,0]undecene-7, 1,5-diazabicyclo[4,3,0]nonene-5, and 2-ethyl-4-methylimidazole are preferred.

[0059] The amount of catalyst used is usually 0.001 to 1% by mass of the reaction solids. However, when these compounds are used as catalysts, they may remain as residues in the resulting modified epoxy resin, potentially degrading the insulation properties of the printed circuit board or shortening the pot life of the composition. Therefore, the nitrogen content derived from the catalyst in the modified epoxy resin is preferably 0.5% by mass or less, and more preferably 0.3% by mass or less. Similarly, the phosphorus content derived from the catalyst in the modified epoxy resin is preferably 0.5% by mass or less, and more preferably 0.3% by mass or less.

[0060] In manufacturing method (A), a reaction solvent may be used, and any solvent that dissolves the modified epoxy resin may be used. Examples include aromatic solvents, ketone solvents, amide solvents, glycol ether solvents, ester solvents, etc. These solvents may be used individually or in combination of two or more.

[0061] Examples of aromatic solvents include benzene, toluene, and xylene.

[0062] Examples of ketone solvents include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, acetylacetone, diisobutyl ketone, isophorone, methylcyclohexanone, and acetophenone.

[0063] Examples of amide solvents include formamide, N-methylformamide, N,N-dimethylformamide (DMF), acetamide, N-methylacetamide, N,N-dimethylacetamide, 2-pyrrolidone, and N-methylpyrrolidone.

[0064] Examples of glycol ether 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 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. Diethylene glycol dialkyl ethers, propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, etc., 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, tripropylene glycol dibutyl ether, etc., ethylene glycol monoalkyl ether acetates such as ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, etc., diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate,Examples include polyethylene glycol monoalkyl ether acetates such as triethylene glycol monobutyl ether acetate, and propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate.

[0065] Examples of ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, benzyl acetate, ethyl propionate, ethyl butyrate, butyl butyrate, valerolactone, and butyrolactone.

[0066] Other solvents include, for example, dioxane, dimethyl sulfoxide, sulfolane, and γ-butyrolactone.

[0067] In manufacturing method (A), the solid content concentration during the reaction is preferably 35 to 95% by mass. More preferably 50 to 90% by mass, and even more preferably 70 to 90% by mass. If a highly viscous product is formed during the reaction, additional solvent can be added to continue the reaction. After the reaction is complete, the solvent can be removed or added as needed.

[0068] The reaction temperature should be within a range that does not decompose the catalyst used. If the reaction temperature is too high, the catalyst may decompose, stopping the reaction or degrading the resulting modified epoxy resin. If the reaction temperature is too low, the reaction may not proceed sufficiently, and the desired molecular weight may not be achieved. 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 using low-boiling point solvents such as acetone or methyl ethyl ketone, the reaction temperature can be ensured by carrying out the reaction under high pressure using an autoclave. If it is necessary to remove the heat of reaction, this is usually done by evaporation, condensation, reflux of the solvent using the heat of reaction, indirect cooling, or a combination of these methods.

[0069] Next, the manufacturing method (B) of the present invention will be described. Method (B) of production is a method for obtaining the modified epoxy resin of the present invention by reacting an epoxy resin (a) represented by general formula (7) with an acid anhydride represented by general formula (8) at a rate of 0.3 to 0.8 moles per mole of alcoholic hydroxyl group equivalent of the epoxy resin. [ka]

[0070] Here, X and n are equivalent to those in general formula (1). L is independently a hydrogen atom or a glycidyl group. T is an acyl group having 2 to 20 carbon atoms.

[0071] This epoxy resin (a) can be obtained by conventionally known methods. For example, there is a method of producing it by reacting a difunctional phenol compound (sometimes referred to as "difunctional phenol compound (a)") with an epihalohydrin in the presence of an alkali metal compound (hereinafter referred to as the "one-step method"), and a method of producing it by reacting a difunctional epoxy resin with a difunctional phenol compound in the presence of a catalyst (hereinafter referred to as the "two-step method"). Epoxy resin (a) may be obtained by either of these production methods.

[0072] The weight-average molecular weight and epoxy equivalent of epoxy resin (a) can be adjusted to the desired range by appropriately adjusting the molar ratio of epihalohydrin to difunctional phenol compound in the one-stage method, and by adjusting the molar ratio of difunctional epoxy resin to difunctional phenol compound in the two-stage method.

[0073] Examples of difunctional phenol compounds (a) used in one-stage and two-stage manufacturing include bisphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, bisphenol C, bisphenol AF, bisphenol acetophenone, bisphenol fluorene, dihydroxybiphenyl ether, dihydroxybiphenyl thioether, dihydroxybenzophenone, phenolphthalein, and phenolphthalein anilide; biphenols such as 4,4'-biphenol and 2,4'-biphenol; dihydroxynaphthalene, hydroquinone, catechol, resorcinol, 1,1-bi-2-naphthol, 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). Furthermore, multiple types of these difunctional phenol compounds may be used in combination.

[0074] First, let me explain the one-step method. In the one-step method, a bifunctional phenol compound and an epihalohydrin are reacted in a non-reactive solvent in the presence of an alkali metal compound. The epihalohydrin is consumed, and a condensation reaction occurs to obtain epoxy resin (a). After the reaction is complete, the by-product salt must be removed by filtration or washing with water. Examples of alkali metal compounds include those used in the production of the bifunctional epoxy resin represented by the general formula (2) above, which is used in the production method (A) of the present invention. The weight-average molecular weight and epoxy equivalent of epoxy resin (a) can be adjusted to the desired range by appropriately adjusting the molar ratio of the difunctional phenol compound to the epihalohydrin. For example, if the weight-average molecular weight of epoxy resin (a) is to be 10,000 or more, the amount of epihalohydrin should be adjusted to 0.985 to 1.015 moles, preferably 0.99 to 1.012 moles, and more preferably 0.995 to 1.01 moles, per mole of difunctional phenol compound. Also, if the epoxy equivalent of epoxy resin (a) is to be 5,000 g / eq. or less, the amount of epihalohydrin should be adjusted to 1.015 to 8 moles, preferably 1.05 to 6 moles, and more preferably 1.1 to 5 moles, per mole of difunctional phenol compound.

[0075] This reaction can be carried out under atmospheric pressure or reduced pressure. The reaction temperature is usually preferably 20-200°C, more preferably 30-170°C, even more preferably 40-150°C, and particularly preferably 50-100°C under atmospheric pressure. Under reduced pressure, the temperature is preferably 20-100°C, more preferably 30-90°C, and even more preferably 35-80°C. Within this temperature range, side reactions are less likely to occur, and the reaction proceeds easily. The reaction pressure is usually atmospheric pressure. If reaction heat needs to be removed, it is usually done by evaporation, condensation, reflux of the solvent, indirect cooling, or a combination of these methods.

[0076] As the reactive solvent, in addition to the reaction solvent exemplified in the production method (A) of the present invention, alcohols such as ethanol, isopropyl alcohol, and butyl alcohol can also be used. One type may be used alone, or two or more types may be used in combination.

[0077] Next, I will explain the two-step method. As the bifunctional epoxy resin used as the raw material epoxy resin for the two-stage method, the same type as the bifunctional epoxy resin represented by the general formula (2) used in the manufacturing method (A) of the present invention is used.

[0078] As the difunctional epoxy resin used as the raw material for the two-stage process, a difunctional epoxy resin represented by the above general formula (2) is preferred, but other difunctional epoxy resins may be used in combination as long as they do not impair the objective of the present invention. Examples of difunctional epoxy resins that can be used in combination include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol acetophenone type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl ether type epoxy resin, and other bisphenol type epoxy resins, biphenol type epoxy resins, diphenyl dicyclopentadiene type epoxy resin, alkylene glycol type epoxy resin, aliphatic cyclic epoxy resin, and the like. These epoxy resins may be substituted with substituents that do not have adverse effects, such as alkyl groups and aryl groups. Multiple types of these epoxy resins may be used in combination.

[0079] In the two-step method, a catalyst can be used, and any compound that has catalytic activity to promote the reaction between epoxy groups and phenolic hydroxyl groups is acceptable. For example, a catalyst similar to the one exemplified in the production method (A) of the present invention can be used. In addition, alkali metal compounds used in the production of the bifunctional epoxy resin represented by the general formula (2) above can also be used. These catalysts may be used individually or in combination of two or more types. The amount used is also the same as the amount exemplified in the production method (A) of the present invention.

[0080] In the two-step method, a solvent may be used, and any solvent that dissolves the epoxy resin and does not adversely affect the reaction is acceptable. For example, a solvent similar to the one exemplified in the manufacturing method (A) of the present invention is an example. These solvents may be used individually or in combination of two or more.

[0081] The amount of solvent used can be appropriately selected depending on the reaction conditions, but for example, in the case of a two-stage process, a solid content concentration of 35 to 95% by mass is preferred. Also, if a highly viscous product is formed during the reaction, the solvent can be added during the reaction to continue the reaction. After the reaction is complete, the solvent can be removed by distillation or other means as needed, or additional solvent can be added.

[0082] The reaction temperature should be within a range that does not decompose the catalyst used. If the reaction temperature is too high, the catalyst may decompose, stopping the reaction or degrading the resulting epoxy resin. If the reaction temperature is too low, the reaction may not proceed sufficiently, and the desired molecular weight may not be achieved. Therefore, the reaction temperature is preferably 50 to 230°C, more preferably 100 to 210°C, and even more preferably 120 to 200°C. The reaction time is usually 1 to 12 hours, and preferably 3 to 10 hours. When using low-boiling point solvents such as acetone or methyl ethyl ketone, the reaction temperature can be ensured by carrying out the reaction under high pressure using an autoclave. If it is necessary to remove the heat of reaction, this is usually done by evaporation, condensation, reflux of the solvent using the heat of reaction, indirect cooling, or a combination of these methods.

[0083] The modified epoxy resin of the present invention can be obtained by acyling the hydroxyl groups in the epoxy resin (a) represented by the general formula (7) obtained in this manner. Acylation may be carried out not only by direct esterification but also by methods such as transesterification.

[0084] Examples of acid components used in the above acylation include organic acids such as acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid, octanoic acid, caprylic acid, lauric acid, stearic acid, oleic acid, benzoic acid, t-butylbenzoic acid, hexahydrobenzoic acid, phenoxyacetic acid, acrylic acid, and methacrylic acid, as well as acid anhydrides of organic acids, halides of organic acids, and esters of organic acids.

[0085] Examples of acid anhydrides of organic acids include acetic anhydride, benzoic acid anhydride, and phenoxyacetic acid anhydride. Examples of esterified organic acids include methyl acetate, ethyl acetate, butyl acetate, methyl benzoate, and ethyl benzoate. Examples of halogenated organic acids include chloride acetate, chloride benzoate, and chloride phenoxyacetate.

[0086] Preferred compounds for esterification include halides of organic acids such as acetate chloride, benzoic acid chloride, and phenoxyacetic acid chloride, as well as acid halides and acid anhydrides of organic acids such as acetic anhydride, benzoic acid anhydride, and phenoxyacetic anhydride. Acid anhydrides such as acetic anhydride and benzoic acid anhydride are more preferred because they do not require washing with water after esterification and avoid the contamination of halogens, which are undesirable in electrical materials applications.

[0087] When reacting the epoxy resin (a) with the above-mentioned acid components such as organic acids, acid anhydrides of organic acids, halides of organic acids, and esterified organic acids used for esterifying the hydroxyl groups of epoxy resin (a), the charging ratio may be the same as the charging ratio for the desired esterification ratio. Alternatively, if the reactivity is low, an excess of the above-mentioned acid components may be charged relative to the hydroxyl groups, and after the reaction reaches the desired esterification ratio, the unreacted acid components may be removed.

[0088] When esterification is performed directly with an acid component, it can be carried out while dehydrating using various esterification catalysts, such as acid catalysts like p-toluenesulfonic acid and phosphoric acid, or metal catalysts like tetraisopropyl titanate, tetrabutyl titanate, dibutyltin oxide, dioctyltin oxide, and zinc chloride. Typically, this is carried out under a nitrogen atmosphere at 100 to 250°C, and more preferably at 130 to 230°C.

[0089] When using acid halides or acid anhydrides for esterification, the resulting acid can be removed by any of the following methods, or by combination of methods: neutralization with a basic compound followed by filtration of the salt; neutralization with a basic compound followed by washing with water; washing with water without neutralization; or removal by distillation or adsorption. When removing acids with a lower boiling point than the reaction solvent, distillation is preferable.

[0090] When esterifying epoxy resin (a) by transesterification, it is generally desirable to carry out the process under a nitrogen atmosphere while de-alcoholizing using known esterification catalysts such as organometallic catalysts like dibutyltin oxide, dioctyltin oxide, stanoxane catalysts, tetraisopropyl titanate, tetrabutyl titanate, lead acetate, zinc acetate, and antimony trioxide, or acid catalysts like hydrochloric acid, sulfuric acid, phosphoric acid, and sulfonic acid, or basic catalysts like lithium hydroxide and sodium hydroxide.

[0091] In the manufacturing method (B) of the present invention, a reaction solvent may be used, and any solvent that dissolves epoxy resin may be used. For example, the solvents exemplified in the manufacturing method (A) of the present invention can be used. These solvents may be the same as those used in the preparation of epoxy resin (a), or they may be different. Furthermore, only one type may be used, or two or more types may be used in combination. The solid content concentration during the reaction is the same as in manufacturing method (A), preferably 35 to 95% by mass, more preferably 50 to 90% by mass, and even more preferably 70 to 90% by mass.

[0092] The resin composition of the present invention is a resin composition comprising at least the modified epoxy resin of the present invention and a curing agent. Furthermore, the resin composition of the present invention may optionally contain various additives such as epoxy resin, inorganic fillers, coupling agents, and antioxidants. The resin composition of the present invention provides a cured product that fully satisfies the various physical properties required for various applications.

[0093] A resin composition can be obtained by blending a curing agent with the modified epoxy resin of the present invention. In the present invention, a curing agent refers to a substance that contributes to the crosslinking reaction and / or chain length extension reaction with the modified epoxy resin. In the present invention, even substances commonly called "curing accelerators" are considered curing agents if they contribute to the crosslinking reaction and / or chain length extension reaction of the modified epoxy resin.

[0094] The curing agent content in the resin composition of the present invention is preferably 0.1 to 100 parts by mass, based on 100 parts by mass of solid content of the modified epoxy resin of the present invention. More preferably, it is 80 parts by mass or less, and even more preferably 60 parts by mass or less.

[0095] In the resin composition of the present invention, if other epoxy resins described later are included, the weight ratio of the solid content of the modified epoxy resin of the present invention to the other epoxy resins is 99 / 1 to 1 / 99. In the present invention, "solid content" means the components excluding the solvent, and includes not only solid modified epoxy resins and other epoxy resins, but also semi-solid and viscous liquid substances. Furthermore, "resin components" means the sum of the modified epoxy resin of the present invention and the other epoxy resins described later.

[0096] There are no particular restrictions on the curing agent used in the resin composition of the present invention; all commonly known epoxy resin curing agents can be used. From the viewpoint of improving heat resistance, preferred curing agents include phenolic curing agents, amide curing agents, imidazoles, and active ester curing agents. These curing agents may be used individually or in combination of two or more types.

[0097] Examples of phenolic curing agents include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 1,4-bis(4-hydroxyphenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)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, Examples include 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allyl or polyallylized dihydroxynaphthalenes, allylated bisphenol A, allylated bisphenol F, allylated phenol novolac, allylated pyrogallol, and the like.

[0098] Examples of amide-based curing agents include dicyandiamide and its derivatives, and polyamide resins.

[0099] Examples of imidazoles 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, and 2,4-diamino-6-[2'-methylimidazole Examples include ru-(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 isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins with the above imidazoles. Although imidazoles have catalytic activity and can generally be classified as curing accelerators as described later, in this invention they are classified as curing agents.

[0100] As active ester-based curing agents, compounds having two or more highly reactive ester groups in one molecule are preferred, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Among these, phenol esters obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group are more preferred. Specific examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of aromatic compounds having a phenolic hydroxyl group include catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyldiphenol, and phenol novolac.

[0101] Other curing agents that can be used in the resin composition of the present invention include, for example, amine-based curing agents, acid anhydride-based curing agents, tertiary amines, organophosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron-halogenated amine complexes, polymercaptan-based curing agents, isocyanate-based curing agents, blocked isocyanate-based curing agents, carbodiimide compounds, and the like. These other curing agents may be used individually or mixed in any combination and ratio of two or more types.

[0102] The resin composition of the present invention may contain epoxy resins other than the modified epoxy resin of the present invention. By using other epoxy resins, it is possible to compensate for deficient physical properties or improve various physical properties. Preferably, the epoxy resin has two or more epoxy groups in its molecule, and more preferably an epoxy resin has three or more epoxy groups. Examples include polyglycidyl ether compounds, polyglycidylamine compounds, polyglycidyl ester compounds, alicyclic general formula epoxy compounds, and other modified epoxy resins. These epoxy resins may be used alone, two or more epoxy resins of the same system may be used in combination, or epoxy resins of different systems may be used in combination.

[0103] As polyglycidyl ether compounds, various epoxy resins can be used, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bisphenol Z type epoxy resin, bisphenol fluorene type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl ether type epoxy resin, naphthalene type epoxy resin, hydroquinone type epoxy resin, resorcinol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alkyl novolac type epoxy resin, styrene-phenol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, phenol aralkyl type epoxy resin, β-naphthol aralkyl type epoxy resin, naphthalenediol aralkyl type epoxy resin, α-naphthol aralkyl type epoxy resin, biphenyl aralkylphenol type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, alkylene glycol type epoxy resin, and aliphatic cyclic epoxy resin.

[0104] 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.

[0105] Examples of polyglycidyl ester compounds include dimer acid type epoxy resins, hexahydrophthalic acid type epoxy resins, trimellitic acid type epoxy resins, and the like.

[0106] Examples of alicyclic epoxy compounds include aliphatic cyclic epoxy resins such as Celoxide 2021 (manufactured by Daicel Chemical Industries, Ltd.).

[0107] Other modified 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 (e.g., divinylbenzene dioxide, trivinylnaphthalene trioxide, etc.), and phenoxy resins.

[0108] In the resin composition of the present invention, when the modified epoxy resin of the present invention is used with other epoxy resins, the amount of the modified epoxy resin in the total components of the epoxy resin as solids is preferably 1 to 99% by mass, more preferably 50% by mass or more, and even more preferably 80% by mass or more.

[0109] The resin composition of the present invention may contain a solvent or reactive diluent to appropriately adjust the viscosity of the resin composition during handling when forming a coating film. In the resin composition of the present invention, the solvent or reactive diluent is used to ensure the handling and workability of the resin composition during molding, and there are no particular restrictions on the amount used. In the present invention, the terms "solvent" and "solvent" mentioned above are used to distinguish them according to their form of use, but they may be the same or different.

[0110] Examples of solvents that may be included in the resin composition of the present invention include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate; ethers such as ethylene glycol monomethyl ether; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; alcohols such as methanol and ethanol; alkanes such as hexane and cyclohexane; and aromatics such as toluene and xylene. The solvents listed above may be used individually or mixed in any combination and ratio of two or more.

[0111] 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 glycidylamines.

[0112] These solvents or reactive diluents are preferably used in an amount of 90% by mass or less as nonvolatile content, and their appropriate type and amount are selected as appropriate depending on the application. For example, in printed circuit 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 preferred, and their amount is preferably 40 to 80% by mass as nonvolatile content. In adhesive film applications, for example, ketones, acetate esters, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferred, and their amount is preferably 30 to 60% by mass as nonvolatile content.

[0113] The resin composition of the present invention may optionally contain a curing accelerator or a catalyst. Examples of curing accelerators or catalysts include phosphorus compounds such as imidazoles, tertiary amines, and phosphines, metal compounds, Lewis acids, and amine complex salts. These may be used individually or in combination of two or more.

[0114] The amount of curing accelerator or catalyst added can be appropriately selected depending on the intended use, but 0.01 to 15 parts by mass are used as needed per 100 parts by mass of epoxy resin component in the resin composition. 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 part by mass. By using a curing accelerator or catalyst, the curing temperature can be lowered and the curing time can be shortened.

[0115] The resin composition of the present invention may use various known flame retardants to improve the flame retardancy of the resulting cured product, provided that reliability is not compromised. Examples of usable flame retardants include halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organometallic salt-based flame retardants. From an environmental standpoint, halogen-free flame retardants are preferred, and phosphorus-based flame retardants are particularly preferred. These flame retardants may be used individually, in combination of two or more flame retardants of the same system, or in combination of flame retardants of different systems.

[0116] The resin composition of the present invention may contain components other than those listed above (which may be 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, UV inhibitors, antioxidants, coupling agents, plasticizers, fluxes, thixotropy-imparting agents, smoothing agents, colorants, pigments, dispersants, emulsifiers, deelasticizing agents, mold release agents, defoaming agents, ion trapping agents, and the like.

[0117] 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 fibers, glass fibers, alumina fibers, silica-alumina fibers, silicon carbide fibers, polyester fibers, cellulose fibers, aramid fibers, and ceramic fibers; and fine particle rubber.

[0118] The resin composition of the present invention may also contain thermoplastic resins other than the modified epoxy resin of the present invention. Examples of thermoplastic resins include modified epoxy resins other than those of the present invention, phenoxy resins, polyurethane resins, polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, ABS resins, AS resins, vinyl chloride resins, polyvinyl acetate resins, polymethyl methacrylate resins, polycarbonate resins, polyacetal resins, cyclic polyolefin resins, polyamide resins, thermoplastic polyimide resins, polyamideimide resins, polytetrafluoroethylene resins, polyetherimide resins, polyphenylene ether resins, modified polyphenylene ether resins, polyethersulfone resins, polysulfone resins, polyetheretherketone resins, polyphenylene sulfide resins, and polyvinyl formal resins. From the viewpoint of compatibility, modified epoxy resins other than those of the present invention and phenoxy resins are preferred, and from the viewpoint of low dielectric properties, polyphenylene ether resins and modified polyphenylene ether resins are preferred.

[0119] Other components include organic pigments such as quinacridone, azo, and phthalocyanine pigments; inorganic pigments such as titanium dioxide, metallic foil pigments, and rust-preventive pigments; UV absorbers such as hindered amine, benzotriazole, and benzophenone pigments; antioxidants such as hindered phenol, phosphorus, sulfur, and hydrazide pigments; and additives such as mold release agents, leveling agents, rheology control agents, pigment dispersants, anti-repellent agents, and defoaming agents, as well as stearic acid, palmitic acid, zinc stearate, and calcium stearate. The amount of these other components is preferably in the range of 0.01 to 20% by mass relative to the total solid content in the resin composition.

[0120] The resin composition of the present invention is obtained by uniformly mixing the above components. The resin composition, which contains epoxy resin, a curing agent, and optionally various other components, can be easily cured in the same manner as conventionally known methods. This cured product exhibits excellent cured properties, with a good balance of low hygroscopicity, dielectric properties, heat resistance, and adhesion. Here, "curing" means intentionally curing the resin composition with heat and / or light, and the degree of curing can be controlled according to the desired physical properties and application. The degree of curing can be fully cured or partially 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%.

[0121] The resin composition of the present invention can be cured in the same way as known epoxy resin compositions to obtain a cured product. Methods for obtaining a cured product can be the same as those for known epoxy resin compositions, and are preferably performed using methods such as casting, injection, potting, dipping, drip coating, transfer molding, compression molding, or laminating the composition into resin sheets, resin-coated copper foil, prepregs, etc., and then heating and pressurizing to form laminates. The curing temperature is usually in the range of 80 to 300°C, and the curing time is usually about 10 to 360 minutes. This heating is preferably performed in two stages: 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. Furthermore, in formulations where the glass transition temperature (Tg) exceeds the secondary heating temperature, it is preferable to perform a tertiary heating at 150 to 280°C for 60 to 120 minutes. Such secondary and tertiary heating can reduce curing defects. When producing resin semi-cured products such as resin sheets, resin-coated copper foil, and prepregs, the curing reaction of the resin composition is usually advanced by heating or other means to the extent that the shape can be maintained. If the resin composition contains a solvent, most of the solvent is usually removed by methods such as heating, reduced pressure, or air drying, but it is also acceptable to leave a solvent content of 5% by mass or less in the resin semi-cured product.

[0122] The prepreg obtained using the resin composition of the present invention will now be described. As the sheet-like substrate, inorganic fibers such as glass, or woven or nonwoven fabrics of organic fibers such as polyester, polyamine, polyacrylic, polyimide, Kevlar, and cellulose can be used, but are not limited thereto. The method for producing the prepreg from the resin composition and substrate of the present invention is not particularly limited, but for example, the above substrate can be impregnated by immersing it in a resin varnish in which the above resin composition has been viscosity-adjusted with a solvent, and then heated and dried to partially cure (B-stage) the resin component. For example, it can be heated and dried at 100 to 200°C for 1 to 40 minutes. Here, the amount of resin in the prepreg is preferably 30 to 80% by mass.

[0123] This document describes a method for manufacturing laminates using prepregs and insulating adhesive sheets. When forming a laminate using prepregs, one or more prepregs are stacked, and metal foil is placed on one or both sides to form a laminate. This laminate is then heated and pressurized to integrate the layers. As the metal foil, single, alloy, or composite metal foils of copper, aluminum, brass, nickel, etc., can be used. The heating and pressurizing conditions for the laminate should be adjusted appropriately to the conditions necessary for the resin composition to harden. However, if the pressure is too low, air bubbles may remain inside the resulting laminate, potentially reducing its electrical properties. Therefore, it is desirable to pressurize under conditions that satisfy moldability. For example, a temperature of 160-220°C and a pressure of 49-490 N / cm² are used. 2 (5~50kgf / cm 2 The heating time can be set to 40 to 240 minutes.

[0124] Furthermore, a multilayer board can be created using the single-layer laminate obtained in this way as an inner layer material. In this case, first, circuits are formed on the laminate using an additive method or a subtractive method, and the formed circuit surface is treated with an acid solution to blacken it and obtain the inner layer material. An insulating layer is formed on one or both sides of the circuit-formed surface of this inner layer material using a prepreg or insulating adhesive sheet, and a conductive layer is formed on the surface of the insulating layer to form a multilayer board.

[0125] When forming an insulating layer with an insulating adhesive sheet, the insulating adhesive sheet is placed on the circuit-forming surfaces of multiple inner layer materials to form a laminate. Alternatively, the insulating adhesive sheet is placed between the circuit-forming surface of the inner layer material and the metal foil to form a laminate. This laminate is then heated and pressurized to form a single unit, thereby forming a hardened insulating adhesive sheet as the insulating layer and creating a multilayer structure of the inner layer material. Alternatively, the hardened insulating adhesive sheet forms the insulating layer between the inner layer material and the metal foil which is the conductive layer. Here, the metal foil can be the same as the one used for the laminate used as the inner layer material. Furthermore, heat and pressure molding can be carried out under the same conditions as for molding the inner layer material. When forming an insulating layer by applying a resin composition to a laminate, the outermost circuit-forming surface resin of the inner layer material is coated with the above resin composition to a thickness of preferably 5 to 100 μm, and then heated and dried at 100 to 200°C for 1 to 90 minutes to form a sheet. This is generally formed by a method called the casting method. It is desirable to form the thickness after drying to 5 to 80 μm. On the surface of the multilayer laminate formed in this way, via holes and circuits can be formed using the additive method or the subtractive method to form a printed wiring board. Furthermore, by repeating the above process using this printed circuit board as an inner layer material, it is possible to form even more layers of laminated boards.

[0126] Furthermore, when forming an insulating layer with prepreg, one or more layers of prepreg are laminated and placed on the circuit-forming surface of the inner layer material, and metal foil is placed on the outside of that to form a laminate. This laminate is then heated and pressurized to form a single unit, thereby forming the cured prepreg as the insulating layer and the outer metal foil as the conductive layer. Here, the same type of metal foil used for the laminated board used as the inner layer material can be used. Furthermore, the heat and pressure molding can be carried out under the same conditions as for molding the inner layer material. On the surface of the multilayer laminated board formed in this way, via holes and circuits can be formed using additive or subtractive methods to create a printed circuit board. Furthermore, by repeating the above process using this printed circuit board as an inner layer material, it is possible to form even more multilayer boards.

[0127] The cured products and laminates for electrical and electronic circuits obtained from the resin composition of the present invention have excellent dielectric properties and thermal conductivity. [Examples]

[0128] 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 represent "parts by mass" and % represents "mass%". The analytical and measurement methods are shown below. Also, all units for all equivalents are "g / eq.".

[0129] (1) Weight average molecular weight (Mw): The results were obtained by GPC measurement. Specifically, a Tosoh Corporation HLC8320GPC was used, with columns (TSKgel SuperH-H, SuperH2000, SuperHM-H, SuperHM-H, all manufactured by Tosoh Corporation) connected in series, and the column temperature was set to 40°C. Tetrahydrofuran (THF) was used as the eluent at a flow rate of 1.0 mL / min, and a differential refractive index detector was used. For the measurement sample, 0.1 g of solid content was dissolved in 10 mL of THF, filtered through a 0.45 μm microfilter, and 50 μL of the resulting sample was used. Data processing was performed using Tosoh Corporation's GPC8020 Model II version 6.00.

[0130] (2) IR (Infrared Absorption Spectrum): Using a Fourier transform infrared spectrophotometer (Perkin Elmer Precisely, Spectrum One FT-IR Spectrometer 1760X), sodium chloride was used as the cell. The sample, dissolved in chloroform, was coated onto the cell, dried, and then measured at wavenumbers of 500-4000 cm⁻¹. -1 The transmittance was measured.

[0131] (3) Epoxy equivalent: Measurements were performed in accordance with JIS K7236 standard. Specifically, a potentiometric titrator was used, cyclohexanone was used as the solvent, and a 0.1 mol / L perchloric acid-acetic acid solution was added. For the solvent-diluted product (resin varnish), the value was calculated as a solid content equivalent from the non-volatile content.

[0132] (4) Non-volatile content: Measurements were taken in accordance with JIS K7235 standard. The drying temperature was 200°C and the drying time was 60 minutes.

[0133] (5) Dielectric properties: Film-like samples were measured using the cavity resonator perturbation method, while plate-like samples were measured using the capacitance method. Examples 1-19 and Comparative Examples 1-3 were evaluated by the dielectric loss tangent measured at 1 GHz using the cavity resonator perturbation method. Specifically, measurements were performed using a PNA network analyzer N5230A (Agilent Technologies, Inc.) and a cavity resonator CP431 (Kanto Electronics Applied Development Co., Ltd.) under a measurement environment of 23°C room temperature and 50% RH humidity, using a test specimen measuring 1.5 mm wide × 80 mm long × 150 μm thick. Examples 20-24 and Comparative Examples 4-6 were evaluated using the dielectric loss tangent measured at 1 GHz by the capacitance method. Specifically, measurements were performed using a material analyzer (manufactured by AGILENT Technologies) in accordance with the IPC-TM-650 2.5.5.9 standard, under a measurement environment of 23°C room temperature and 50% RH humidity, using a 30 mm square x 1 mm thick test specimen.

[0134] (6) Solubility: The modified epoxy resin was dissolved in a mixed solvent of methyl ethyl ketone (MEK):acetone = 2:1 (by weight) to create a resin varnish with a resin content of 40%, and its condition was visually assessed after being held in a constant temperature bath at 25°C for 24 hours. Transparent: ○, Cloudy: △, Separation: ×

[0135] (7) Adhesiveness: A modified epoxy resin solution was applied to copper foil (Mitsui Mining & Smelting Co., Ltd., 3EC 35#) and dried in an oven at 150°C for 30 minutes. A mild steel plate (Nippon Test Panel Co., Ltd., JIS.G.3141 SPCC-SB, 0.8 mm thick, sandblasted) was placed on the resulting modified epoxy resin-coated copper foil, hot-pressed at 200°C, and measured for peel strength according to JIS.C6481.

[0136] (8) Heat resistance: Measurements were 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 using a differential scanning calorimetry system EXSTAR6000 DSC6200 (manufactured by SII Nanotechnology Co., Ltd.) under a heating rate of 10°C / min, in the range of 20 to 280°C for two cycles. The measurement was then expressed as the midpoint glass transition temperature (Tmg) of the measurement chart obtained from the second scan.

[0137] The abbreviations used in the examples and comparative examples are as follows:

[0138] [Bifunctional epoxy resin] A1: Hydroquinone-type epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., YDC-1312, epoxy equivalent weight 175, m≒0.05) [ka] A2: Bisphenol F type liquid epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., YDF-170, epoxy equivalent weight 156, m≒0.09) A3: Biphenyl-type epoxy resin (manufactured by Mitsubishi Chemical Corporation, YX-4000, epoxy equivalent 186, melting point 105℃, m≒0.05) A4: Bisphenol A type liquid epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., YD-128, epoxy equivalent weight 186, m≒0.11) A5: Bisphenol A type semi-solid epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., YD-134, epoxy equivalent 250, m≒0.47) A6: Bisphenol A type solid epoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd., YD-7910, epoxy equivalent 2500, m≒14) Here, m has the same meaning as m in the general formula (2) above.

[0139] [Diester compounds] B1: 3,3-bis(p-acetoxyphenyl)-1H,3H-isobenzofuran-3-one (activity equivalent 201) obtained in Synthesis Example 1 [ka] B2: 4,4'-Diacetoxybiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd., activity equivalent 135) [ka] B3: 4,4'-diacetoxybenzophenone (activity equivalent 149) obtained in Synthesis Example 2. [ka] B4: 1,1-bis(4-acetoxyphenyl)-3,3,5-trimethylcyclohexane (activity equivalent 197) obtained in Synthesis Example 3 [ka] B5: 1,4-Diacetoxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd., activity equivalent 97) [ka] B6: 10-(2,5-diacetoxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (activity equivalent 204) obtained in Synthesis Example 4 [ka]

[0140] [Bifunctional phenolic compounds] C1: Bisphenol fluorene (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl group equivalent 175) [ka] C2: Bisphenol acetophenone (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl group equivalent 145) [ka] C3: Bisphenol AF (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl group equivalent 168) [ka] C4: Dihydroxydiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl group equivalent 101) [ka] C5:9,9-Bis(4-hydroxy-3-methylphenyl)fluorene (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl group equivalent 189) [ka]

[0141] [catalyst] D1: N,N'-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) D2: 2-Ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd., Curesol 2E4MZ)

[0142] [Solvents] S1: Cyclohexanone S2: Methyl ethyl ketone (MEK)

[0143] [Acid anhydride] E1: Acetic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) E2: Benzoic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0144] [Hardening agent] H1: Phenolic novolac resin (manufactured by Aica Kogyo Co., Ltd., Showol BRG-557, hydroxyl group equivalent 105) H2: 2-Ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd., Curesol 2E4MZ)

[0145] Synthesis Example 1 In a glass reaction vessel equipped with a stirrer, thermometer, nitrogen gas introduction device, condenser, and dropping device, 100 parts of phenolphthalein (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hydroxyl equivalent 159), 66 parts of acid anhydride E1, and 50 parts of pyridine were charged at room temperature. The mixture was heated to 60°C while stirring and nitrogen gas was introduced, and the reaction was carried out for 2 hours. Subsequently, the mixture was dried under reduced pressure at 150°C and 1.3 kPa (10 torr) for 2 hours to obtain 120 parts of diester compound B1.

[0146] Synthesis Example 2 In a glass reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet, condenser, and dropper, 100 parts of 4,4'-dihydroxybenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl equivalent 107), 98 parts of acid anhydride E1, and 74 parts of pyridine were charged at room temperature. The mixture was heated to 60°C while stirring and nitrogen gas was introduced, and the reaction was carried out for 2 hours. Subsequently, the mixture was dried under reduced pressure at 150°C and 1.3 kPa (10 torr) for 2 hours to obtain 132 parts of diester compound B3.

[0147] Synthesis Example 3 In a glass reaction vessel equipped with a stirrer, thermometer, nitrogen gas introduction device, condenser, and dropping device, 100 parts of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hydroxyl equivalent 155), 68 parts of acid anhydride E1, and 51 parts of pyridine were charged at room temperature. The mixture was heated to 60°C while stirring and nitrogen gas was introduced, and the reaction was carried out for 2 hours. Subsequently, the mixture was dried under reduced pressure at 150°C and 1.3 kPa (10 torr) for 2 hours to obtain 121 parts of diester compound B4.

[0148] Synthesis Example 4 In a glass reaction vessel equipped with a stirrer, thermometer, nitrogen gas introduction device, condenser, and dropping device, 100 parts of 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Chemical Co., Ltd., HCA-HQ, hydroxyl group equivalent 162), 64 parts of acid anhydride E1, and 49 parts of pyridine were charged at room temperature. The mixture was heated to 60°C while stirring and nitrogen gas was introduced, and the reaction was carried out for 2 hours. Subsequently, the mixture was dried under reduced pressure at 150°C and 1.3 kPa (10 torr) for 2 hours to obtain 120 parts of diester compound B6.

[0149] Example 1 In a glass reaction vessel equipped with a stirrer, thermometer, nitrogen gas introduction device, condenser, and dropper, 100 parts of bifunctional epoxy resin A1, 55 parts of diester compound B1, 48 parts of bifunctional phenol compound C1, and 51 parts of reaction solvent S1 were charged at room temperature. The temperature was raised to 130°C while stirring and nitrogen gas was introduced. After adding 0.1 parts of catalyst D1, the temperature was raised to 145°C and the reaction was carried out at the same temperature for 7 hours. After the reaction was complete, the mixture was diluted and mixed using 51 parts of diluent solvent S1 and 202 parts of S2 to obtain a modified epoxy resin varnish (R1) with a non-volatile content of 40%.

[0150] Examples 2-16, Comparative Examples 1-3 A resin varnish was obtained by performing the same procedure as in Example 1, according to the amount (parts) of each raw material and the reaction time shown in Tables 1 and 2. The "molar ratio" in the table represents the molar ratio of the difunctional epoxy resin to the diester compound and the difunctional phenol compound.

[0151] [Table 1]

[0152] [Table 2]

[0153] Example 17 100 parts (40 parts solids) of the resin varnish (RH3) obtained in Comparative Example 3 were mixed with 600 parts of reaction solvent S1. After raising the temperature to 100°C, 3 parts of acid anhydride E1 were added and the reaction was carried out for 4 hours. The resulting resin varnish was added to methanol, and the precipitated insoluble matter was filtered off. The filtrate was dried in a vacuum dryer at 150°C and 0.4 kPa (3 torr) for 1 hour to obtain a modified epoxy resin. To the obtained modified epoxy resin, 21 parts of diluent S1 and 41 parts of S2 were added and uniformly dissolved to obtain a resin varnish (R17) with a non-volatile content of 40%.

[0154] Example 18 The procedure was carried out in the same manner as in Example 18, except that 8 parts of acid anhydride E1, 22 parts of diluent solvent S1, and 43 parts of S2 were used to obtain resin varnish (R18).

[0155] Example 19 The procedure was carried out in the same manner as in Example 18, except that 18 parts of E2 were used instead of acid anhydride E1, 24 parts of diluent solvent S1, and 48 parts of S2, to obtain resin varnish (R19). Table 3 summarizes the amount (in parts) of each raw material used. [Table 3]

[0156] The resin varnishes R1-R19 and RH1-RH3 obtained in Examples 1-19 and Comparative Examples 1-3 were applied to an iron plate to a thickness of 100 μm after drying, and dried in a drying oven at 150°C for 1 hour to obtain a resin film. The epoxy equivalent, Mw, and adhesion were measured for the resin varnish, and the heat resistance, dielectric properties, and solubility were measured for the resin film. The results are shown in Table 4. In the table, "acylation rate" represents the content (mol%) of acyl groups in the total Z. However, since Example 15 (R15) did not form a resin film, the heat resistance, dielectric properties, and adhesion were not measured. The examples using resin varnishes RH1 to RH3 are comparative examples.

[0157] [Table 4]

[0158] Examples 20-22, Comparative Example 4 A resin composition was obtained by blending 30 parts (12 parts solids) of the modified epoxy resin varnish (R1, R3, R6, RH1) obtained in Examples 1, 3, 6, and Comparative Example 1, 2 parts of another epoxy resin A4, 2.5 parts of curing agent H1 in a 50% MEK solution, and 0.6 parts of H2 in a 20% MEK solution. These were then applied to iron plates to achieve film thicknesses of 100 μm and 150 μm after drying, and dried in a drying oven at 150°C for 1 hour to obtain a polymer film-like cured product. Dielectric properties and heat resistance were measured, and the results are shown in Table 5.

[0159] [Table 5]

[0160] Example 23 250 parts (100 parts solids) of the modified epoxy resin varnish (R15) obtained in Example 15, 29.2 parts of curing agent H1, and 0.3 parts of H2 were mixed and dissolved in a mixed solvent prepared with MEK, propylene glycol monomethyl ether, and N,N-dimethylformamide to obtain a resin composition varnish. The obtained resin composition varnish was impregnated into glass cloth (manufactured by Nitto Boseki Co., Ltd., WEA 7628 XS13, 0.18 mm thick). The impregnated glass cloth was dried in a hot air circulating oven at 150°C for 9 minutes to obtain a prepreg.

[0161] The obtained prepreg was loosened and sieved to obtain a 100-mesh pass prepreg powder. The obtained prepreg powder was placed in a fluororesin mold and subjected to a 2 MPa vacuum press at a temperature of 130°C for 15 minutes + 190°C for 80 minutes to obtain a 30 mm square x 1 mm thick test specimen. The dielectric properties and heat resistance of the test specimen were measured, and the results are shown in Table 6.

[0162] Example 24 The same procedure as in Example 23 was followed, except that R16 was used as the modified epoxy resin varnish, to obtain prepregs and test specimens. The same tests as in Example 23 were performed, and the results are shown in Table 6.

[0163] Comparative Example 5 The same procedure as in Example 23 was followed, except that 100 parts of A5 epoxy resin were used, to obtain prepregs and test specimens. The same tests as in Example 23 were performed, and the results are shown in Table 6.

[0164] Comparative Example 6 The same procedure as in Example 23 was followed, except that 100 parts of A6 were used as the epoxy resin, to obtain prepregs and test specimens. The same tests as in Example 23 were performed, and the results are shown in Table 6.

[0165] [Table 6]

[0166] As can be seen from Table 4, the modified epoxy resin of the present invention exhibits excellent dielectric properties, solubility, and adhesion. Furthermore, as can be seen from Tables 5 and 6, the cured product made from the resin composition of the present invention also exhibits excellent dielectric properties and heat resistance. [Industrial applicability]

[0167] The modified epoxy resins and resin compositions of the present invention are applicable to a wide range of fields, including adhesives, paints, construction materials for civil engineering, and insulating materials for electrical and electronic components. In particular, they are useful as insulating casting materials, lamination materials, and encapsulation materials in the electrical and electronic field, and are especially suitable for laminates for electrical and electronic circuits such as multilayer printed circuit boards and capacitors, adhesives such as film adhesives and liquid adhesives, semiconductor encapsulation materials, underfill materials, interchip fill materials for 3D-LSIs, insulating sheets, prepregs, and heat dissipation substrates.

Claims

1. A modified epoxy resin characterized by being represented by the following general formula (1), having an epoxy equivalent of 500 to 50,000 g / eq., and a weight-average molecular weight of 5,000 to 200,000. 【Chemistry 1】 In the formula, X is a divalent group (Xa) of the remaining skeleton obtained by removing two glycidyloxy groups from a bifunctional epoxy resin selected from hydroquinone-type epoxy resin, bisphenol F-type epoxy resin, or biphenyl-type epoxy resin, and a divalent group (Xb) selected from the following remaining skeleton obtained by removing two acyloxy groups from a diester compound or the following remaining skeleton obtained by removing two hydroxyl groups from a bifunctional phenol compound, wherein the divalent group (Xa) is 40 mol% or more and the divalent group (Xb) is less than 60 mol%. 【Chemistry 2】 Y is independently a hydrogen atom, an acyl group having 2 to 20 carbon atoms, or a glycidyl group. Z is an acyl group having 2 to 20 carbon atoms or a hydrogen atom, with 20 to 70 mol% being the above acyl group. n is the average value of the number of repetitions, between 1 and 500.

2. A resin composition characterized by comprising the modified epoxy resin described in claim 1 and a curing agent.

3. The resin composition according to claim 2, comprising 0.1 to 100 parts by mass of a curing agent as solid content per 100 parts by mass of the solid content of a modified epoxy resin.

4. The resin composition according to claim 2, comprising a modified epoxy resin, another epoxy resin, and a curing agent, wherein the mass ratio of the solid content of the modified epoxy resin to the other epoxy resin is 99 / 1 to 1 / 99.

5. The resin composition according to claim 4, comprising 0.1 to 100 parts by mass of a curing agent as solid content, with respect to 100 parts by mass of the total solid content of the modified epoxy resin and other epoxy resins.

6. The resin composition according to claim 2, wherein the curing agent is at least one selected from the group consisting of acrylic acid ester resins, melamine resins, urea resins, phenolic resins, acid anhydrides, amine compounds, imidazole compounds, amide compounds, cationic polymerization initiators, organophosphines, polyisocyanate compounds, blocked isocyanate compounds, carbodiimide compounds, and active ester curing agents.

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

8. A laminate for electrical and electronic circuits made using the resin composition described in claim 2.

9. A method for producing a modified epoxy resin according to claim 1, characterized by reacting a bifunctional epoxy resin represented by the following general formula (2) with a compound represented by the following general formula (3). 【Transformation 3】 Here, X1 is the divalent group (Xa) of the remaining skeleton obtained by removing two glycidyloxy groups from a bifunctional epoxy resin selected from hydroquinone-type epoxy resin, bisphenol F-type epoxy resin, or biphenyl-type epoxy resin. X² is a divalent group (Xb) selected from the following: 【Chemistry 4】 G is a glycidyl group, and Q is an acyl group having 2 to 20 carbon atoms or a hydrogen atom, with 20 to 70 mol% being the acyl group. The compound represented by general formula (3) may also be a mixture of two or more compounds selected from compounds where both Qs are acyl groups, compounds where one Q is an acyl group, and compounds where both Qs are hydrogen atoms. m is the average value of the number of repetitions, and is between 0 and 6.

10. A method for producing a modified epoxy resin according to claim 1, characterized in that 0.3 to 0.8 moles of an acid anhydride represented by the following general formula (8) are reacted with 1 mole of alcoholic hydroxyl group equivalent of an epoxy resin represented by the following general formula (7). 【Transformation 5】 Here, X and n are equivalent to those in formula (1). L is independently a hydrogen atom or a glycidyl group. T is an acyl group having 2 to 20 carbon atoms.

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