Active ester compound production method, active ester compound, and resin composition

Abstract

The present disclosure addresses the problem of providing an active ester compound production method that makes it possible to produce an active ester compound in which halogen ion content is reduced. Provided as a solution is an active ester compound production method wherein: a polyvalent carboxylic acid halide, a polyvalent phenolic hydroxyl group-containing compound, and an aromatic monohydroxy compound are reacted in the presence of a basic catalyst; and the amount of the basic catalyst is greater than 1.00 mole per 1 mole of the total of hydroxyl groups in the polyvalent phenolic hydroxyl group-containing compound and the aromatic monohydroxy compound.

Description

Method for producing active ester compound, active ester compound, and resin composition

[0001] The present disclosure relates to a method for producing an active ester compound, an active ester compound, and a resin composition.

[0002] Epoxy resin compositions containing an epoxy resin and its curing agent, such as an active ester compound, have been widely used in electronic component applications such as semiconductors and multilayer printed circuit boards because the cured products exhibit excellent heat resistance and insulating properties. In addition, in electronic component applications, insulating materials with excellent heat resistance and dielectric properties are required due to the trend toward higher frequencies and smaller sizes in electronic components.

[0003] For example, Patent Documents 1 to 4 disclose epoxy resin compositions that contain an epoxy resin and an active ester compound, etc., and that have both heat resistance and dielectric properties.

[0004] JP 2009-235165 A JP 2004-169021 A JP 2012-246367 A JP 2011-074120 A

[0005] In electronic components, in addition to heat resistance, dielectric properties, and the like, insulation reliability is also required more and more due to the progress of miniaturization of wiring and advanced design. It is known that the presence of halogen ions in insulating materials, in particular, can contribute to the occurrence of wiring breakage and ion migration due to acid generation and electron transfer, thereby potentially reducing insulation reliability. Therefore, there is a need to reduce the halogen ions contained in materials for electronic components. Therefore, an object of the present disclosure is to provide a method for producing an active ester compound capable of producing an active ester compound with reduced halogen ions.

[0006] The present inventors have found that the above-mentioned problems can be solved by adjusting the amount of a catalyst within a predetermined range in a method for producing an active ester compound, and have completed the present invention.

[0007] [1] A method for producing an activated ester compound, comprising reacting a polycarboxylic acid halide, a polyphenolic hydroxyl group-containing compound, and an aromatic monohydroxy compound in the presence of a basic catalyst, wherein the amount of the basic catalyst added is more than 1.00 moles per mole of total hydroxyl groups in the polyphenolic hydroxyl group-containing compound and the aromatic monohydroxy compound.

[0008] [2] The method for producing an active ester compound according to [1], wherein the amount of the basic catalyst is more than 1.00 mol and not more than 10 mol per 1 mol of the total hydroxyl groups in the polyhydric phenolic hydroxyl group-containing compound and the aromatic monohydroxy compound.

[0009] [3] The method for producing an active ester compound according to [1] or [2], wherein the basic catalyst is a metal hydroxide.

[0010] [4] The method for producing an active ester compound according to [3], wherein the basic catalyst is an alkali metal hydroxide.

[0011] [5] The method for producing an active ester compound according to [4], wherein the basic catalyst is sodium hydroxide or potassium hydroxide.

[0012] [6] The method for producing an active ester compound according to any one of [1] to [5], wherein the polycarboxylic acid halide is an aromatic dicarboxylic acid halide.

[0013] [7] The method for producing an active ester compound according to [6], wherein the aromatic dicarboxylic acid halide is an aromatic dicarboxylic acid chloride.

[0014] [8] The method for producing an active ester compound according to [7], wherein the aromatic dicarboxylic acid chloride is one or more compounds selected from the group consisting of isophthalic acid dichloride, terephthalic acid dichloride, 1,4-naphthalenedicarboxylic acid dichloride, 2,3-naphthalenedicarboxylic acid dichloride, and 2,6-naphthalenedicarboxylic acid dichloride.

[0015] [9] The method for producing an active ester compound according to any one of [1] to [8], wherein the polyhydric phenolic hydroxyl group-containing compound is a compound having a molecular structure in which two or more phenol compounds are linked via an alicyclic hydrocarbon group.

[0016]

[10] The method for producing an active ester compound according to any one of [1] to [9], wherein the aromatic monohydroxy compound is one or more compounds selected from the group consisting of phenol compounds, naphthol compounds, and anthracenol compounds.

[0017]

[11] The method for producing an active ester compound according to

[10] , wherein the aromatic monohydroxy compound is one or more compounds selected from the group consisting of phenol, alkylphenol, aralkylphenol, and naphthol.

[0018]

[12] The method for producing an active ester compound according to any one of [1] to

[11] , wherein the polyhydric carboxylic acid halide is reacted with the polyhydric phenolic hydroxyl group-containing compound in an amount of 0.05 mol to 0.75 mol of phenolic hydroxyl groups and the aromatic monohydroxy compound in an amount of 0.25 mol to 0.95 mol, relative to 1 mol of acid halide groups in the polyhydric carboxylic acid halide.

[0019]

[13] An active ester compound, wherein a polycarboxylic acid halide, a polyphenolic hydroxyl group-containing compound, an aromatic monohydroxy compound, and a basic catalyst are used as synthesis raw materials, and the amount of the basic catalyst added to the synthesis raw materials is more than 1.00 mole per mole of the total hydroxyl groups in the polyphenolic hydroxyl group-containing compound and the aromatic monohydroxy compound.

[0020]

[14] The active ester compound according to

[13] , wherein the amount of hydrolyzable chlorine is 150 ppm by mass or less.

[0021]

[15] A resin composition containing the active ester compound according to

[13] or

[14] and an epoxy resin.

[0022] According to the present disclosure, it is possible to provide a method for producing an active ester compound that can produce an active ester compound containing reduced halogen ions.

[0023] The method for producing an active ester compound, the active ester compound, and the resin composition of the present disclosure will be described in detail below with reference to examples based on embodiments thereof.

[0024] [Terminology] Unless otherwise specified, the following terms are applicable in this specification. In this specification, the term "reaction raw material" refers to a compound used to obtain a target compound through a chemical reaction such as synthesis or decomposition, and partially constitutes the chemical structure of the target compound, excluding substances that serve as chemical reaction auxiliaries, such as solvents and catalysts. In particular, in this specification, the term "reaction raw material" refers to a precursor for obtaining a target activated ester compound through a chemical reaction. On the other hand, in this specification, the term "synthesis raw material" refers to all compounds used to obtain a target compound through a chemical reaction such as synthesis or decomposition, and also includes substances that serve as chemical reaction auxiliaries, such as solvents and catalysts. Furthermore, the "alkyl group" in this specification may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an isohexyl group, a (n-)heptyl group, a (n-)octyl group, a (n-)nonyl group, a (n-)decyl group, a (n-)undecyl group, a (n-)dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, and an adamantyl group. As used herein, examples of an "alkenyl group" include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a pentynyl group, a hexynyl group, a vinyl group, an allyl group, and an isopropenyl group. As used herein, examples of an "alkoxy group" include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group. As used herein, examples of an "aryl group" include a phenyl group, a biphenyl group, a naphthyl group, a phenalenyl group, a phenanthrenyl group, an anthryl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group.Furthermore, in the "aryl group", a hydrogen atom on the aromatic ring in the aryl group may be substituted with, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. Examples of the "aralkyl group" in this specification include a benzyl group, a diphenylmethyl group, a biphenylmethyl group, and a naphthylmethyl group. A hydrogen atom on the aromatic ring in the aralkyl group may be substituted with, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. Examples of the "alkylene group" in this specification include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a propylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, and a dodecylene group. Examples of the "halogen atom" in this specification include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In this specification, the expression "a to b" in the description of a numerical range means from a to b, unless otherwise specified.

[0025] <Method for Producing an Active Ester Compound> The method for producing an active ester compound of this embodiment is characterized in that a polycarboxylic acid halide, a polyphenolic hydroxyl group-containing compound, and an aromatic monohydroxy compound are reacted in the presence of a basic catalyst, and the amount of the basic catalyst is more than 1.00 mol per 1 mol of the total hydroxyl groups in the polyphenolic hydroxyl group-containing compound and the aromatic monohydroxy compound. According to this method for producing an active ester compound, an active ester compound containing a reduced amount of halogen ions can be produced.

[0026] Electronic components such as printed circuit boards require high insulation reliability. However, there are several causes of insulation degradation that reduce insulation reliability, one of which is ion migration. Ion migration is a phenomenon in which an electrode metal dissolves into an insulating portion due to an electrochemical reaction and precipitates between electrodes. It is believed that one of the causes of ion migration is the deposition of electrode metal due to the exchange of electrons between halogen ions and the electrode metal. Therefore, it is believed that reducing the amount of halogen ions contained in an insulating material can suppress the occurrence of ion migration and improve reliability. By using the production method of this embodiment, halogen ions that are inevitably mixed into or remain in the active ester compound can be reduced, and electronic components made from the active ester compound obtained by this production method exhibit excellent insulation reliability. Below, the raw materials and production conditions used in the production method of the active ester compound of this embodiment are described in detail.

[0027] [Polycarboxylic Acid Halide] In the method for producing an activated ester compound of this embodiment, a polycarboxylic acid halide is used. The polycarboxylic acid halide of this embodiment is a compound having two or more acid halide groups [—C(═O)—X (X represents a halogen atom)]. The number of acid halide groups in the polycarboxylic acid halide is preferably 2 to 3, and more preferably 2, per molecule. Furthermore, examples of the halogen atom in the acid halide group, i.e., X in [—C(═O)—X], include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The polycarboxylic acid halide is preferably an aromatic dicarboxylic acid halide. Examples of aromatic dicarboxylic acid halides include, but are not limited to, halides of dicarboxylic acids having an aromatic ring such as isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl)sulfone, 2,2-bis(p-carboxyphenyl)propane, and 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane. These compounds may be used alone or in combination of two or more.

[0028] Examples of aromatic dicarboxylic acid halides include aromatic dicarboxylic acid fluorides, aromatic dicarboxylic acid chlorides, aromatic dicarboxylic acid bromides, aromatic dicarboxylic acid iodides, etc. Among these, aromatic dicarboxylic acid chlorides are preferred because of their ease of industrial availability.

[0029] Examples of aromatic dicarboxylic acid chlorides include dicarboxylic acid dichlorides such as isophthalic acid dichloride, terephthalic acid dichloride, 1,4-naphthalenedicarboxylic acid dichloride, 2,3-naphthalenedicarboxylic acid dichloride, 2,6-naphthalenedicarboxylic acid dichloride, 5-tert-butylisophthalic acid dichloride, 5-bromoisophthalic acid dichloride, 5-fluoroisophthalic acid dichloride, 5-chloroisophthalic acid dichloride, 4,4'-dicarboxybiphenyl dichloride, 4,4'-dicarboxydiphenyl ether dichloride, 4,4'-dicarboxytetraphenylsilane dichloride, 4,4'-sulfonyldibenzoyl chloride, 2,2-bis(p-carboxyphenyl)propane dichloride, and 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dichloride. Among these, the aromatic dicarboxylic acid chloride is preferably one or more compounds selected from the group consisting of isophthalic acid dichloride, terephthalic acid dichloride, 1,4-naphthalenedicarboxylic acid dichloride, 2,3-naphthalenedicarboxylic acid dichloride, and 2,6-naphthalenedicarboxylic acid dichloride.

[0030] When reacting a polycarboxylic acid halide, a polyphenolic hydroxyl group-containing compound, and an aromatic monohydroxy compound in the presence of a basic catalyst, the amount of polycarboxylic acid halide is preferably such that the number of moles of the functional group (phenolic hydroxyl group) of the polyphenolic hydroxyl group-containing compound is small relative to the number of moles of the functional group (acid halide group) of the polycarboxylic acid halide, and the amount (molar number) of the aromatic monohydroxy compound used is small. This amount significantly reduces the dielectric tangent of the cured product using the resulting active ester compound. Furthermore, the amount of polycarboxylic acid halide is preferably such that the number of moles of the functional group (acid halide group) of the polycarboxylic acid halide is equal to or less than the sum of the number of moles of the functional group (phenolic hydroxyl group) of the polyphenolic hydroxyl group-containing compound and the amount (molar number) of the aromatic monohydroxy compound used. This amount reduces the hydrolyzable ions of the resulting active ester compound.

[0031] [Polyphenolic Hydroxyl Group-Containing Compound] In the method for producing an active ester compound of the present embodiment, a polyphenolic hydroxyl group-containing compound is used. Note that the "phenolic hydroxyl group" refers to a hydroxyl group (-OH) directly bonded to a carbon atom in an aromatic ring.

[0032] The polyhydric phenolic hydroxyl group-containing compound is preferably a compound having two or more phenolic hydroxyl groups, and more preferably a compound having a molecular structure in which two or more phenolic compounds are linked via an alicyclic hydrocarbon group. As the compound having a molecular structure in which phenolic compounds are linked via an alicyclic hydrocarbon group, a compound whose reaction raw materials are an unsaturated alicyclic hydrocarbon compound having two double bonds in one molecule and a phenolic compound is preferred, and examples thereof include a structure obtained by polyaddition reaction of an unsaturated alicyclic hydrocarbon compound having two double bonds in one molecule and a phenolic compound.

[0033] Examples of the alicyclic hydrocarbon group include divalent monocyclic alicyclic hydrocarbon groups such as a cyclohexanediyl group, a cyclooctanediyl group, a cyclononanediyl group, and a cyclodecanediyl group; a bicyclo[1.1.0]butanediyl group, a tricyclo[2.2.1.0]heptanediyl group, a bicyclo[3.2.1]octanediyl group, a bicyclo[2.2.2]octanediyl group, an adamantanediyl group, a bicyclo[4.3.2]undecanediyl group, a tricyclo[5.3.1.1]dodecanediyl group, a tricyclo[5.2.1.0]octanediyl group, a ２，６ ] Divalent polycyclic alicyclic hydrocarbon groups such as a decanediyl group, an adamantanediyl group, a norbornane group, or an isobornane group are preferred. The alicyclic hydrocarbon group may have bonded thereto, as a substituent, an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group; an aromatic hydrocarbon group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group; a halogen atom; or a hydroxy group.

[0034] The phenolic compound includes, but is not limited to, phenol and substituted phenolic compounds substituted with one or more alkyl groups, alkenyl groups, allyl groups, aryl groups, alkoxy groups, aralkyl groups, or halogen groups. Specific examples of the phenolic compound include, but are not limited to, cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, methoxyphenol, benzylphenol, chlorophenol, bromophenol, naphthol, and dihydroxynaphthalene. These compounds may be used alone or in combination of two or more. Among these, phenol is particularly preferred because of its excellent fluidity and curability.

[0035] Specific examples of the unsaturated alicyclic hydrocarbon compound include dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorborn-2-ene, α-pinene, β-pinene, and limonene. These compounds may be used alone or in combination of two or more. Among these compounds, dicyclopentadiene is preferred as the unsaturated alicyclic hydrocarbon compound in terms of the balance of properties, particularly heat resistance and moisture absorption.

[0036] The combination of a phenol compound and an unsaturated alicyclic hydrocarbon compound in a compound having a molecular structure in which a phenol compound is linked via an alicyclic hydrocarbon group is not particularly limited, but is preferably a combination of phenol and dicyclopentadiene, i.e., dicyclopentadienephenol.

[0037] The polyhydric phenolic hydroxyl group-containing compound is preferably a compound having a weight average molecular weight of 200 to 2000. More preferably, the weight average molecular weight of the polyhydric phenolic hydroxyl group-containing compound is 300 to 1300.

[0038] A preferred polyhydric phenolic hydroxyl group-containing compound of this embodiment is a compound having a molecular structure in which two or more phenolic compounds are linked via an alicyclic hydrocarbon group, and preferably a compound having a weight average molecular weight of 300 to 1300. The polyhydric phenolic hydroxyl group-containing compound preferably has a structure represented by the following general formula (1), for example: (In the above general formula (1), M １ represents an optionally substituted alicyclic hydrocarbon group, preferably a group selected from the group consisting of the following formulae (I) to (IV), and R １ and R ２ each independently represents an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group or a naphthyl group; a halogen atom; or a hydroxy group, n1 represents an integer from 1 to 10, and m11 and m12 represent integers of 0 to 3. * in the above general formula (1) represents a bond bonding to another atom. (In the above formulas (I) to (IV), R ３ each independently represents a hydroxyl group, an amino group, an alkyl group having 1 to 15 carbon atoms, or an alkoxy group having 1 to 15 carbon atoms; L １ and L ２ each independently represents an alkylene group having 1 to 15 carbon atoms, provided that one or more —CH ２ - may be substituted with -O- or -C(=O)-, m1 represents an integer of 0 to 6, and m2 represents an integer of 0 to 4.

[0039] In the method for producing an active ester compound of this embodiment, the polyphenolic hydroxyl group-containing compound is preferably added in an amount such that 0.05 mol or more and 0.75 mol or less of phenolic hydroxyl groups are reacted with 1 mol of acid halide groups in the polycarboxylic acid halide. From the viewpoint of dielectric properties, the polyphenolic hydroxyl group-containing compound is preferably added in an amount such that 0.1 mol or more of phenolic hydroxyl groups are reacted with 1 mol of acid halide groups in the polycarboxylic acid halide, and even more preferably 0.15 mol or more of phenolic hydroxyl groups are reacted with 1 mol of acid halide groups in the polycarboxylic acid halide. Furthermore, from the viewpoint of solvent solubility, the polyphenolic hydroxyl group-containing compound is preferably added in an amount such that 0.75 mol or less of phenolic hydroxyl groups are reacted with 1 mol of acid halide groups in the polycarboxylic acid halide, and even more preferably 0.7 mol or less of phenolic hydroxyl groups are reacted with 1 mol of acid halide groups in the polycarboxylic acid halide. The range of the amount of the polyhydric phenolic hydroxyl group-containing compound to be added is preferably from 0.1 mol to 0.75 mol, and even more preferably from 0.15 mol to 0.7 mol. The upper and lower limits can be adjusted as appropriate.

[0040] [Aromatic Monohydroxy Compound] In the method for producing an active ester compound of this embodiment, an aromatic monohydroxy compound is used. The aromatic monohydroxy compound serves as an end-capping agent during the synthesis of the active ester compound, and can prevent the elongation of the active ester compound. Therefore, an active ester compound with an appropriate degree of polymerization can be produced.

[0041] The aromatic monohydroxy compound is preferably one or more compounds selected from the group consisting of phenol compounds, naphthol compounds, and anthracenol compounds, and the aromatic monohydroxy compound is preferably one or more compounds selected from the group consisting of phenol, alkylphenol, aralkylphenol, and naphthol.

[0042] The phenol compound in the aromatic monohydroxy compound is not limited, but includes phenol, alkylphenol, arylphenol, aralkylphenol, alkenylphenol, alkoxyphenol, halogenated phenol, and the like.

[0043] The alkylphenol is not particularly limited, but examples thereof include o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, n-butylphenol, s-butylphenol, t-butylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,4,5-trimethylphenol, and 3,4,5-trimethylphenol.

[0044] The arylphenol is not particularly limited, but examples thereof include o-phenylphenol, m-phenylphenol, and p-phenylphenol.

[0045] The aralkylphenol is not particularly limited, but examples thereof include o-benzylphenol, m-benzylphenol, and p-benzylphenol.

[0046] The alkenylphenol is not particularly limited, but examples thereof include o-vinylphenol, m-vinylphenol, p-vinylphenol, o-allylphenol, m-allylphenol, and p-allylphenol.

[0047] The alkoxyphenol is not particularly limited, but examples thereof include o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, o-ethoxyphenol, m-ethoxyphenol, p-ethoxyphenol, etc. As the alkoxyphenol, o-methoxyphenol and p-methoxyphenol are preferred.

[0048] The halogenated phenol is not particularly limited, but examples thereof include o-chlorophenol, m-chlorophenol, p-chlorophenol, and the like.

[0049] The naphthol compound is not limited to, but examples thereof include naphthols such as α-naphthol and β-naphthol. The aromatic monohydroxy compound is preferably α-naphthol or β-naphthol, from the viewpoint of reducing the dielectric loss tangent of a cured product using the active ester compound.

[0050] The anthracenol compound is not particularly limited, but examples thereof include 1-anthracenol and 2-anthracenol.

[0051] In the method for producing an active ester compound of this embodiment, the aromatic monohydroxy compound is preferably reacted in an amount of 0.25 to 0.95 moles per mole of acid halide group in the polycarboxylic acid halide. From the viewpoint of dielectric properties, the aromatic monohydroxy compound is preferably reacted in an amount of 0.25 moles or more, and even more preferably 0.28 moles or more, per mole of acid halide group in the polycarboxylic acid halide. Furthermore, from the viewpoint of solvent solubility, the aromatic monohydroxy compound is preferably reacted in an amount of 0.95 moles or less, and even more preferably 0.92 moles or less, per mole of acid halide group in the polycarboxylic acid halide. The aromatic monohydroxy compound is preferably reacted in an amount of 0.28 to 0.92 moles per mole of acid halide group in the polycarboxylic acid halide. The above upper and lower limits can be adjusted as appropriate.

[0052] [Basic Catalyst] In the method for producing an activated ester compound of the present embodiment, the polycarboxylic acid halide, the polyphenolic hydroxyl group-containing compound, and the aromatic monohydroxy compound are reacted in the presence of a basic catalyst.

[0053] The basic catalyst is preferably an inorganic basic catalyst.

[0054] The inorganic basic catalyst is preferably a metal hydroxide, more preferably an alkali metal hydroxide. Examples of alkali metal hydroxides include sodium hydroxide, potassium hydroxide, and rubidium hydroxide. Among these, sodium hydroxide or potassium hydroxide is preferred from the viewpoint of productivity because they can be used in the form of an aqueous solution.

[0055] In the method for producing an activated ester compound according to this embodiment, the amount of the basic catalyst is greater than 1.00 moles per mole of the total hydroxyl groups in the polyphenolic hydroxyl group-containing compound and the aromatic monohydroxy compound. When the amount of the basic catalyst is within the above-mentioned lower limit, generation of halogen ions is prevented, and an activated ester compound can be produced in which halogen ions that may cause ion migration are reduced. From the same viewpoint, the amount of the basic catalyst is preferably 1.01 moles or more, more preferably 1.02 moles or more, and even more preferably 1.03 moles or more per mole of the total hydroxyl groups in the polyphenolic hydroxyl group-containing compound and the aromatic monohydroxy compound. Furthermore, from the viewpoint of reactivity, the amount of the basic catalyst is preferably 10 moles or less, more preferably 5 moles or less, even more preferably 4 moles or less, and even more preferably 3 moles or less, per mole of the total hydroxyl groups in the polyphenolic hydroxyl group-containing compound and the aromatic monohydroxy compound. As in the method for producing an activated ester compound of this embodiment, when the amount of basic catalyst added exceeds 1.00 moles per mole of the total hydroxyl groups in the polyphenolic hydroxyl group-containing compound and the aromatic monohydroxy compound, it is presumed that the reactivity is improved and the halogen ions are reduced. Furthermore, the excess basic catalyst (i.e., the amount of basic catalyst exceeding 1.00 moles per mole of the total hydroxyl groups in the polyphenolic hydroxyl group-containing compound and the aromatic monohydroxy compound) does not contribute to the reaction between the polycarboxylic acid halide, the polyphenolic hydroxyl group-containing compound, and the aromatic monohydroxy compound, and is simply removed in a subsequent step (e.g., a neutralization step) without affecting the physical properties of the activated ester compound produced. In other words, it is presumed that increasing the amount of basic catalyst added only reduces the halogen ions in the activated ester, with little change in other physical properties of the activated ester. On the other hand, it is presumed that too much excess basic catalyst promotes hydrolysis, impairs separation, and reduces productivity, so it is preferable not to add too much basic catalyst.The amount of the basic catalyst to be added is preferably more than 1.00 mol and not more than 10 mol, more preferably more than 1.00 mol and not more than 5 mol, even more preferably 1.01 mol or more and not more than 5 mol, still more preferably 1.02 mol or more and not more than 4 mol, and particularly preferably 1.03 mol or more and not more than 3 mol, per mol of the total hydroxyl groups in the polyhydric phenolic hydroxyl group-containing compound and the aromatic monohydroxy compound. The upper and lower limits can be adjusted as appropriate.

[0056] The basic catalyst may be used in the form of an aqueous solution. In this case, the concentration of the basic catalyst-containing aqueous solution is preferably in the range of 3.0 to 50% by mass based on the total amount of the basic catalyst-containing aqueous solution.

[0057] [Reaction Conditions, etc.] In the method for producing an activated ester compound of the present embodiment, the reaction temperature when the raw materials, i.e., a polycarboxylic acid halide, a polyphenolic hydroxyl group-containing compound, and an aromatic monohydroxy compound, are reacted in the presence of a basic catalyst is not particularly limited, and can be, for example, 10 to 80°C.

[0058] In the method for producing an activated ester compound of the present embodiment, the reaction pressure when the starting materials, i.e., a polycarboxylic acid halide, a polyphenolic hydroxyl group-containing compound, and an aromatic monohydroxy compound, are reacted in the presence of a basic catalyst is not particularly limited, and can be, for example, 0 to 202,650 Pa.

[0059] In the method for producing an activated ester compound of this embodiment, the reaction time is not particularly limited and can be, for example, 0.5 to 24 hours.

[0060] Furthermore, the method for producing an active ester compound of the present embodiment can be carried out under atmospheric pressure or a nitrogen atmosphere, although this is not a limitation. The method for producing an active ester compound of the present embodiment is preferably carried out under a nitrogen atmosphere.

[0061] The method for reacting a polycarboxylic acid halide, a polyphenolic hydroxyl group-containing compound, and an aromatic monohydroxy compound in the presence of a basic catalyst is not particularly limited, but may include, for example, a method in which the polyphenolic hydroxyl group-containing compound and the aromatic monohydroxy compound are mixed in the presence of an organic solvent and reacted while continuously or intermittently adding a basic catalyst or an aqueous solution thereof. The organic solvent is not particularly limited, and examples thereof include ketones such as methyl isobutyl ketone, acetone, methyl ethyl ketone (MEK), cyclohexanone, and acetophenone; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane; cyclic ethers such as dioxane and tetrahydrofuran; aromatic solvents such as benzene, toluene, and xylene; and organic halogen compounds such as dichloromethane. These organic solvents may be used alone or in combination.

[0062] The method for producing an active ester compound of this embodiment may include a step of neutralizing the reaction product after reacting a polycarboxylic acid halide, a polyphenolic hydroxyl group-containing compound, and an aromatic monohydroxy compound in the presence of a basic catalyst (neutralization step). Hydrochloric acid, ammonium chloride, sulfuric acid, nitric acid, phosphoric acid, sodium monophosphate, sodium diphosphate, etc. can be used in the neutralization step. Furthermore, the method for producing an active ester compound of this embodiment may include a step of washing the reaction product with water after reacting a polycarboxylic acid halide, a polyphenolic hydroxyl group-containing compound, and an aromatic monohydroxy compound in the presence of a basic catalyst (water-washing step). By providing the water-washing step, a reduction in the total amount of chlorine can be expected.

[0063] <Activated Ester Compound> The activated ester compound of this embodiment is characterized in that it uses a polycarboxylic acid halide, a polyphenolic hydroxyl group-containing compound, an aromatic monohydroxy compound, and a basic catalyst as synthesis raw materials, and the amount of basic catalyst added as the synthesis raw materials is greater than 1.00 moles per mole of the total hydroxyl groups in the polyphenolic hydroxyl group-containing compound and the aromatic monohydroxy compound. The active ester compound of this embodiment contains only trace amounts of halogen ions, and the active ester compound of this embodiment contains fewer halogen ions than conventional active ester compounds. Therefore, the occurrence of ion migration in electronic components made from the active ester compound can be suppressed, and the reliability of products using resin compositions containing the active ester compound of this embodiment can be improved. In this invention, the term "synthetic raw materials" refers to all compounds used to obtain a target compound through a chemical reaction such as synthesis or decomposition, and also includes substances that serve as chemical reaction aids, such as solvents and catalysts.

[0064] The number average molecular weight (Mn) of the active ester compound of this embodiment is preferably in the range of 300 to 15,000, more preferably in the range of 400 to 14,000, and even more preferably in the range of 500 to 13,000. The weight average molecular weight (Mw) of the active ester compound is preferably in the range of 300 to 50,000, more preferably in the range of 400 to 40,000, and even more preferably in the range of 500 to 30,000. From the viewpoint of solvent solubility, the active ester compound of this embodiment preferably has a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) calculated from gel permeation chromatography (GPC) measurement of 1.01 to 3, and more preferably 1.02 to 2. The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) were measured using gel permeation chromatography (hereinafter abbreviated as "GPC") under the measurement conditions described in the "-GPC measurement conditions-" section below.

[0065] The amount of the basic catalyst in the raw material for synthesizing the active ester compound of this embodiment is more than 1.00 moles per mole of the total hydroxyl groups in the polyphenolic hydroxyl group-containing compound and the aromatic monohydroxy compound. When the amount of the basic catalyst is within the above lower limit, the amount of halogen ions in the active ester compound is reduced, thereby improving the reliability of products using this active ester compound. From the viewpoint of improving reliability, the amount of the chlorine catalyst is preferably 1.01 moles or more, more preferably 1.02 moles or more, and even more preferably 1.03 moles or more, per mole of the total hydroxyl groups in the polyphenolic hydroxyl group-containing compound and the aromatic monohydroxy compound. Furthermore, from the viewpoint of reactivity, the amount of the chlorine catalyst is preferably 10 moles or less, more preferably 5 moles or less, even more preferably 4 moles or less, and even more preferably 3 moles or less, per mole of the total hydroxyl groups in the polyphenolic hydroxyl group-containing compound and the aromatic monohydroxy compound. The range of the blending amount of the chlorine catalyst is preferably more than 1.00 mol and not more than 10 mol, more preferably more than 1.00 mol and not more than 5 mol, even more preferably 1.01 mol to 5 mol, still more preferably 1.02 mol to 4 mol, and particularly preferably 1.03 mol to 3 mol, per mol of the total hydroxyl groups in the polyhydric phenolic hydroxyl group-containing compound and the aromatic monohydroxy compound. The above upper and lower limits can be appropriately changed.

[0066] The polycarboxylic acid halide, polyphenolic hydroxyl group-containing compound, aromatic monohydroxy compound, and basic catalyst, which are reaction raw materials for the active ester compound, and the basic catalyst, which is a synthesis raw material for the active ester compound, can all be described by reference to the contents of the polycarboxylic acid halide, polyphenolic hydroxyl group-containing compound, aromatic monohydroxy compound, and basic catalyst described in relation to the above-mentioned method for producing an active ester compound.

[0067] In the active ester compound of this embodiment, the amount of the polyhydric phenolic hydroxyl group-containing compound to be blended can be determined by reference to the description of the amount of the polyhydric phenolic hydroxyl group-containing compound explained in relation to the method for producing the active ester compound described above.

[0068] In the active ester compound of this embodiment, the content of the aromatic monohydroxy compound blended can be referred to in relation to the above-described method for producing an active ester compound.

[0069] The active ester compound of the present embodiment preferably has a total chlorine content of 200 ppm by mass or less. Here, in this specification, "total chlorine" refers to the combined amount of hydrolyzable chlorine and free chlorine, and "total chlorine amount" refers to the total amount of hydrolyzable chlorine and free chlorine contained in the active ester compound.

[0070] From the viewpoint of improving the reliability of resin compositions and the like using the active ester compound, the total chlorine content of the active ester compound is more preferably 190 ppm by mass or less, and even more preferably 180 ppm by mass or less. Furthermore, from the viewpoint of industrially advantageous production of the active ester compound, the total chlorine content may be 0.1 ppm by mass or more. As described above, the total chlorine content of the active ester compound can be reduced to the above upper limit or less by adjusting the amount of the basic catalyst. The total chlorine content can be determined by taking a sample of the active ester compound so that its solid content is 5 g and placing it in a heat-resistant and pressure-resistant (stainless steel copper) SUS can, adding 50 g of water, heating at a high temperature and high pressure of 160°C for 20 hours, measuring the chloride ions in the resulting water, and then calculating the total chlorine content using the following formula: Chloride ions in water [ppm by mass] x 10 = total chlorine [ppm by mass]

[0071] The active ester compound of the present embodiment preferably has a free chlorine content of 30 mass ppm or less. In this specification, "free chlorine" refers to anionized chlorine, and "amount of free chlorine" refers to the amount of anionized chlorine.

[0072] From the viewpoint of improving the reliability of resin compositions and the like using the active ester compound, the amount of free chlorine in the active ester compound is more preferably 25 ppm by mass or less, and even more preferably 20 ppm by mass or less. Furthermore, from the viewpoint of industrially advantageous production of an active ester compound, the amount of free chlorine may be 1 ppm by mass or more. The amount of free chlorine can be measured by adding tetrahydrofuran (THF) and 3 mL of a 30 wt % aqueous solution of acetic acid, adding dropwise a 0.002 mol % / L aqueous solution of silver nitrate, and performing potentiometric titration using an AT-310J titrator manufactured by Kyoto Electronics Manufacturing Co., Ltd.

[0073] The active ester compound of the present embodiment preferably has a hydrolyzable chlorine content of 150 ppm by mass or less. When a substance containing hydrolyzable chlorine is exposed to harsh conditions such as high temperature and high humidity, the hydrolyzable chlorine is decomposed to liberate chlorine ions, which causes ion migration and adversely affects the reliability of the product. Therefore, the amount of hydrolyzable chlorine is preferably small.

[0074] From the viewpoint of improving reliability, the amount of hydrolyzable chlorine in the active ester compound is more preferably 140 ppm by mass or less, and even more preferably 130 ppm by mass. Furthermore, from the viewpoint of industrially advantageous production of the active ester compound, the amount of hydrolyzable chlorine may be 0.1 ppm by mass or more. The amount of hydrolyzable chlorine can be calculated using the following formula: (amount of hydrolyzable chlorine) = (total amount of chlorine) - (amount of free chlorine).

[0075] Halogen ions can be one of the causes of ion migration, and among halogen ions, chloride ions are particularly frequently found in the manufacturing environment of electronic components such as printed wiring boards. Therefore, reducing chloride ions is thought to significantly suppress the occurrence of ion migration, and as a result, to improve reliability.

[0076] The active ester compound of the present embodiment is preferably represented by the following general formula (i). (In the above general formula (i), X １ and X ２each independently represents an optionally substituted benzene ring or naphthalene ring; M １ represents an optionally substituted alicyclic hydrocarbon group, preferably a group selected from the group consisting of the following formulae (I) to (IV), and L ３ , L ４ , L ５ and L ６ each independently represents —C(═O)—O— or —O—(O═)C—; R １ ~R ４ each independently represents an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group or a naphthyl group; a halogen atom; or a hydroxy group; n is the average value of the repeating units and is 0.05 to 2.5; and m11 to m14 each represent an integer of 0 or more and 3 or less. (In the above formulas (I) to (IV), R ３ each independently represents a hydroxyl group, an amino group, an alkyl group having 1 to 15 carbon atoms, or an alkoxy group having 1 to 15 carbon atoms; L １ and L ２ each independently represents an alkylene group having 1 to 15 carbon atoms, provided that one or more —CH ２ - may be substituted with -O- or -C(=O)-, m1 represents an integer of 0 to 6, and m2 represents an integer of 0 to 4.

[0077] The active ester compound of the present embodiment is preferably represented by the following general formula (ii): (In the above general formula (ii), X is a benzene ring or a naphthalene ring, k is 0 or 1, and n is the average value of the repeating units and is 0.05 to 2.5.) When the active ester compound has a structure represented by general formula (ii), it is more preferable, in particular, because the dielectric tangent of the cured product is low and the solution viscosity when dissolved in an organic solvent is low. In particular, in the above general formula (ii), the value of n, i.e., the average value of the repeating units, is preferably in the range of 0.25 to 2.4. In addition, in the above general formula (ii), it is preferable that the value of k is 0, in order to make the effects of the present invention more pronounced.

[0078] Here, n in the general formula (ii) can be determined as follows. [Method of determining n in general formula (ii)] By GPC measurement performed under the following conditions, the ratios (β1 / α1, β2 / α2, β3 / α3, β4 / α4) of the styrene-equivalent molecular weights (α1, α2, α3, α4) corresponding to n=1, n=2, n=3, and n=4, respectively, to the theoretical molecular weights (β1, β2, β3, β4) for n=1, n=2, n=3, and n=4, respectively, are determined, and the average values ​​of these (β1 / α1 to β4 / α4) are calculated. The number average molecular weight (Mn) determined by GPC is multiplied by this average value to determine the average molecular weight. Next, the value of n is calculated by using the molecular weight of the general formula (ii) as the average molecular weight.

[0079] - GPC measurement conditions - Measurement device: "HLC-8220 GPC" manufactured by Tosoh Corporation Column: Guard column "H" manufactured by Tosoh Corporation ＸＬ-L" + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation Detector: RI (differential refractive index) Data processing: "GPC-8020 Model II Version 4.10" manufactured by Tosoh Corporation Measurement conditions: Column temperature: 40°C Developing solvent: tetrahydrofuran Flow rate: 1.0 ml / min Standard: In accordance with the measurement manual for the "GPC-8020 Model II Version 4.10," the following monodisperse polystyrene with a known molecular weight was used. (Polystyrene used) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" Sample: 50 μl of a 1.0% by mass tetrahydrofuran solution (equivalent to resin solids) filtered through a microfilter.

[0080] <Resin Composition> The resin composition of this embodiment is characterized by containing the active ester compound of this embodiment and an epoxy resin. The resin composition exhibits excellent curability, with a shorter gel time, an index of curability, than a resin composition not containing the active ester compound of this embodiment. The resin composition of this embodiment uses an active ester compound with a reduced amount of halogen ions as an impurity, which is presumably why the reaction is less inhibited by impurities and more easily progresses. The gel time is the time required for curing, and shortening the gel time can shorten the production time for cured products of the resin composition, etc. This leads to improved production efficiency. Furthermore, shortening the production time reduces the power used to cure the resin composition, leading to reduced environmental impacts such as reduced carbon dioxide emissions. Generally, in industrial production, multiple cured products of resin compositions are repeatedly produced, and shortening the gel time in a single production run of cured products significantly shortens the overall production time. Therefore, this shortened production time significantly reduces the environmental impact.

[0081] [Active Ester Compound] The resin composition of this embodiment contains the above-described active ester compound. The above-described description of the active ester compound is incorporated herein by reference. In the resin composition of this embodiment, the content of the active ester compound is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass, based on the total mass of the resin composition.

[0082] [Epoxy Resin] The above-mentioned epoxy resins include novolac-type epoxy resins obtained by glycidyl etherifying novolac resins such as cresol novolac, phenol novolac, α-naphthol novolac, β-naphthol novolac, bisphenol A novolac, and biphenyl novolac; bisphenol-type epoxy resins obtained by glycidyl etherifying bisphenols such as bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, bisphenol fluorene, and hydrogenated bisphenol A; and bisphenol-type epoxy resins obtained by glycidyl etherifying biphenols such as biphenol and tetramethylbiphenol. biphenol-type epoxy resins obtained by glycidyl etherifying polyhydric naphthols such as dihydroxynaphthalene, binaphthol, and bis(dihydroxynaphthyl)methane; naphthalene-type epoxy resins obtained by glycidyl etherifying polyhydric naphthols such as dihydroxynaphthalene, binaphthol, and bis(dihydroxynaphthyl)methane; aralkyl-type phenolic resins obtained by glycidyl etherifying aralkyl-type phenolic resins having a structure in which phenols such as phenol and naphthol are bonded via aralkyl groups; glycidyl ethers of polyaddition products of unsaturated alicyclic hydrocarbon compounds containing two double bonds in one molecule and phenols; and epoxy resins having a benzopyran structure in their molecular structure.

[0083] Among these, the epoxy resin of the present embodiment is preferably a glycidyl etherified product of a polyaddition reaction between an unsaturated alicyclic hydrocarbon compound containing two double bonds in one molecule and a phenol (hereinafter abbreviated as "epoxy resin (A')"), since it has a low melt viscosity and also provides a cured product with good heat resistance.

[0084] Specific examples of phenols include cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, naphthol, dihydroxynaphthalene, etc. Among these, phenol is particularly preferred because of its excellent fluidity and curability.

[0085] The unsaturated alicyclic hydrocarbon compound is not particularly limited as long as it is an unsaturated alicyclic hydrocarbon compound having two or more unsaturated double bonds in one molecule, and examples thereof include dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorborn-2-ene, α-pinene, β-pinene, and limonene. Among these, dicyclopentadiene is preferred from the viewpoint of balance of properties, particularly heat resistance and hygroscopicity. Furthermore, since dicyclopentadiene is contained in petroleum fractions, industrial dicyclopentadiene may contain other aliphatic or aromatic dienes as impurities. However, in consideration of heat resistance, curability, moldability, and the like, a product with a dicyclopentadiene purity of 90% by weight or more is desirable.

[0086] The epoxy resin (A') can be produced by polyaddition of an unsaturated alicyclic hydrocarbon compound with a phenol in a molar ratio of the former / the latter = 1 / (5 or more) to produce a raw material polyhydric phenol, which is then glycidyl etherified. In this case, the polyaddition catalyst used in producing the polyhydric phenol can be an inorganic acid such as hydrochloric acid or sulfuric acid, an organic acid such as paratoluenesulfonic acid, or AlCl ３ , B.F. ３ Lewis acids such as these can be used. The high-molecular-weight polyhydric phenol compound obtained by the polyaddition reaction can be subjected to molecular distillation to obtain the desired polyhydric phenol mixture. The molecular distillation method can be carried out by selectively separating the low-molecular-weight region using a thin-film distiller or the like under high-temperature, reduced-pressure conditions of 250°C or higher and 0.5 Torr or lower.

[0087] The polyhydric phenol thus obtained is then reacted with epihalohydrin to obtain the desired epoxy resin. Specifically, this reaction involves first adding and dissolving 2 to 15 equivalents of epihalohydrin relative to the hydroxyl groups of the polyhydric phenol, preferably 3 to 10 equivalents in view of its superior effect in reducing melt viscosity. Then, 0.8 to 1.2 equivalents of a 10 to 50% aqueous NaOH solution relative to the hydroxyl groups in the polyaddition reaction product are added dropwise at a temperature of 50 to 80°C over a period of 3 to 5 hours. After the addition, stirring is continued at that temperature for approximately 0.5 to 2 hours, and the resulting solution is allowed to stand, after which the lower layer of saline is discarded. The excess epihalohydrin is then recovered by distillation to obtain a crude resin. An organic solvent such as toluene or MIBK is added to the resulting resin, and the resulting resin is then washed, dehydrated, filtered, and desolvated to obtain the desired resin. Furthermore, a solvent such as dioxane or DMSO may be used in combination during the reaction to reduce the amount of chlorine impurities.

[0088] The epihalohydrin used here is most commonly epichlorohydrin, but other epiiodohydrin, epibromohydrin, β-methylepichlorohydrin, etc. can also be used.

[0089] Furthermore, in this embodiment, when the epoxy resin (A') is used as the epoxy resin to be incorporated into the resin composition, particularly for build-up adhesive film applications, it is preferable to use a naphthalene-type epoxy resin obtained by glycidyl etherifying the aforementioned bis(dihydroxynaphthyl)methane in combination, since this improves the breaking strength of the cured product and also improves the crosslink density of the cured product. Here, the amount of the naphthalene-type epoxy resin used is preferably 30 to 100 parts by mass per 100 parts by mass of the epoxy resin (A'). This appropriately suppresses the solution viscosity of the resin composition, improves degassing properties, particularly during vacuum lamination in the production of build-up adhesive films, and effectively prevents the occurrence of voids. In the resin composition of this embodiment, the content of the epoxy resin (e.g., epoxy resin (A')) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass, based on the total resin composition.

[0090] [Other Components] In addition to the active ester compound and epoxy resin, the resin composition of the present embodiment may contain a resin curing agent such as an amine compound, an amide compound, an acid anhydride compound, or a phenol compound, within a range that does not impair the effects of the present invention. In the resin composition of the present embodiment, the content of the resin curing agent can be 0.01 to 10 mass % with respect to the entire resin composition.

[0091] Examples of the amine compounds that can be used here include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, and BF ３ Examples of the amide-based compound include dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, and the like. In the resin composition of this embodiment, the content of the amine-based compound can be 0.01 to 10 mass% based on the entire resin composition. Examples of the amide-based compound include dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, and the like. In the resin composition of this embodiment, the content of the amide-based compound can be 0.01 to 10 mass% based on the entire resin composition.

[0092] Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. In the resin composition of this embodiment, the content of the acid anhydride compound can be 0.01 to 10% by mass with respect to the entire resin composition.

[0093] Examples of phenolic compounds include phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resins, dicyclopentadiene-phenol adduct resins, phenol aralkyl resins, α-naphthol aralkyl resins, β-naphthol aralkyl resins, biphenyl aralkyl resins, trimethylolmethane resins, tetraphenylolethane resins, naphthol novolac resins, naphthol-phenol co-condensed novolac resins, naphthol-cresol co-condensed novolac resins, and aminotriazine-modified phenolic resins. Specific examples of the aminotriazine-modified phenolic resins include copolymers of an amino group-containing triazine compound such as melamine or benzoguanamine, a phenol such as phenol or cresol, and formaldehyde. In the resin composition of this embodiment, the content of the phenolic compound can be 10 to 90% by mass based on the total resin composition.

[0094] Among these, polyhydric phenol compounds are preferred, and phenol novolac resins, cresol novolac resins, phenol aralkyl resins, α-naphthol aralkyl resins, β-naphthol aralkyl resins, biphenyl aralkyl resins, and aminotriazine-modified phenol resins are preferred, as they result in a cured product with a lower linear expansion coefficient, and are resistant to thermal and physical impacts and have excellent toughness.

[0095] The resin composition of the present embodiment may further contain a curing accelerator in addition to the above-described components.

[0096] Examples of the curing accelerator that can be used here include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, etc. Among these, imidazoles are preferred because they have a significant effect of reducing the linear expansion coefficient of the cured product.

[0097] The amount of the curing accelerator to be added can be adjusted appropriately depending on the target curing time, etc., but is preferably in the range of 0.1 to 7% by mass relative to the total mass of the epoxy resin component, the curing agent component, and the curing accelerator.

[0098] In addition to the above-described components, the resin composition of this embodiment can further contain an organic solvent depending on the intended use. For example, when the resin composition is used as a varnish for laminates, the impregnation into the substrate is improved, and when used as a build-up film, the coating properties on the substrate sheet are improved. Examples of organic solvents that can be used here include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0099] The resin composition of the present embodiment may contain, in addition to the above-described components, inorganic fillers, modifiers, flame retardants, and the like, as appropriate, depending on the intended use.

[0100] Examples of inorganic fillers used here include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, magnesium hydroxide, etc. Among these, fused silica is particularly preferred because it can increase the filling rate of the inorganic filler. Here, fused silica can be used in either crushed or spherical form, but in order to increase the amount of fused silica blended and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use spherical silica. Furthermore, in order to increase the amount of spherical silica blended, it is preferable to appropriately adjust the particle size distribution of the spherical silica.

[0101] The desirable range of the blending ratio of the inorganic filler varies depending on the application and the desired properties, but for example, when used as a semiconductor encapsulant, a higher blending ratio is preferable in consideration of the linear expansion coefficient and flame retardancy, and a range of 65 to 95 mass % and particularly 85 to 95 mass % relative to the total amount of the resin composition is preferred. Furthermore, when used as a conductive paste or conductive film, a conductive filler such as silver powder or copper powder can be used.

[0102] As the thermosetting resin and thermoplastic resin used as the modifier, various types can be used, and examples thereof include phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene ether resin, polyphenylene sulfide resin, polyester resin, polystyrene resin, polyethylene terephthalate resin, etc.

[0103] Examples of the flame retardant include halogen compounds, phosphorus atom-containing compounds, nitrogen atom-containing compounds, and inorganic flame retardant compounds. Specific examples of the flame retardant include halogen compounds such as tetrabromobisphenol A epoxy resins and brominated phenol novolac epoxy resins; phosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris(2,6 dimethylphenyl)phosphate, and resorcinol diphenyl phosphate; phosphorus atom-containing compounds such as ammonium polyphosphate, polyphosphoric acid amide, red phosphorus, guanidine phosphate, and condensed phosphate ester compounds such as dialkylhydroxymethylphosphonate; nitrogen atom-containing compounds such as melamine; and inorganic flame retardant compounds such as aluminum hydroxide, magnesium hydroxide, zinc borate, and calcium borate. However, since the resin composition of the present embodiment is characterized by exhibiting excellent flame retardant effect without using a halogen-based flame retardant that has a high environmental impact, when the above-mentioned flame retardant is used, it is preferable to use a phosphorus atom-containing compound, a nitrogen atom-containing compound, or an inorganic flame retardant compound.

[0104] The resin composition of the present embodiment can be obtained by uniformly mixing an epoxy resin, an active ester compound, and other compounding ingredients as needed. In this case, as described above, viscosity may be adjusted by adding an organic solvent as needed for the purpose of improving workability, depending on the intended use, and heat curing conditions.

[0105] The conditions for heat curing the resin composition of this embodiment are not particularly limited, and curing can be performed under conditions for curing ordinary phenolic resins. As long as the temperature is equal to or higher than the softening temperature of the resin component, the curing can usually be performed at a temperature of 120°C to 250°C. In particular, a temperature range of 130 to 200°C is preferred from the viewpoint of improving moldability. In addition, in order to obtain a friction material with excellent heat resistance, it is preferable to bake the composition after molding.

[0106] The resin composition of the present embodiment described above in detail can be used as a resin composition for resist ink, a binder for friction materials, a resin composition for copper-clad laminates, an interlayer insulating material for build-up printed circuit boards, an adhesive film for build-up, a resin composition for sealing materials for electronic components, a conductive paste, a resin casting material, an adhesive, a coating material such as an insulating paint, and the like.

[0107] [Characteristics of Resin Composition] The resin composition of this embodiment preferably has a total chlorine content of 200 ppm by mass or less. From the viewpoint of reliability, the total chlorine content of the resin composition is more preferably 190 ppm by mass or less. Furthermore, from the viewpoint of industrially advantageous production, the total chlorine content of the resin composition may be 1 ppm by mass or more. The total chlorine content can be measured in the same manner as the total chlorine content of the active ester compound.

[0108] The resin composition of this embodiment preferably has a dielectric constant of 4 or less at 1 GHz, and a dielectric constant of 3.5 or less at 10 GHz.

[0109] The resin composition of this embodiment preferably has a dielectric loss tangent of 0.02 or less at 1 GHz and a dielectric loss tangent of 0.015 or less at 10 GHz. The dielectric loss tangent can be measured by a cavity resonance method using a network analyzer "E8362C" manufactured by Agilent Technologies, Inc., in accordance with JIS-C-6481.

[0110] From the viewpoint of heat resistance, the resin composition of the present embodiment preferably has a glass transition temperature (Tg) of 130° C. or higher. The glass transition temperature (Tg) can be measured using a viscoelasticity measuring device (DMA: "EXTRA6000" manufactured by SII Corporation; frequency 1 Hz, temperature rise rate 3° C. / min).

[0111] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to the following examples in any way.

[0112] <Measurement and Evaluation Methods> Measurement and evaluation were carried out by the following methods.

[0113] [Measurement of Total Chlorine] A sample was collected in a heat-resistant and pressure-resistant (stainless steel copper) SUS can so that the solid content of the active ester compound was 5 g, 50 g of water was added, and the sample was heated at a high temperature and pressure of 160°C for 20 hours. After cooling to 30°C or below, 3 mL of a 30% by mass aqueous acetic acid solution was added, and a 0.002 mol% / L aqueous silver nitrate solution was added dropwise using an AT-310J (manufactured by Kyoto Electronics Manufacturing Co., Ltd.) to measure the chloride ions in the water by potentiometric titration. The chloride ions in the obtained water were used to calculate the total amount of chlorine according to the following formula: Chloride ions in water [ppm by mass] x 10 = total chlorine [ppm by mass]

[0114] [Measurement of Free Chlorine] A sample was collected so that the solid content of the active ester compound was approximately 10 g, and 100 mL of tetrahydrofuran (THF) and 3 mL of a 30% by mass aqueous solution of acetic acid were added thereto. Using an AT-310J titrator manufactured by Kyoto Electronics Manufacturing Co., Ltd., a silver nitrate aqueous solution having a concentration of 0.002 mol % / L was added dropwise thereto, and potentiometric titration was performed to determine the amount of free chlorine.

[0115] [Calculation of Hydrolyzable Chlorine] From the total chlorine amount and the free chlorine amount determined by the above measurement methods, the hydrolyzable chlorine amount was calculated according to the following formula: (Hydrolyzable chlorine) = (Total chlorine) - (Chlorine ions)

[0116] [Gel Time] Using an automatic curing property measuring device (manufactured by Matsuo Sangyo Co., Ltd., model name: Madoka), the resin composition was stirred at 160°C at a rotation speed of 100 rpm and a revolution speed of 40 rpm, and the number of seconds until the stirring torque exceeded 50% of the maximum was measured to determine the gel time at 160°C.

[0117] [Dielectric Constant and Dielectric Loss Tangent] The cured resin was dried and then stored in a dryer at 80°C for 24 hours, and then the dielectric constant and dielectric loss tangent of the cured resin were measured at 1 GHz and 10 GHz using an impedance material analyzer "HP4291B" manufactured by Agilent Technologies Inc. according to a method in accordance with JIS-C-6481.

[0118] [Glass Transition Temperature (Tg)] The cured resin was evaluated using a viscoelasticity measuring device (DMA: "EXTRA6000" manufactured by SII Corporation; frequency 1 Hz, temperature rise rate 3°C / min) to determine the temperature at which the change in elastic modulus was maximum (the rate of change in tan δ was greatest) as the glass transition temperature.

[0119] Example 1 Synthesis of Active Ester Compound The following raw materials were used: Polycarboxylic acid halide: isophthalic acid chloride Polyphenolic hydroxyl group-containing compound: dicyclopentadiene phenol resin (hydroxyl group equivalent: 165 g / eq) Aromatic monohydroxy compound: α-naphthol 80.6 g (0.56 mol) of α-naphthol, 184.8 g of dicyclopentadiene phenol resin (hydroxyl group equivalent: 165 g / eq, hydroxyl groups: 1.12 mol), and 1,123.9 g of toluene were charged into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer, and the system was purged with nitrogen under reduced pressure to allow dissolution. Next, 170.5 g of isophthalic acid chloride (acid chloride groups: 1.68 mol) was charged and allowed to dissolve. Subsequently, 0.94 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen gas, the system was controlled to below 60°C, and 346.1 g (1.73 mol) of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued under these conditions for 1.0 hour. After the reaction was completed, the mixture was allowed to stand for separation, and the aqueous layer was removed. Water was then added to the toluene phase containing the dissolved reactants, and the mixture was stirred for approximately 10 minutes. The mixture was then allowed to stand for separation, and the aqueous layer was removed. This procedure was repeated until the pH of the aqueous layer reached 7. Water was then removed using decane and dehydration, yielding an active ester compound A in a toluene solution with a non-volatile content of 61-63%. Example 2 - Preparation of Resin Composition and Cured Resin - The epoxy resin and active ester compound A were kneaded at 150°C for 60 minutes in the formulation shown in Table 2 below, and a catalyst (Curesol 1B2MZ, 0.5 parts by mass per 100 parts by mass of epoxy resin) was added to obtain a resin composition. The obtained resin composition was injection molded under conditions of a mold temperature of 180°C, a molding pressure of 4 MPa, and a curing time of 20 minutes to obtain a cured resin product, which was then further heated at 175°C for 5 hours to obtain a cured resin product.

[0120] Comparative Example 1 - Synthesis of active ester compound - Except for changing the amount of aqueous sodium hydroxide solution to 336.0 g (1.68 mol), active ester compound B was obtained in the same manner as in Example 1. Comparative Example 2 - Preparation of resin composition and cured resin - Except for using active ester compound B in Comparative Example 1 instead of active ester compound A, a resin composition was obtained in the same manner as in Example 1, and a cured resin was obtained from the resin composition in the same manner as in Example 1.

[0121] The synthesis conditions and evaluation results of the active ester compounds in Example 1 and Comparative Example 1 are shown in Table 1.

[0122]

[0123] Table 1 shows that when the amount of the basic catalyst added exceeds 1.00 moles per mole of the total hydroxyl groups in the polyhydric phenolic hydroxyl group-containing compound and the aromatic monohydroxy compound, the total chlorine amount, the free chlorine amount, and the hydrolyzable chlorine amount in the active ester compound are all significantly reduced compared to the comparative examples.

[0124] Table 2 shows the preparation conditions for the resin compositions in Example 2 and Comparative Example 2, each containing the active ester compound A of Example 1 and the active ester compound B of Comparative Example 1, as well as the evaluation results of the resin compositions and cured resin products.

[0125]

[0126] Table 2 shows that when a resin composition is used that uses an active ester compound in which the amount of basic catalyst blended is more than 1.00 moles per mole of the total hydroxyl groups in the polyhydric phenolic hydroxyl group-containing compound and the aromatic monohydroxy compound, the gel time is shortened and the reactivity is improved.

[0127] This application claims the benefit of Japanese Patent Application No. 2024-24875, filed on February 21, 2024, the contents of which are incorporated herein by reference.

[0128] According to the present disclosure, it is possible to provide a method for producing an active ester compound that can produce an active ester compound containing reduced halogen ions.

Claims

1. A method for producing an activated ester compound, comprising reacting a polycarboxylic acid halide, a polyphenolic hydroxyl group-containing compound, and an aromatic monohydroxy compound in the presence of a basic catalyst, wherein the amount of the basic catalyst is greater than 1.00 moles per mole of the total hydroxyl groups in the polyphenolic hydroxyl group-containing compound and the aromatic monohydroxy compound.

2. The method for producing an active ester compound according to claim 1, wherein the amount of the basic catalyst is more than 1.00 moles and not more than 10 moles per mole of the total hydroxyl groups in the polyhydric phenolic hydroxyl group-containing compound and the aromatic monohydroxy compound.

3. The method for producing an active ester compound according to claim 1, wherein the basic catalyst is a metal hydroxide.

4. The method for producing an active ester compound according to claim 3, wherein the basic catalyst is an alkali metal hydroxide.

5. The method for producing an active ester compound according to claim 4, wherein the basic catalyst is sodium hydroxide or potassium hydroxide.

6. The method for producing an active ester compound according to claim 1, wherein the polycarboxylic acid halide is an aromatic dicarboxylic acid halide.

7. The method for producing an active ester compound according to claim 6, wherein the aromatic dicarboxylic acid halide is an aromatic dicarboxylic acid chloride.

8. The method for producing an active ester compound according to claim 7, wherein the aromatic dicarboxylic acid chloride is one or more compounds selected from the group consisting of isophthalic acid dichloride, terephthalic acid dichloride, 1,4-naphthalenedicarboxylic acid dichloride, 2,3-naphthalenedicarboxylic acid dichloride, and 2,6-naphthalenedicarboxylic acid dichloride.

9. A method for producing an active ester compound according to claim 1, wherein the polyhydric phenolic hydroxyl group-containing compound is a compound having a molecular structure in which two or more phenolic compounds are linked via an alicyclic hydrocarbon group.

10. The method for producing an active ester compound according to claim 1, wherein the aromatic monohydroxy compound is one or more compounds selected from the group consisting of phenol compounds, naphthol compounds, and anthracenol compounds.

11. The method for producing an active ester compound according to claim 10, wherein the aromatic monohydroxy compound is one or more compounds selected from the group consisting of phenol, alkylphenol, aralkylphenol, and naphthol.

12. The method for producing an active ester compound according to claim 1, wherein the polyvalent carboxylic acid halide is reacted with the polyvalent phenolic hydroxyl group-containing compound in a proportion of 0.05 mol to 0.75 mol of phenolic hydroxyl groups and the aromatic monohydroxy compound in a proportion of 0.25 mol to 0.95 mol per mol of acid halide groups in the polyvalent carboxylic acid halide.

13. An active ester compound, wherein the synthesis raw materials are a polycarboxylic acid halide, a polyphenolic hydroxyl group-containing compound, an aromatic monohydroxy compound, and a basic catalyst, and the amount of the basic catalyst added to the synthesis raw materials is more than 1.00 mole per mole of the total hydroxyl groups in the polyphenolic hydroxyl group-containing compound and the aromatic monohydroxy compound.

14. The active ester compound according to claim 13, having a hydrolyzable chlorine content of 150 ppm by mass or less.

15. A resin composition comprising the active ester compound according to claim 13 and an epoxy resin.

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