WO2020032102A1 - Novel onium compound - Google Patents

Novel onium compound Download PDF

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Publication number
WO2020032102A1
WO2020032102A1 PCT/JP2019/031116 JP2019031116W WO2020032102A1 WO 2020032102 A1 WO2020032102 A1 WO 2020032102A1 JP 2019031116 W JP2019031116 W JP 2019031116W WO 2020032102 A1 WO2020032102 A1 WO 2020032102A1
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group
phenolate
bis
thermosetting resin
hydroxy
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PCT/JP2019/031116
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French (fr)
Japanese (ja)
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将範 大賀
賢治 大橋
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北興化学工業株式会社
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Priority to JP2020535834A priority Critical patent/JPWO2020032102A1/en
Publication of WO2020032102A1 publication Critical patent/WO2020032102A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
    • C07C39/16—Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used

Definitions

  • the present invention relates to a thermosetting resin-based composition having good curability and a thermosetting resin-based cured product having good adhesiveness and heat resistance.
  • thermosetting resin-based composition represented by an epoxy resin or the like can provide a molded article having excellent mechanical, chemical and electrical properties.
  • epoxy resin-based compositions are preferably used because of their excellent adhesive properties.
  • the performance of the thermosetting resin composition is also required to be more excellent.
  • thermosetting resin-based composition for sealing materials is particularly important in adhesion to copper and aluminum.
  • thermosetting resin composition for semiconductor encapsulation is required to have higher heat resistance than ever.
  • thermosetting resin composition having a short molding cycle that is, having high curability is required from the viewpoint of cost reduction and energy saving.
  • the curing accelerator contained as a component in the thermosetting resin composition when added, promotes the curing of the thermosetting resin composition, as well as the curability and adhesion of the molded product as a cured product. Since various properties such as heat resistance and heat resistance are affected, it is extremely important to select a suitable curing accelerator.
  • thermosetting resin that provides a thermosetting resin-based composition having an excellent balance of curability, adhesiveness, heat resistance, and the like.
  • adhesiveness, the curability, and the heat resistance tend to be in a trade-off relationship, and it has been difficult to satisfy these at the same time.
  • thermosetting resins there are phosphorus-based or imidazole-based curing accelerators for existing thermosetting resins, especially for epoxy resins.However, it is possible to obtain cured products with high curing power and high electrical reliability.
  • Phosphorus compounds are generally known. Among them, triphenylphosphine and tris (4-methylphenyl) are used as a curing accelerator for a thermosetting resin which gives a thermosetting resin composition having good adhesiveness. Phosphine (see Non-Patent Document 1).
  • a quaternary phosphonium salt comprising a phosphonium cation and an anionic residue is also known as a phosphorus-based curing accelerator.
  • anionic residues include carboxylate and phenolate, respectively.
  • Phosphonium carboxylate see Patent Literature 1
  • phosphonium phenolate see Patent Literature 2 and Patent Literature 3.
  • Thermosetting resin-based compositions containing these are all curable and adhesive. And heat resistance were not simultaneously satisfied.
  • an object of the present invention is to provide a thermosetting resin-based composition having good curability and a thermosetting resin-based cured product having good adhesiveness and heat resistance.
  • a thermosetting resin composition having good curability by blending an onium phenolate comprising a residue (hereinafter, sometimes referred to as “onium salt of the present invention”) as a curing accelerator, and an adhesive property It has been found that a thermosetting resin-based cured product having good heat resistance can be obtained, and the present invention has been completed.
  • the anion residue of the phenol derivative refers to a phenolate anion in which a proton has been removed from the phenolic hydroxyl group of the phenol derivative.
  • R 1 to R 4 are the same or different and each represent a substituted or unsubstituted hydrocarbon group having 1 to 16 carbon atoms, and Q represents a phosphorus atom or a nitrogen atom.
  • An onium phenolate comprising an anionic residue of at least one phenol derivative selected from the group consisting of phenol derivatives represented by the following general formulas (2) to (5).
  • R 5 , R 6 and R 7 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group.
  • c is the same or different, a and c each represent an integer of 0 to 4, b represents an integer of 0 to 3.
  • a plurality of R 5 , R 6 and R 7 may be the same or different, and p represents an integer of 0 to 4.
  • R 8 , R 9 and R 10 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group; f is the same or different and represents an integer of 0 to 4.
  • R 8 , R 9 , and R 10 are the same or different.
  • R 11 represents a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms (alkyl group), or a phenyl group which may be substituted with an alkyl group or a methoxy group.
  • R 12 , R 13 , R 14 and R 15 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group;
  • H, i, j are the same or different and each represent an integer of 0 to 4.
  • a plurality of each of R 12 , R 13 , R 14 and R 15 may be the same or different, and X is a single bond, a divalent saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms (alkyl group) or a saturated alicyclic hydrocarbon group (cycloalkyl group).
  • R 16 , R 17 , R 18 and R 19 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group; , L, m, and n are the same or different and each represent an integer of 0 to 4. When k, 1, m, and n represent an integer of 2 or more, a plurality of R 16 , R 17 , R 18 and R 19 may be the same or different.
  • R 1 to R 4 are the same or different and are butyl, phenyl, 4-methylphenyl, 4-methoxyphenyl, benzyl, methoxymethyl, and carboxy.
  • thermosetting resin comprising at least the onium phenolate according to any one of [1] to [8].
  • thermosetting resin composition containing at least the curing accelerator for thermosetting resin according to [9] and a thermosetting resin.
  • thermosetting resin composition according to [10] or [11], further comprising a thermosetting resin curing agent.
  • thermosetting resin is one or more curing agents for a thermosetting resin selected from a phenol resin, a polyamine, an acid anhydride, and benzoxazine.
  • Thermosetting resin composition is one or more curing agents for a thermosetting resin selected from a phenol resin, a polyamine, an acid anhydride, and benzoxazine.
  • thermosetting resin-based composition according to [12] or [13], wherein the curing accelerator for the thermosetting resin includes the curing accelerator for the thermosetting resin and the curing accelerator for the thermosetting resin.
  • a thermosetting resin composition which is a master batch reacted with a part of a curing agent.
  • thermosetting resin-based cured product obtained by curing the thermosetting resin-based composition according to any one of [10] to [14].
  • thermosetting resin composition and the cured product containing the onium salt-containing thermosetting resin curing accelerator of the present invention as a component compared with the case where a conventional curing accelerator is used, the curability, adhesiveness and This is useful because the heat resistance is improved.
  • FIG. 1 is a diagram showing an IR spectrum of tetraphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate.
  • FIG. 2 is a view showing an IR spectrum of tetrabutylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate.
  • FIG. 3 shows an IR spectrum of tetrabutylphosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate.
  • FIG. FIG. 4 is a diagram showing an IR spectrum of tetrabutylphosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate.
  • FIG. 5 is a diagram showing an IR spectrum of tetrabutylphosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate.
  • FIG. 6 is a diagram showing an IR spectrum of tetrabutylammonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate.
  • FIG. 7 is a view showing an IR spectrum of butyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate.
  • FIG. 8 is a view showing an IR spectrum of benzyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate.
  • FIG. 9 is a view showing an IR spectrum of methoxymethyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate.
  • substituted or unsubstituted hydrocarbon group means a hydrocarbon group having 1 to 16 carbon atoms, which may be an aliphatic hydrocarbon group which may have a substituent, Containing aromatic hydrocarbon groups.
  • the hydrocarbon group has a substituent, the number of carbon atoms of the hydrocarbon group does not include the number of carbon atoms contained in the substituent.
  • the aliphatic hydrocarbon group which may have a substituent may be a linear or branched saturated aliphatic hydrocarbon group, or a linear or branched unsaturated aliphatic group. It may be a hydrocarbon group.
  • aliphatic hydrocarbon group examples include methyl, ethyl, n-propyl, isopropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-ethylpropyl, and alkyl groups.
  • n-butyl group isobutyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethyl-2-methylbutyl group, n-pentyl group, neopentyl group, 2-pentyl, 3-pentyl, tert-pentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methyl Rupentyl group, 1-ethylpentyl group, 2-ethylpentyl group, n-hexyl group, isohexyl group, 2-hexyl group, 3-hex
  • the aliphatic hydrocarbon group which may have a substituent may be an alicyclic hydrocarbon group.
  • the alicyclic hydrocarbon group may be an alicyclic saturated hydrocarbon group or an alicyclic unsaturated hydrocarbon group.
  • the alicyclic hydrocarbon group as a cycloalkyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and other alicyclic saturated hydrocarbon groups
  • the cycloalkenyl group include an alicyclic unsaturated hydrocarbon group such as a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.
  • the aromatic hydrocarbon group which may have a substituent may be a monocyclic or polycyclic aromatic hydrocarbon. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthracenyl group as the aryl group.
  • examples of the substituent which may be substituted on the aliphatic hydrocarbon group include an alkoxy group having 1 to 4 carbon atoms, an aryl group, an aryloxy group, a hydroxyl group, a carboxy group, an acyl group, an amino group, a halogen atom and the like. Is mentioned.
  • Specific examples of the aliphatic hydrocarbon group having a substituent include a methoxymethyl group and an ethoxymethyl group as an alkoxy-substituted alkyl group, and a benzyl group and the like as an aryl-substituted alkyl group.
  • the substituent which may be substituted on the aromatic hydrocarbon group includes an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, an aryloxy group, a hydroxyl group, a carboxy group, An acyl group, an amino group, a halogen atom and the like can be mentioned.
  • aromatic hydrocarbon group having a substituent examples include an alkyl group-substituted aryl group such as a tolyl group, a dimethylphenyl group, an ethylphenyl group, a propylphenyl group, an n-butylphenyl group, a t-butylphenyl group, Examples of the alkoxy-substituted aryl group include a methoxyphenyl group, an ethoxyphenyl group, an n-butoxyphenyl group, and a t-butoxyphenyl group.
  • the aliphatic hydrocarbon group or the aromatic hydrocarbon group has a substituent
  • the position of the substituent and the number of the substituent are not particularly limited. When it has two or more substituents, they may be the same or different.
  • the divalent saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms (alkyl group) or saturated alicyclic hydrocarbon group (cycloalkyl group) includes methylene, ethylene, propylene, n- Examples thereof include a butylene group, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornylene group, and an adamantylene group.
  • the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
  • R 1 to R 4 are the same or different and each represent a substituted or unsubstituted hydrocarbon group having 1 to 16 carbon atoms, and Q represents a phosphorus atom or a nitrogen atom.
  • An onium phenolate comprising an anionic residue of at least one phenol derivative selected from the group consisting of phenol derivatives represented by the following general formulas (2) to (5).
  • R 5 , R 6 and R 7 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group.
  • c is the same or different, a and c each represent an integer of 0 to 4, b represents an integer of 0 to 3.
  • R 5 , R 6 , and R 7 may be the same or different, and p represents an integer of 0 to 4.
  • R 8 , R 9 and R 10 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group; f is the same or different and represents an integer of 0 to 4.
  • R 8 , R 9 , and R 10 are the same or different.
  • R 11 represents a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms (alkyl group), or a phenyl group which may be substituted with an alkyl group or a methoxy group.
  • R 12 , R 13 , R 14 and R 15 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group;
  • H, i, j are the same or different and each represent an integer of 0 to 4.
  • a plurality of each of R 12 , R 13 , R 14 and R 15 may be the same or different, and X is a single bond, a divalent saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms (alkyl group) or a saturated alicyclic hydrocarbon group (cycloalkyl group).
  • R 16 , R 17 , R 18 and R 19 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group; , L, m, and n are the same or different and each represent an integer of 0 to 4. When k, 1, m, and n represent an integer of 2 or more, a plurality of R 16 , R 17 , R 18 and R 19 may be the same or different.
  • ⁇ Onium cation ⁇ Q in the onium cation of the general formula (1) is a phosphorus atom or a nitrogen atom.
  • R 1 to R 4 in the onium cation of the general formula (1) are the same or different and represent a substituted or unsubstituted hydrocarbon group having 1 to 16 carbon atoms.
  • the substituent represented by R 1 to R 4 is a substituted or unsubstituted hydrocarbon group having 1 to 16 carbon atoms. It is preferably from 1 to 12, more preferably from 1 to 6 carbon atoms.
  • hydrocarbon group in addition to the above substituents, specifically, ethyl group, propyl group, n-butyl group, octyl group, dodecyl group, allyl group, cyclohexyl group, methoxymethyl group, benzyl group, carboxyethyl group, phenyl Groups, 4-methylphenyl group and 4-methoxyphenyl group are preferable, and n-butyl group, benzyl group, methoxymethyl group, carboxyethyl group and phenyl group are particularly preferable.
  • Examples of the onium cation of the general formula (1) include tetrabutylphosphonium cation, tetraphenylphosphonium cation, tetrakis (4-methylphenyl) phosphonium cation, tetrakis (4-methoxyphenyl) phosphonium cation, and phenyltris (4-methylphenyl) phosphonium Cation, phenyltris (4-methoxyphenyl) phosphonium cation, phenyltributylphosphonium cation, (4-methylphenyl) triphenylphosphonium cation, (4-methoxyphenyl) triphenylphosphonium cation, butyltriphenylphosphonium cation, tetrabutylammonium cation , Tetraphenylammonium cation, tetrakis (4-methylphenyl) ammonium cation, tetrakis (4-meth
  • tetrakis (methoxymethyl) phosphonium cation tetrakis (carboxyethyl) phosphonium cation, tetrabenzylphosphonium cation, phenyltris (methoxymethyl) phosphonium cation, phenyltris (carboxyethyl) phosphonium cation, phenyltribenzylphosphonium cation, (methoxymethyl) ) Triphenylphosphonium cation, (carboxyethyl) triphenylphosphonium cation, benzyltriphenylphosphonium cation, tetrakis (methoxymethyl) ammonium cation, tetrakis (carboxyethyl) ammonium cation, tetrabenzylammonium cation, phenyltris (methoxymethyl) ammonium cation , Phenyltris (carbox
  • tetrabutylphosphonium cation tetraphenylphosphonium cation, butyltriphenylphosphonium cation, (4-methylphenyl) triphenylphosphonium cation, (4-methoxyphenyl) triphenylphosphonium cation, tetrabutylammonium cation, tetraphenylammonium Cations, butyltriphenylammonium cations, (4-methylphenyl) triphenylammonium cations, and (4-methoxyphenyl) triphenylammonium cations are preferred.
  • (methoxymethyl) triphenylphosphonium cation (carboxyethyl) triphenylphosphonium cation, benzyltriphenylphosphonium cation, (methoxymethyl) triphenylammonium cation, (carboxyethyl) triphenylammonium cation, and benzyltriphenylammonium cation preferable.
  • Phenolate anion (anion residue) Since it is presumed that the proton at the position where the resulting phenolate anion can be most stably present is removed from the phenolic hydroxyl group of the phenol derivative. Since it may form an intramolecular hydrogen bond, it is difficult to estimate from which phenolic hydroxyl group a proton is released, but it can be estimated by NMR measurement in some cases.
  • R 5 , R 6 , and R 7 are the same or different and are each a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, Or an amino group.
  • a, b and c are the same or different, a and c each represent an integer of 0 to 4, and b represents an integer of 0 to 3.
  • a, b, and c represent an integer of 2 or more, each of a plurality of R 5 , R 6 , and R 7 may be the same or different.
  • P represents an integer of 0 to 4.
  • saturated aliphatic hydrocarbon group (alkyl group) having 1 to 4 carbon atoms as R 5 , R 6 and R 7 in the phenolate anion of the general formula (2)
  • a methyl group, an ethyl group or a hydroxyl group having 1 to 2 carbon atoms is preferable, and a methyl group or a hydroxyl group is particularly preferable.
  • the integers a to c indicating the number of substituents of R 5 , R 6 , and R 7 substituted on the aromatic ring may be the same or different.
  • c is an integer of 2 or more
  • each of a plurality of R 5 , R 6 , and R 7 may be the same or different, and specifically, is preferably an integer of 0 to 2.
  • the integers a to c are 1, preferred substituents for R 5 , R 6 and R 7 are a methyl group or a hydroxyl group.
  • the integer of a to c is 2, the substituent of R 5 , R 6 and R 7 is preferably a methyl group.
  • the position of the substituent of R 5 , R 6 , and R 7 may be any position on the aromatic ring, but when R 5 , R 6 , or R 7 is an alkyl group, it may be the meta position of the methylene group.
  • R 5 , R 6 , and R 7 are hydroxyl groups, they are preferably in the ortho or para position of the methylene group, and the position of the hydroxyl group forming phenol may be any position on the aromatic ring, It is preferably at the ortho or para position of the methylene group.
  • P p indicating an index of the degree of polymerization of the phenol derivative is an integer from 0 to 4.
  • the phenol derivative is a phenol monomer trimer
  • the phenol derivative is a phenol monomer tetramer. That is, p + 2 is the degree of polymerization of the phenol derivative.
  • p is preferably an integer of 1 or 2.
  • More preferred phenolate anions of the general formula (2) include the above-mentioned general formulas (2′-2) and (2′-3) where p is an integer of 1 or 2, and more preferred general formula ( As the phenolate anion of 2), the following formulas (2′-2-1), (2′-2-2), and (2′-2) wherein R 5 , R 6 , and R 7 are a methyl group or a hydroxyl group. -3) and (2'-3-1).
  • R 8 , R 9 , and R 10 are the same or different and are each a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or Represents an amino group; d, e, and f are the same or different and each represents an integer of 0 to 4; When d, e, and f each represent an integer of 2 or more, a plurality of R 8 , R 9 , and R 10 may be the same or different.
  • R 11 is a substituent representing a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms (alkyl group), or a phenyl group which may be substituted with an alkyl group or a methoxy group.
  • R 8 , R 9 , and R 10 in the phenolate anion of the general formula (3) as the saturated aliphatic hydrocarbon group (alkyl group) having 1 to 4 carbon atoms, specifically, in addition to the above-mentioned substituents, And a methyl group, an ethyl group or a hydroxyl group having 1 to 2 carbon atoms is preferable, and a methyl group or a hydroxyl group is particularly preferable.
  • the integers of d to f indicating the number of substituents of R 8 , R 9 and R 10 substituted on the aromatic ring may be the same or different.
  • d to f are integers of 2 or more, each of R 8 , R 9 , and R 10 may be the same or different, and specifically, is preferably an integer of 0 to 2.
  • the integer of d to f is 1, preferred substituents for R 8 , R 9 and R 10 are a methyl group or a hydroxyl group.
  • the substituent of R 8 , R 9 , and R 10 is preferably a methyl group.
  • the position of the alkyl group having 1 to 4 carbon atoms of R 8 , R 9 and R 10 may be any position on the aromatic ring, but is preferably the ortho position of the hydroxyl group.
  • the saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms (alkyl group) represented by R 11 in the phenolate anion of the general formula (3) is, in addition to the above-mentioned substituents, specifically, a C 1 to C 4 alkyl group.
  • Alkyl groups are preferred. More specifically, it is more preferably a methyl group or an ethyl group.
  • the phenyl group which may be substituted by the alkyl group or the methoxy group of R 11 in the phenolate anion is an alkyl group having 1 to 4 carbon atoms which may be substituted by the phenyl group. Specifically, a methyl group is preferred. Therefore, as the phenyl group which may be substituted with an alkyl group or a methoxy group, more specifically, a phenyl group, a 4-methylphenyl group, or a 4-methoxyphenyl group is preferable, and a phenyl group is more preferable. preferable.
  • R 11 in the phenolate anion of the general formula (3) is preferably a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, and particularly preferably a hydrogen atom or a methyl group.
  • More preferred phenolate anions of the general formula (3) include the following general formulas (3′-1) and (3′-2).
  • R 12 , R 13 , R 14 and R 15 in the phenolate anion of the general formula (4) are the same or different and are a hydrogen atom, a saturated aliphatic hydrocarbon group (alkyl group) having 1 to 4 carbon atoms, a hydroxyl group, or Represents an amino group; g, h, i, and j are the same or different and each represent an integer of 0 to 4; When g, h, i, and j each represent an integer of 2 or more, a plurality of R 12 , R 13 , R 14 , and R 15 may be the same or different.
  • X represents a single bond, a divalent saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms or a saturated alicyclic hydrocarbon group, or a phenylene group.
  • 1 to 4 carbon atoms 2 is preferably a methyl group, an ethyl group, or a hydroxyl group, particularly preferably a methyl group or a hydroxyl group.
  • the integers of g to j indicating the number of substituents of R 12 , R 13 , R 14 and R 15 substituted on the aromatic ring may be the same or different.
  • the integers of g to j are an integer of 2 or more, each of R 12 , R 13 , R 14 , and R 15 may be the same or different, and specifically, is preferably an integer of 0 to 2.
  • the integer of g to j is 1, a preferred substituent for R 12 , R 13 , R 14 and R 15 is a methyl group or a hydroxyl group.
  • the substituent of R 12 , R 13 , R 14 and R 15 is preferably a methyl group.
  • R 12 , R 13 , R 14 , and R 15 may be any position on the aromatic ring, but is preferably the ortho position of the hydroxyl group.
  • divalent saturated aliphatic hydrocarbon group or saturated alicyclic hydrocarbon group having 1 to 16 carbon atoms represented by X in the phenolate anion of the general formula (4) in addition to the substituents described above, specific examples include Preferably has 1 to 6 carbon atoms.
  • X in the phenolate anion of the general formula (4) specifically, a single bond, that is, two molecules of a bis (4-hydroxyphenyl) methyl group directly bonded, a methylene group, a cyclohexylene group, or A phenylene group is preferred, and a single bond or a phenylene group is particularly preferred.
  • More preferred phenolate anions of the general formula (4) include the following formulas (4′-1) and (4′-2).
  • R 16 , R 17 , R 18 , and R 19 in the phenolate anion of the general formula (5) are the same or different and are a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, an amino group.
  • k, l, m, and n are the same or different and each represents an integer of 0 to 4. When k, l, m, and n each represent an integer of 2 or more, each of a plurality of R 16 , R 17 , R 18 , and R 19 may be the same or different.
  • saturated aliphatic hydrocarbon group (alkyl group) having 1 to 4 carbon atoms as R 16 , R 17 , R 18 and R 19 in the phenolate anion of the general formula (5)
  • a methyl group, an ethyl group, or a hydroxyl group having 1 to 2 carbon atoms is preferable, and a methyl group or a hydroxyl group is particularly preferable.
  • the integers of k to n indicating the number of substituents of R 16 , R 17 , R 18 and R 19 substituted on the aromatic ring may be the same or different.
  • k to n are an integer of 2 or more, each of R 16 , R 17 , R 18 , and R 19 may be the same or different, and specifically, is preferably an integer of 0 to 2.
  • the integer of k to n is 1, a preferred substituent for R 16 , R 17 , R 18 and R 19 is a methyl group or a hydroxyl group.
  • the substituent of R 16 , R 17 , R 18 and R 19 is preferably a methyl group.
  • R 16 , R 17 , R 18 , and R 19 may be any position on the aromatic ring, but is preferably an ortho position of a hydroxyl group.
  • a more preferred phenolate anion of the general formula (5) includes the following formula (5′-1).
  • the salt of the above-mentioned onium cation and the anionic residue of the phenol derivative can be easily produced by a known method based on the description of the present specification.
  • the above-mentioned salt may be formed using one or two or more kinds of alkali metal salts of a tetra-substituted onium halide and a crystalline phenol derivative.
  • the tetra-substituted onium phenolate may be formed after two or more kinds of alkali metal salts of the tetra-substituted onium halide and the crystalline phenol derivative are first mixed, or two or more kinds may be formed. May be mixed. Production examples according to this production method are described in Production Examples 1, 7, 8, and 9.
  • a salt may be formed by neutralizing with 1 mol of a phenol derivative per 1 mol of the tetra-substituted onium hydroxide. Production examples according to this production method are described in Production Examples 2, 3, 4, 5, and 6.
  • the obtained reactant is treated with water, an alcohol-based organic solvent (methanol, ethanol, Propanol, butanol, etc., ketone organic solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, etc.), ether organic solvents (tetrahydrofuran, diethyl ether, dibutyl ether, 2-methyltetrahydrofuran, cyclopentyl methyl ether, dioxane, etc.), It may be washed with a nonpolar solvent (benzene, toluene, xylene, hexane, heptane, etc.) or a mixed solvent thereof, and purified by recrystallization.
  • a nonpolar solvent benzene, toluene, xylene, hexane, heptane, etc.
  • a mixed solvent thereof purified by recrystallization.
  • the commercially available tetra-substituted onium halide, tetra-substituted onium hydroxide, phenol derivative, and solvent may all be used.
  • the onium salt of the present invention obtained by these methods usually contains a 1: 1 (molar ratio) salt of an onium cation and an anionic residue of a phenol derivative as a main component, and has a general formula (2 ′′ -1) to (2 ′′ -5), general formula (3 ′′), general formula (4 ′′), and general formula (5 ′′).
  • the present invention relates to an onium phenolate comprising an onium cation represented by the general formula (1) and an anionic residue of a phenol derivative represented by the general formulas (2) to (5) (for example, the general formula (2 ") -1) to (2 "-5), a curing accelerator for a thermosetting resin containing at least an onium phenolate represented by the general formula (3"), the general formula (4 "), or the general formula (5")) (Hereinafter may be referred to as “curing accelerator for thermosetting resin of the present invention”).
  • thermosetting resin composition and the cured product containing the curing accelerator for thermosetting resin of the present invention as components have good curability, adhesiveness, and heat resistance.
  • the onium salt of the present invention is difficult to homogenize with the curing agent, for example, for the purpose of facilitating homogenization and the like, a master batch obtained by previously reacting the onium salt of the present invention with the curing agent is heated. It may be used as a curing accelerator for a curable resin.
  • the curing accelerator for the thermosetting resin of the present invention besides the onium salt of the present invention, a solvent, a filler, an additive, etc. which are usually used for the curing accelerator for the thermosetting resin, as long as the effect is not affected. It may further include.
  • the curing accelerator for a thermosetting resin of the present invention may be used in combination with a curing accelerator for a thermosetting resin, in addition to the onium salt.
  • Examples of the onium salts of the present invention represented by the general formulas (2 ′′ -1) to (2 ′′ -5) include tetraphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, tetrakis (4-methylphenyl) phosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, tetrakis (4-methoxyphenyl) phosphonium 2,6-bis (2-hydroxy-5-methyl Benzyl) -4-methylphenolate, tetrabutylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, phenyltris (4-methylphenyl) phosphonium 2,6-bis (2 -Hydroxy-5-methylbenzyl) -4-methylphenolate, phenyltris (4-methoxyphenyl) Phosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate
  • Examples of the onium salt of the present invention represented by the general formula (3 ′′) include tetraphenylphosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate and tetrakis (4-methylphenyl) phosphonium 4- [bis (4-hydroxyphenyl) Methyl] phenolate, tetrakis (4-methoxyphenyl) phosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, tetrabutylphosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, phenyltris (4-methylphenyl ) Phosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, phenyltris (4-methoxyphenyl) phosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, phenyltributylphosphonium 4- Bis (4-hydroxyphenyl) methyl] phenolate, (4-methylphenyl) tripheny
  • Examples of the onium salt of the present invention represented by the general formula (4 ′′) include tetraphenylphosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate and tetrakis (4-methylphenyl) phosphonium 4- [1 , 2,2-Tris (4-hydroxyphenyl) ethyl] phenolate, tetrakis (4-methoxyphenyl) phosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, tetrabutylphosphonium 4- [ 1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, phenyltris (4-methylphenyl) phosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, phenyltris (4 -Methoxyphenyl) phosphonium 4- [1,2,2-tri (4-hydroxyphenyl) ethyl]
  • the onium salt of the present invention represented by the general formula (5 ′′) includes the following general formula (5 ′′ -1). (Wherein, Q and R 1 to R 4 are as defined above.)
  • thermosetting resin-based composition comprising at least the curing accelerator for a thermosetting resin of the present invention and a thermosetting resin (hereinafter, referred to as a “single-curing thermosetting resin of the present invention”).
  • Resin-based composition ").
  • a further aspect of the present invention is a thermosetting resin composition further including a curing agent for a thermosetting resin. Hereinafter, these may be referred to as “the thermosetting resin composition of the present invention”.
  • thermosetting resins ⁇ ⁇ ⁇ ⁇ ⁇ Epoxy resins, maleimide resins, cyanate resins, isocyanate resins, and curing agents for thermosetting resins, which are preferable examples of the thermosetting resin that is a component of the thermosetting resin composition of the present invention, will be described below.
  • the epoxy resin is not particularly limited, and a general-purpose epoxy resin having two or more epoxy groups in one molecule can be used.
  • phenol, cresol, xylenol, catechol, resorcin, bisphenol A, A phenol such as bisphenol F and / or a naphthol such as naphthol and dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde are condensed or co-condensed in the presence of an acidic catalyst.
  • epoxy resins may be used alone or as a mixture of two or more kinds, may be used as they are, may be appropriately added with a solvent or an additive, or may be a commercially available product. Good.
  • the maleimide resin is not particularly limited, and a general-purpose maleimide resin having two or more maleimide groups in one molecule can be used.
  • a general-purpose maleimide resin having two or more maleimide groups in one molecule can be used.
  • maleimide resins may be used alone or as a mixture of two or more kinds, may be used as they are, may be appropriately added with a solvent or an additive, or may be a commercially available product. Good.
  • the cyanate resin is not particularly limited, and a general-purpose cyanate resin having two or more cyanate groups in one molecule can be used.
  • a general-purpose cyanate resin having two or more cyanate groups in one molecule can be used.
  • 1,3-dicyanatobenzene, Anatobenzene, 1,3,5-tricyanatobenzene, bis (3,5-dimethyl-4-cyanatophenyl) methane 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-disi Anatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4′-dicyanatobiphenyl, bis (4- Cyanatophenyl) methane, 2,2′-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ether,
  • cyanate resins may be used alone or as a mixture of two or more kinds, may be used as they are, may be appropriately added with a solvent or an additive, or may be a commercially available product. Good.
  • the isocyanate resin is not particularly limited, and a general-purpose isocyanate resin having two or more isocyanate groups in one molecule can be used.
  • polyisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate
  • polypropylene Isocyanate resins in which terminal isocyanate groups of terminal oligomers of isocyanate groups obtained by reaction with a polyol such as glycol or polytetramethylene glycol are blocked with phenols, alcohols, and the like.
  • isocyanate resins may be used alone or as a mixture of two or more kinds, may be used as they are, may be appropriately added with a solvent or an additive, or may be a commercially available product. Good.
  • thermosetting resin examples include a phenol resin-based curing agent, an amine-based curing agent, an acid anhydride-based curing agent, a benzoxazine-based curing agent, and dicyandiamide. Further, a thermosetting resin other than the thermosetting resin used as a main component of the thermosetting resin composition may be used as a curing agent for the thermosetting resin.
  • the phenolic resin-based curing agent is not particularly limited, and a general-purpose phenolic resin having two or more phenolic hydroxyl groups in one molecule, which is generally used as a curing agent, can be used.
  • catechol Compounds having two or more phenolic hydroxyl groups in one molecule such as resorcin, hydroquinone, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F
  • phenols such as phenylphenol and aminophenol and / or naphthols such as naphthol and dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde
  • the amine-based curing agent is not particularly limited, and general-purpose aromatic amines, aliphatic amines, and the like can be used. Examples thereof include triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, and trimethylhexaamine.
  • Aliphatic polyamines such as methylenediamine and 2-methylpentamethylenediamine, alicyclic rings such as isophoronediamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, and 1,2-diaminocyclohexane
  • piperazine-type polyamines such as N-aminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, diethyltoluenediamine, dimethylthiotoluenediamine, 4,4′-diamino-3, 3'-diethyldiphenyl Methane, bis (methylthio) toluenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, trimethylenebis (4-aminobenzoate), polytetramethylene oxide-
  • the acid anhydride-based curing agent is not particularly limited, and a general-purpose acid anhydride can be used.
  • a general-purpose acid anhydride can be used.
  • the benzoxazine-based curing agent is not particularly limited, and a general-purpose benzoxazine resin can be used.
  • a general-purpose benzoxazine resin can be used.
  • These hardeners can be used alone or as a mixture of two or more, and may be used as they are, and may be used as a hardener composition by appropriately adding a solvent or an additive. Alternatively, a commercially available product may be used.
  • thermosetting resin-based composition of the present invention does not affect the effect, in addition to the curing accelerator for thermosetting resin, the thermosetting resin, and / or the curing agent for thermosetting resin of the present invention. As long as it is included, it may further contain a solvent, a filler, an additive, and the like which are usually used in the thermosetting resin composition.
  • the thermosetting resin composition can contain various known inorganic fillers in order to reduce the coefficient of linear expansion. Examples of the inorganic filler include fused silica, crystalline silica, alumina, aluminum nitride, and the like. These inorganic fillers may be surface-treated with a coupling agent such as a silane coupling agent.
  • thermosetting resin-based composition a resin other than the thermosetting resin may be included.
  • the content of the onium salt of the present invention in the thermosetting resin-based composition is less than 0.5 part by weight, the curing power of the composition may not be sufficiently exhibited. Since the storage stability of the product may be deteriorated, the content is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the thermosetting resin. More preferably, the amount is 0.7 to 5 parts by weight.
  • the content of the curing agent is determined by the reactive group equivalent in the thermosetting resin (for example, in the case of an epoxy resin, the epoxy equivalent in the resin) and the equivalent of the curing agent. In general, the equivalent ratio of the reactive group equivalent to the curing agent equivalent is set to 1.0: 0.9 to 1.0: 1.2 in consideration of the equivalent ratio of
  • thermosetting resin composition of the present invention when used for a prepreg, it is preferable that each component be in a varnish state in which the components are dissolved or dispersed in an organic solvent.
  • organic solvent used in producing the varnish examples include, for example, alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • Solvent butyl acetate, ester solvents such as propylene glycol monomethyl ether acetate, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene, xylene and mesitylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide And other aprotic polar solvents.
  • ester solvents such as propylene glycol monomethyl ether acetate
  • ether solvents such as tetrahydrofuran
  • aromatic hydrocarbon solvents such as toluene, xylene and mesitylene
  • dimethylformamide dimethylacetamide
  • N-methylpyrrolidone dimethylsulfoxide
  • other aprotic polar solvents such as toluene, xylene and mesitylene
  • dimethylformamide dimethylacetamide
  • N-methylpyrrolidone dimethylsulfoxide
  • thermosetting resin-based composition is not particularly limited, and the composition can be prepared by uniformly mixing the above components.
  • a method of uniformly stirring and mixing the thermosetting resin and the onium salt of the present invention at a temperature of about 20 to 150 ° C. can be mentioned, and in some cases, a solvent used in the production of the varnish is exemplified. May be used.
  • a curing agent for a thermosetting resin it is preferable that the mixture of the curing agent and the curing accelerator is heated and then cooled, then mixed with the thermosetting resin, heated, and cooled.
  • thermosetting resin Before the mixture of the curing agent and the curing accelerator is mixed with the thermosetting resin, it can be accurately measured by cooling in advance, and the handling becomes easy.
  • a master batch obtained by heating and dissolving the curing accelerator in a part of the curing agent at a high concentration and then cooling may be used as the curing accelerator.
  • This masterbatch has relatively good solubility in the curing agent.
  • the components of the curing agent, the curing accelerator, and the thermosetting resin may be mixed at once in each mixing step, or may be mixed a plurality of times little by little. Also, when the above-mentioned solvent, additive, inorganic filler, and the like are mixed, they can be similarly mixed once or at a plurality of times at any time.
  • a kneader such as a roll or a kneader may be used to facilitate uniform stirring and mixing.
  • thermosetting resin composition of the present invention exhibits high catalytic activity and can be cured in a short time.
  • thermosetting resin composition can be measured and evaluated by a conventional method for evaluating curability. For example, it can be measured and evaluated by a gel time measurement method based on JIS K 6910 and EIMS T-901 and a torque measurement method based on JIS K 6300-2. In the present invention, the curability was evaluated by a torque measurement method based on JIS K6300-2.
  • thermosetting resin-based cured product In the present invention, the thermosetting resin-based cured product, the thermosetting resin-based composition, the fluidity of the thermosetting resin is lost by heating under specific conditions according to the thermosetting resin-based composition , A cured solid.
  • the solid obtained by curing the thermosetting resin composition of the present invention may be referred to as “the thermosetting resin-based cured product of the present invention”.
  • thermosetting resin-based cured product of the present invention can be obtained by heating the above-described thermosetting resin-based composition of the present invention under ordinary curing conditions of the thermosetting resin-based composition. Usually, it can be obtained by heating at a curing temperature of about 100 to 250 ° C. for a curing time of 30 seconds to 15 hours, and the conditions can be appropriately changed.
  • thermosetting resin-based cured product of the present invention the curing accelerator for the thermosetting resin contained in the thermosetting resin-based cured product is incorporated into the curing by its own phenolic hydroxyl group. Accelerators do not adversely affect heat resistance and adhesion as impurities in the cured product. Therefore, the thermosetting resin-based cured product of the present invention is excellent in heat resistance and adhesiveness.
  • the adhesiveness of the thermosetting resin-based cured product can be measured and evaluated by an ordinary adhesive method. For example, an evaluation method based on a cross-cut method according to JIS @ K # 5600, an evaluation method based on a tensile shear adhesive strength based on JIS @ K # 6850, an evaluation method based on a peel adhesive strength based on JIS @ K # 6854, and the like can be given. In the present invention, the adhesiveness was evaluated by an evaluation method using a cross cut method based on JIS K5600.
  • the heat resistance of the thermosetting resin-based cured product can be measured and evaluated by a conventional heat resistance method.
  • a conventional heat resistance method For example, an evaluation method based on dynamic mechanical properties (also referred to as dynamic viscoelasticity) according to JIS K7244, an evaluation method based on thermomechanical analysis based on JIS K7197, and an evaluation method based on differential scanning calorimetry according to JIS K7121 And the like.
  • heat resistance was evaluated based on dynamic mechanical properties (also referred to as dynamic viscoelasticity) in accordance with JIS ⁇ K ⁇ 7244.
  • thermosetting resin composition of the present invention will be described in detail below with reference to examples and test examples, but the present invention is not limited to these examples.
  • FIG. 4 shows IR spectrum data of the obtained product. From these data, the obtained product is tetrabutylphosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate represented by the formula (3 ′′ -1) (hereinafter, referred to as “TBP-TPM”). And the yield was calculated to be 96%.
  • Bu represents a butyl group.
  • FIG. 5 shows IR spectrum data of the obtained product. From these data, the obtained product was identified as tetrabutylphosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate (hereinafter referred to as “TBP-TPE”) represented by the formula (4 ′′ -1). "), And the yield was calculated to be 96%.
  • Bu represents a butyl group.
  • FIG. 6 shows IR spectrum data of the obtained product.
  • FIG. 7 shows IR spectrum data of the obtained product. From these data, the obtained product is the target butyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate of the formula (2 ′′ -2-3) (Hereinafter, referred to as “TPPB-3PC”), and the yield was calculated to be 98%.
  • TPPB-3PC target butyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate of the formula (2 ′′ -2-3)
  • FIG. 8 shows IR spectrum data of the obtained product.
  • the obtained product was the target benzyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate represented by the formula (2 ′′ -2-4) (Hereinafter, referred to as “TPPZ-3PC”), and the yield was calculated to be 91%.
  • TPPZ-3PC target benzyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate represented by the formula (2 ′′ -2-4)
  • TPPZ-3PC target benzyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate represented by the formula (2 ′′ -2-4)
  • the obtained product was the target methoxymethyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylpheno represented by the formula (2 ′′ -2-5).
  • TPPMO-3PC target methoxymethyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylpheno represented by the formula (2 ′′ -2-5).
  • thermosetting resin composition (The equivalent ratio of epoxy equivalent to hydroxyl equivalent was 1.0: 1.0). The obtained thermosetting resin composition was heated and cured at 150 ° C. for 8 hours to obtain a thermosetting resin-based cured product.
  • thermosetting resin composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1, except that 10.3 parts by weight of TBP-3PC was used instead of 11.7 parts by weight of TPP-3PC.
  • thermosetting resin composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1, except that 12.4 parts by weight of TBP-4PC was used instead of 11.7 parts by weight of TPP-3PC.
  • thermosetting resin composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1 except that 9.4 parts by weight of TBP-TPM was used instead of 11.7 parts by weight of TPP-3PC.
  • thermosetting resin composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1, except that 11.2 parts by weight of TBP-TPE was used instead of 11.7 parts by weight of TPP-3PC.
  • thermosetting resin composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1, except that 10.0 parts by weight of TBA-3PC was used instead of 11.7 parts by weight of TPP-3PC.
  • Example 7> A thermosetting resin composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1 except that 11.3 parts by weight of TPP-3PC was used instead of 11.7 parts by weight of TPP-3PC.
  • Example 8> A thermosetting resin-based composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1 except that 11.9 parts by weight of TPP-3PC was used instead of 11.7 parts by weight of TPP-3PC.
  • Example 9> A thermosetting resin composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1, except that 11.1 parts by weight of TPP-3PC was used instead of 11.7 parts by weight of TPP-3PC.
  • thermosetting resin composition and a thermosetting resin were prepared in the same manner as in Example 1 except that 4.2 parts by weight of triphenylphosphine (hereinafter referred to as “TPP”) was used instead of 11.7 parts by weight of TPP-3PC.
  • TPP triphenylphosphine
  • thermosetting resin system was prepared in the same manner as in Example 1 except that 4.9 parts by weight of tris (4-methylphenyl) phosphine (hereinafter, referred to as “TPTP”) was used instead of 11.7 parts by weight of TPP-3PC.
  • TPTP tris (4-methylphenyl) phosphine
  • thermosetting resin composition Same as Example 1 except that 7.3 parts by weight of bis (tetrabutylphosphonium) pyromellitate (hereinafter referred to as “BTBP-pyromellitate”) described in Patent Document 1 was used instead of 11.7 parts by weight of TPP-3PC.
  • BTBP-pyromellitate bis (tetrabutylphosphonium) pyromellitate
  • thermosetting resin system was prepared in the same manner as in Example 1 except that 4.7 parts by weight of 2-ethyl-4-methylimidazole (hereinafter referred to as "2E4MZ") was used instead of 11.7 parts by weight of TPP-3PC.
  • 2E4MZ 2-ethyl-4-methylimidazole
  • thermosetting resin composition and a thermosetting resin-based cured product were obtained.
  • thermosetting resin composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1 except that 15.0 parts by weight of TBP-TD2131 was used instead of 11.7 parts by weight of TPP-3PC. .
  • thermosetting resin composition was evaluated by a torque measurement method at a temperature of 175 ° C. and an amplitude angle of ⁇ 1 ° using a Curastometer 7P manufactured by JSR Trading Co., Ltd.
  • tc (10), tc (90), and tc ( ⁇ 80) were evaluated as indices of curability according to JIS K 6300-2.
  • tc (10), tc (90), and tc ( ⁇ 80) are as defined in Table 1. That is, it can be said that the smaller the tc ( ⁇ 80), the better the curability.
  • thermosetting resin-based composition was applied on a copper substrate using a bar coater so as to have a film thickness of 40 to 60 ⁇ m, and cured at 150 ° C. for 8 hours in a convection oven to conduct an adhesion test.
  • a cured product was prepared.
  • a cross cut test (according to JIS K 5600) was performed using the obtained cured product for an adhesiveness test, and the adhesiveness was determined in six steps of classifications 0 to 5 according to the criteria of the same standard. The smaller the classification value, the better.
  • thermosetting resin-based cured product was subjected to dynamic mechanical properties according to JIS K 7244 at a temperature rise of 5 ° C./min, a frequency of 1 Hz, and a bending mode using DMS6100 manufactured by SII Nano Technology Co., Ltd. (Also referred to as dynamic viscoelasticity).
  • thermosetting resin composition and the cured product containing the onium salt of the present invention have tc ( ⁇ 80) of 2 or less and adhesiveness of 1 or less. And the glass transition temperature was 149 ° C. or higher, and all showed excellent results in curability, adhesiveness, and heat resistance.
  • thermosetting resin composition and the cured product containing the onium salt of the present invention are useful because they have better curability, adhesiveness and heat resistance than the case where a conventional curing accelerator is used.
  • thermosetting resin composition and the cured product of the present invention can simultaneously satisfy curability, adhesiveness and heat resistance, for example, resin sealing of various small electric / electronic parts and semiconductor parts Useful for

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Abstract

The present invention addresses the problem of providing: a thermosetting resin-based composition having good curability; and a thermosetting resin-based cured product having good adhesion and heat resistance. To solve the problem, an onium salt represented by general formula (2'-2) and comprising an onium cation and an anion residue of at least one phenol derivative selected from the group consisting of phenol derivatives; a curing accelerator containing the onium salt; a thermosetting resin-based composition containing the onium salt; and a thermosetting resin-based cured product are provided.

Description

新規オニウム化合物New onium compounds
　本発明は、硬化性が良好となる熱硬化性樹脂系組成物、および接着性、耐熱性が良好となる熱硬化性樹脂系硬化物に関する。 {Circle over (1)} The present invention relates to a thermosetting resin-based composition having good curability and a thermosetting resin-based cured product having good adhesiveness and heat resistance.
　従来、エポキシ樹脂等に代表される熱硬化性樹脂系組成物は、優れた機械的、化学的および電気的性質を有する成形体等が得られるため、半導体素子の絶縁封止材料、プリント基板材料、塗料、航空機や自動車の複合材料等に広く使用されている。特に半導体素子の絶縁封止の分野では、エポキシ樹脂系組成物が接着性等に優れるため好適に用いられているが、半導体素子の高集積化への要求が高く、半導体パッケージの構造も進歩し続けている。このため、熱硬化性樹脂系組成物の性能も、より優れたものが要求されている。 Conventionally, a thermosetting resin-based composition represented by an epoxy resin or the like can provide a molded article having excellent mechanical, chemical and electrical properties. Widely used for paints, composite materials for aircraft and automobiles, etc. In particular, in the field of insulating sealing of semiconductor devices, epoxy resin-based compositions are preferably used because of their excellent adhesive properties. However, there is a high demand for high integration of semiconductor devices, and the structure of semiconductor packages has been advanced. continuing. For this reason, the performance of the thermosetting resin composition is also required to be more excellent.
　例えば半導体パッケージの場合、半導体素子が回路基板上に固定され、半導体素子の電極パッドと回路基板上の電極パッドとの間はワイヤにより電気的に接続される。この電極パッドやワイヤは、銅やアルミニウムが広く用いられているが、半導体素子の小型化が進み、固定面積が小さくなったことから、リフロー時の熱ストレスにより、封止樹脂と半導体素子の界面で剥離が発生し、発生した内部応力により電極パッドやワイヤが断線してしまうことがある。電極パッドやワイヤの断線を防止するために、封止材料用途の熱硬化性樹脂系組成物は、特に銅やアルミニウムへの接着性が重要となる。 In the case of a semiconductor package, for example, a semiconductor element is fixed on a circuit board, and an electrode pad of the semiconductor element and an electrode pad on the circuit board are electrically connected by a wire. Copper and aluminum are widely used for the electrode pads and wires. However, as the size of the semiconductor element has been reduced and the fixed area has been reduced, the interface between the sealing resin and the semiconductor element has been reduced due to thermal stress during reflow. In some cases, peeling may occur, and the electrode pads or wires may be disconnected due to the generated internal stress. In order to prevent disconnection of the electrode pads and wires, the thermosetting resin-based composition for sealing materials is particularly important in adhesion to copper and aluminum.
　また、現在用いられているシリコン（Ｓｉ）半導体はその材料物性値からくる性能限界のため、半導体素子の性能を向上させることは困難となっており、より高温で動作可能なシリコンカーバイト（ＳｉＣ）半導体への変換が進められている。これに伴い、半導体封止用の熱硬化性樹脂系組成物にこれまで以上の耐熱性が要求されている。 Further, it is difficult to improve the performance of a semiconductor device because of the performance limit of a currently used silicon (Si) semiconductor due to its material properties, and a silicon carbide (SiC) operable at a higher temperature. ) Conversion to semiconductors is underway. Along with this, a thermosetting resin composition for semiconductor encapsulation is required to have higher heat resistance than ever.
　さらに、半導体用封止材料の用途においては、低コスト化と省エネルギー化といった観点から、成形サイクルが短い、つまり硬化性が高い熱硬化性樹脂系組成物が要求されている。 Furthermore, in the application of the sealing material for semiconductors, a thermosetting resin composition having a short molding cycle, that is, having high curability is required from the viewpoint of cost reduction and energy saving.
　熱硬化性樹脂系組成物に成分として含まれる硬化促進剤は、添加することによって、熱硬化性樹脂系組成物の硬化を促進させるほかに、その成形体である硬化物の硬化性、および接着性、耐熱性など諸特性にも影響を与えるため、適する硬化促進剤の選択は極めて重要である。 The curing accelerator contained as a component in the thermosetting resin composition, when added, promotes the curing of the thermosetting resin composition, as well as the curability and adhesion of the molded product as a cured product. Since various properties such as heat resistance and heat resistance are affected, it is extremely important to select a suitable curing accelerator.
　そのような状況下にあって、硬化性、接着性、耐熱性等のバランスに優れた熱硬化性樹脂系組成物を与える熱硬化性樹脂用の硬化促進剤が求められている。しかし、接着性と、硬化性および耐熱性はトレードオフの関係になりやすく、これらを同時に満たすことは困難であった。 Under such circumstances, there is a need for a curing accelerator for a thermosetting resin that provides a thermosetting resin-based composition having an excellent balance of curability, adhesiveness, heat resistance, and the like. However, the adhesiveness, the curability, and the heat resistance tend to be in a trade-off relationship, and it has been difficult to satisfy these at the same time.
　既存の熱硬化性樹脂用硬化促進剤、特にエポキシ樹脂用の硬化促進剤としては、リン系、あるいはイミダゾール系があるが、硬化力が高く、かつ電気的信頼性の高い硬化物を得ることが出来るリン系が一般的に知られており、その中でも接着性が良好となる熱硬化性樹脂系組成物を与える熱硬化性樹脂用硬化促進剤として、トリフェニルホスフィン、トリス（４－メチルフェニル）ホスフィン（非特許文献１参照）が挙げられる。また、リン系硬化促進剤としては、前記３級ホスフィンの他、ホスホニウムカチオンとアニオン残基からなる４級ホスホニウム塩も知られており、その中には、アニオン残基がそれぞれ、カルボキシレートおよびフェノラートとなるホスホニウムカルボキシレート（特許文献１参照）、ホスホニウムフェノラート（特許文献２、特許文献３参照）が挙げられるが、これらを配合した熱硬化性樹脂系組成物は、いずれも硬化性、接着性および耐熱性が同時に満足するものではなかった。 There are phosphorus-based or imidazole-based curing accelerators for existing thermosetting resins, especially for epoxy resins.However, it is possible to obtain cured products with high curing power and high electrical reliability. Phosphorus compounds are generally known. Among them, triphenylphosphine and tris (4-methylphenyl) are used as a curing accelerator for a thermosetting resin which gives a thermosetting resin composition having good adhesiveness. Phosphine (see Non-Patent Document 1). In addition to the tertiary phosphine, a quaternary phosphonium salt comprising a phosphonium cation and an anionic residue is also known as a phosphorus-based curing accelerator. Among them, anionic residues include carboxylate and phenolate, respectively. Phosphonium carboxylate (see Patent Literature 1) and phosphonium phenolate (see Patent Literature 2 and Patent Literature 3). Thermosetting resin-based compositions containing these are all curable and adhesive. And heat resistance were not simultaneously satisfied.
国際公開第２０１８／０２１５４８号パンフレットWO 2018/021548 pamphlet 特開２０００－０８６８６７号公報JP 2000-086867 A 特開２０００－２７３１５５号公報JP 2000-273155 A
　本発明は、上記の従来技術に伴う問題点を解決しようとするものである。すなわち、硬化性が良好となる熱硬化性樹脂系組成物、および接着性、耐熱性が良好となる熱硬化性樹脂系硬化物を提供することにある。 The present invention is to solve the above-mentioned problems with the conventional technology. That is, an object of the present invention is to provide a thermosetting resin-based composition having good curability and a thermosetting resin-based cured product having good adhesiveness and heat resistance.
　このような状況に鑑み、本発明者らは鋭意検討した。その結果、下記一般式（１）で表されるオニウムカチオンと、下記の一般式（２）から一般式（５）で表されるフェノール誘導体からなる群から選ばれる少なくとも１種のフェノール誘導体のアニオン残基からなるオニウムフェノラート（以下、「本発明のオニウム塩」ということがある）を、硬化促進剤として配合することにより、硬化性が良好となる熱硬化性樹脂系組成物、および接着性、耐熱性が良好となる熱硬化性樹脂系硬化物が得られること等を見いだし、本発明を完成するに至った。
　なお、フェノール誘導体のアニオン残基とは、フェノール誘導体のフェノール性水酸基からプロトンが外れて、フェノラートアニオンとなったものをいう。 In view of such a situation, the present inventors diligently studied. As a result, an onium cation represented by the following general formula (1) and an anion of at least one phenol derivative selected from the group consisting of the phenol derivatives represented by the following general formulas (2) to (5) A thermosetting resin composition having good curability by blending an onium phenolate comprising a residue (hereinafter, sometimes referred to as “onium salt of the present invention”) as a curing accelerator, and an adhesive property It has been found that a thermosetting resin-based cured product having good heat resistance can be obtained, and the present invention has been completed.
In addition, the anion residue of the phenol derivative refers to a phenolate anion in which a proton has been removed from the phenolic hydroxyl group of the phenol derivative.
　すなわち、本発明は以下の内容をその要旨とするものである。
［１］下記の一般式（１）
Figure JPOXMLDOC01-appb-C000010
 （式中、Ｒ１～Ｒ４は、同一または異なって、炭素数１～１６の置換または非置換の炭化水素基を示し、Ｑはリン原子または窒素原子を示す。）で表されるオニウムカチオンと、
下記の一般式（２）から一般式（５）で表されるフェノール誘導体からなる群から選ばれる少なくとも１種のフェノール誘導体のアニオン残基からなるオニウムフェノラート。
Figure JPOXMLDOC01-appb-C000011
 （式中、Ｒ５、Ｒ６、Ｒ７は同一または異なって、水素原子、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）、水酸基、またはアミノ基を示す。ａ、ｂ、ｃは同一または異なって、ａ、ｃは０から４のいずれかの整数を示し、ｂは０から３のいずれかの整数を示す。また、ａ、ｂ、ｃが２以上の整数を示すとき、複数の各Ｒ５、Ｒ６、Ｒ７は、同一または異なっていてもよい。また、ｐは０から４の整数を示す。）
Figure JPOXMLDOC01-appb-C000012
 （式中、Ｒ８、Ｒ９、Ｒ１０は同一または異なって、水素原子、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）、水酸基、またはアミノ基を示し、ｄ、ｅ、ｆは同一または異なって、０から４のいずれかの整数を示す。また、ｄ、ｅ、ｆが２以上の整数を示すとき、複数の各Ｒ８、Ｒ９、Ｒ１０は、同一または異なっていてもよい。Ｒ１１は、水素原子、炭素数１～１６の飽和脂肪族炭化水素基（アルキル基）、またはアルキル基もしくはメトキシ基で置換してもよいフェニル基を示す。）
Figure JPOXMLDOC01-appb-C000013
 （式中、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５は同一または異なって、水素原子、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）、水酸基、またはアミノ基を示し、ｇ、ｈ、ｉ、ｊは同一または異なって、０から４のいずれかの整数を示す。また、ｇ、ｈ、ｉ、ｊが２以上の整数を示すとき、複数の各Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５は、同一または異なっていてもよい。Ｘは単結合、炭素数１～１６の２価の飽和脂肪族炭化水素基（アルキル基）もしくは飽和脂環式炭化水素基（シクロアルキル基）、またはフェニレン基を示す。）
Figure JPOXMLDOC01-appb-C000014
 （式中、Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９は同一または異なって、水素原子、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）、水酸基、またはアミノ基を示し、ｋ、ｌ、ｍ、ｎは同一または異なって、０から４のいずれかの整数を示す。また、ｋ、ｌ、ｍ、ｎが２以上の整数を示すとき、複数の各Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９は、同一または異なっていてもよい。） That is, the present invention has the following contents as its gist.
[1] The following general formula (1)
Figure JPOXMLDOC01-appb-C000010
 Wherein R 1 to R 4 are the same or different and each represent a substituted or unsubstituted hydrocarbon group having 1 to 16 carbon atoms, and Q represents a phosphorus atom or a nitrogen atom. When,
An onium phenolate comprising an anionic residue of at least one phenol derivative selected from the group consisting of phenol derivatives represented by the following general formulas (2) to (5).
Figure JPOXMLDOC01-appb-C000011
 (Wherein, R 5 , R 6 and R 7 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group. c is the same or different, a and c each represent an integer of 0 to 4, b represents an integer of 0 to 3. When a, b, and c each represent an integer of 2 or more, , A plurality of R 5 , R 6 and R 7 may be the same or different, and p represents an integer of 0 to 4.)
Figure JPOXMLDOC01-appb-C000012
 (Wherein, R 8 , R 9 and R 10 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group; f is the same or different and represents an integer of 0 to 4. When d, e, and f each represent an integer of 2 or more, a plurality of R 8 , R 9 , and R 10 are the same or different. R 11 represents a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms (alkyl group), or a phenyl group which may be substituted with an alkyl group or a methoxy group.
Figure JPOXMLDOC01-appb-C000013
 (Wherein, R 12 , R 13 , R 14 and R 15 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group; , H, i, j are the same or different and each represent an integer of 0 to 4. When g, h, i, j represents an integer of 2 or more, a plurality of each of R 12 , R 13 , R 14 and R 15 may be the same or different, and X is a single bond, a divalent saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms (alkyl group) or a saturated alicyclic hydrocarbon group (cycloalkyl group). Group) or a phenylene group.)
Figure JPOXMLDOC01-appb-C000014
 (Wherein, R 16 , R 17 , R 18 and R 19 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group; , L, m, and n are the same or different and each represent an integer of 0 to 4. When k, 1, m, and n represent an integer of 2 or more, a plurality of R 16 , R 17 , R 18 and R 19 may be the same or different.)
〔２〕前記一般式（１）において、Ｒ１～Ｒ４が、同一または異なって、ブチル基、フェニル基、４－メチルフェニル基、４－メトキシフェニル基、ベンジル基、メトキシメチル基、およびカルボキシエチル基から選ばれる置換基である〔１〕に記載のオニウムフェノラート。 [2] In the above general formula (1), R 1 to R 4 are the same or different and are butyl, phenyl, 4-methylphenyl, 4-methoxyphenyl, benzyl, methoxymethyl, and carboxy. The onium phenolate according to [1], which is a substituent selected from an ethyl group.
〔３〕前記一般式（１）において、Ｒ１～Ｒ４が全てフェニル基である〔１〕に記載のテトラフェニルオニウムフェノラート。 [3] The tetraphenylonium phenolate according to [1], wherein in the general formula (1), R 1 to R 4 are all phenyl groups.
〔４〕前記一般式（１）において、Ｒ１～Ｒ４が全てブチル基である〔１〕に記載のテトラブチルオニウムフェノラート。 [4] The tetrabutylonium phenolate according to [1], wherein in the general formula (1), R 1 to R 4 are all butyl groups.
〔５〕前記一般式（２）が、下記式（２ａ）～（２ｄ）からなる群から選ばれる１種のフェノール誘導体であることを特徴とする〔１〕～〔４〕のいずれかに記載のオニウムフェノラート。
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-I000016
[5] The method according to any one of [1] to [4], wherein the general formula (2) is one kind of phenol derivative selected from the group consisting of the following formulas (2a) to (2d). Onium phenolate.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-I000016
〔６〕前記一般式（３）が下記式（３ａ）または下記式（３ｂ）のいずれか１種のフェノール誘導体であることを特徴とする〔１〕～〔４〕のいずれかに記載のオニウムフェノラート。
Figure JPOXMLDOC01-appb-C000017
 [6] The onium according to any of [1] to [4], wherein the general formula (3) is a phenol derivative of any one of the following formulas (3a) and (3b). Phenolate.
Figure JPOXMLDOC01-appb-C000017
〔７〕前記一般式（４）が下記式（４ａ）または下記式（４ｂ）のいずれか１種のフェノール誘導体であることを特徴とする〔１〕～〔４〕のいずれかに記載のオニウムフェノラート。
Figure JPOXMLDOC01-appb-C000018
 [7] The onium according to any one of [1] to [4], wherein the general formula (4) is a phenol derivative of any one of the following formulas (4a) and (4b): Phenolate.
Figure JPOXMLDOC01-appb-C000018
〔８〕前記一般式（５）が下記式（５ａ）のフェノール誘導体であることを特徴とする〔１〕～〔４〕のいずれかに記載のオニウムフェノラート。
Figure JPOXMLDOC01-appb-C000019
 [8] The onium phenolate according to any one of [1] to [4], wherein the general formula (5) is a phenol derivative of the following formula (5a).
Figure JPOXMLDOC01-appb-C000019
〔９〕〔１〕～〔８〕のいずれかに記載のオニウムフェノラートを少なくとも含む、熱硬化性樹脂用硬化促進剤。 [9] A curing accelerator for a thermosetting resin, comprising at least the onium phenolate according to any one of [1] to [8].
〔１０〕〔９〕に記載の熱硬化性樹脂用硬化促進剤と、熱硬化性樹脂とを少なくとも含む、熱硬化性樹脂系組成物。 [10] A thermosetting resin composition containing at least the curing accelerator for thermosetting resin according to [9] and a thermosetting resin.
〔１１〕前記熱硬化性樹脂が、エポキシ樹脂、マレイミド樹脂、シアネート樹脂、およびイソシアネート樹脂から選ばれる１種または２種以上の熱硬化性樹脂である、〔１０〕に記載の熱硬化性樹脂系組成物。 [11] The thermosetting resin according to [10], wherein the thermosetting resin is one or two or more thermosetting resins selected from an epoxy resin, a maleimide resin, a cyanate resin, and an isocyanate resin. Composition.
〔１２〕さらに熱硬化性樹脂用硬化剤を含む、〔１０〕または〔１１〕に記載の熱硬化性樹脂系組成物。 [12] The thermosetting resin composition according to [10] or [11], further comprising a thermosetting resin curing agent.
〔１３〕前記熱硬化性樹脂用硬化剤が、フェノール樹脂、ポリアミン、酸無水物、およびベンゾオキサジンから選ばれる１種または２種以上の熱硬化性樹脂用硬化剤である、〔１２〕に記載の熱硬化性樹脂系組成物。 [13] The curing agent according to [12], wherein the curing agent for a thermosetting resin is one or more curing agents for a thermosetting resin selected from a phenol resin, a polyamine, an acid anhydride, and benzoxazine. Thermosetting resin composition.
〔１４〕〔１２〕または〔１３〕に記載の熱硬化性樹脂系組成物であって、熱硬化性樹脂用硬化促進剤が、前記熱硬化性樹脂用硬化促進剤と前記熱硬化性樹脂用硬化剤の一部と反応させたマスターバッチである、熱硬化性樹脂系組成物。 [14] The thermosetting resin-based composition according to [12] or [13], wherein the curing accelerator for the thermosetting resin includes the curing accelerator for the thermosetting resin and the curing accelerator for the thermosetting resin. A thermosetting resin composition which is a master batch reacted with a part of a curing agent.
〔１５〕〔１０〕～〔１４〕のいずれかに記載の熱硬化性樹脂系組成物を硬化して得られる熱硬化性樹脂系硬化物。 [15] A thermosetting resin-based cured product obtained by curing the thermosetting resin-based composition according to any one of [10] to [14].
　本発明のオニウム塩を含む熱硬化性樹脂用硬化促進剤を成分として含有する熱硬化性樹脂系組成物および硬化物は、従来の硬化促進剤を用いた場合に比べ、硬化性、接着性および耐熱性が良好となるため有用である。 The thermosetting resin composition and the cured product containing the onium salt-containing thermosetting resin curing accelerator of the present invention as a component, compared with the case where a conventional curing accelerator is used, the curability, adhesiveness and This is useful because the heat resistance is improved.
図１は、テトラフェニルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラートのＩＲスペクトルを示す図である。FIG. 1 is a diagram showing an IR spectrum of tetraphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate. 図２は、テトラブチルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラートのＩＲスペクトルを示す図である。FIG. 2 is a view showing an IR spectrum of tetrabutylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate. 図３は、テトラブチルホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラートのＩＲスペクトルを示す図である。FIG. 3 shows an IR spectrum of tetrabutylphosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate. FIG. 図４は、テトラブチルホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラートのＩＲスペクトルを示す図である。FIG. 4 is a diagram showing an IR spectrum of tetrabutylphosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate. 図５は、テトラブチルホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラートのＩＲスペクトルを示す図である。FIG. 5 is a diagram showing an IR spectrum of tetrabutylphosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate. 図６は、テトラブチルアンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラートのＩＲスペクトルを示す図である。FIG. 6 is a diagram showing an IR spectrum of tetrabutylammonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate. 図７は、ブチルトリフェニルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラートのＩＲスペクトルを示す図である。FIG. 7 is a view showing an IR spectrum of butyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate. 図８は、ベンジルトリフェニルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラートのＩＲスペクトルを示す図である。FIG. 8 is a view showing an IR spectrum of benzyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate. 図９は、メトキシメチルトリフェニルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラートのＩＲスペクトルを示す図である。FIG. 9 is a view showing an IR spectrum of methoxymethyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate.
　以下、本発明について詳細に説明する。
　本発明において、置換もしくは非置換の炭化水素基とは、炭素数が１～１６の炭化水素基であって、置換基を有してもよい脂肪族炭化水素基、及び置換基を有してもよい芳香族炭化水素基を含む。なお、炭化水素基が置換基を有する場合、炭化水素基の炭素数には、置換基に含まれる炭素数は含まれないものとする。
　本発明において、置換基を有してもよい脂肪族炭化水素基は、直鎖状又は分岐鎖状の飽和脂肪族炭化水素基であっても、直鎖状又は分岐鎖状の不飽和脂肪族炭化水素基であってもよい。脂肪族炭化水素基として具体的には、アルキル基としてメチル基、エチル基、ｎ－プロピル基、イソプロピル基、１，１－ジメチルプロピル基、１，２－ジメチルプロピル基、１－エチルプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、１－メチルブチル基、２－メチルブチル基、３－メチルブチル基、１－エチルブチル基、２－エチルブチル基、１，１－ジメチルブチル基、２，２－ジメチルブチル基、１，２－ジメチルブチル基、２，３－ジメチルブチル基、３，３－ジメチルブチル基、２－エチル－２－メチルブチル基、ｎ－ペンチル基、ネオペンチル基、２－ペンチル基、３－ペンチル基、ｔｅｒｔ－ペンチル基、１－メチルペンチル基、２－メチルペンチル基、３－メチルペンチル基、４－メチルペンチル基、１－エチルペンチル基、２－エチルペンチル基、ｎ－ヘキシル基、イソヘキシル基、２－ヘキシル基、３－ヘキシル基、１－メチルヘキシル基、２－メチルヘキシル基、１－エチルヘキシル基、２－エチルヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ウンデシル基、ｎ－ドデシル基、ｎ－トリデシル基、ｎ－テトラデシル基、ｎ－ペンタデシル基、ｎ－ヘキサデシル基等の飽和脂肪族炭化水素基や、アルケニル基として、ビニル基、アリル基等、アルキニル基として、エチニル基、ブチニル基等の不飽和脂肪族炭化水素基が挙げられる。
　本発明において、置換基を有してもよい脂肪族炭化水素基は、脂環式炭化水素基であってもよい。また、脂環式炭化水素基は脂環式飽和炭化水素基であっても、脂環式不飽和炭化水素基であってもよい。脂環式炭化水素基として具体的には、シクロアルキル基として、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、ノルボルニル基、アダマンチル基等の脂環式飽和炭化水素基や、シクロアルケニル基として、シクロブテニル基、シクロペンテニル基、シクロヘキセニル基等の脂環式不飽和炭化水素基を挙げることができる。
　本発明において、置換基を有してもよい芳香族炭化水素基は単環又は多環の芳香族炭化水素であってもよい。芳香族炭化水素基として具体的には、アリール基としてフェニル基、ナフチル基、アントラセニル基等を挙げることができる。 Hereinafter, the present invention will be described in detail.
In the present invention, the term “substituted or unsubstituted hydrocarbon group” means a hydrocarbon group having 1 to 16 carbon atoms, which may be an aliphatic hydrocarbon group which may have a substituent, Containing aromatic hydrocarbon groups. When the hydrocarbon group has a substituent, the number of carbon atoms of the hydrocarbon group does not include the number of carbon atoms contained in the substituent.
In the present invention, the aliphatic hydrocarbon group which may have a substituent may be a linear or branched saturated aliphatic hydrocarbon group, or a linear or branched unsaturated aliphatic group. It may be a hydrocarbon group. Specific examples of the aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-ethylpropyl, and alkyl groups. n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethyl-2-methylbutyl group, n-pentyl group, neopentyl group, 2-pentyl, 3-pentyl, tert-pentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methyl Rupentyl group, 1-ethylpentyl group, 2-ethylpentyl group, n-hexyl group, isohexyl group, 2-hexyl group, 3-hexyl group, 1-methylhexyl group, 2-methylhexyl group, 1-ethylhexyl group, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, Examples thereof include a saturated aliphatic hydrocarbon group such as n-hexadecyl group, an alkenyl group such as a vinyl group and an allyl group, and an alkynyl group such as an ethynyl group and a butynyl group.
In the present invention, the aliphatic hydrocarbon group which may have a substituent may be an alicyclic hydrocarbon group. Further, the alicyclic hydrocarbon group may be an alicyclic saturated hydrocarbon group or an alicyclic unsaturated hydrocarbon group. Specifically as the alicyclic hydrocarbon group, as a cycloalkyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, norbornyl group, adamantyl group and other alicyclic saturated hydrocarbon groups, Examples of the cycloalkenyl group include an alicyclic unsaturated hydrocarbon group such as a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.
In the present invention, the aromatic hydrocarbon group which may have a substituent may be a monocyclic or polycyclic aromatic hydrocarbon. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthracenyl group as the aryl group.
　本発明において、脂肪族炭化水素基に置換してもよい置換基としては、炭素数１～４のアルコキシ基、アリール基、アリールオキシ基、水酸基、カルボキシ基、アシル基、アミノ基、ハロゲン原子等が挙げられる。置換基を有する脂肪族炭化水素基としては、具体的にアルコキシ置換アルキル基として、メトキシメチル基、エトキシメチル基等や、アリール置換アルキル基としてベンジル基等を挙げることができる。
　本発明において、芳香族炭化水素基に置換してもよい置換基としては、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、アリール基、アリールオキシ基、水酸基、カルボキシ基、アシル基、アミノ基、ハロゲン原子等が挙げられる。置換基を有する芳香族炭化水素基としては、具体的にアルキル基置換アリール基としてトリル基、ジメチルフェニル基、エチルフェニル基、プロピルフェニル基、ｎ－ブチルフェニル基、ｔ－ブチルフェニル基等や、アルコキシ基置換アリール基として、メトキシフェニル基、エトキシフェニル基、ｎ－ブトキシフェニル基、ｔ－ブトキシフェニル基等が挙げられる。
　脂肪族炭化水素基又は芳香族炭化水素基が置換基を有する場合、置換基の位置及び置換基の数は特に制限されない。また２以上の置換基を有する場合、それらは同一であっても異なっていてもよい。 In the present invention, examples of the substituent which may be substituted on the aliphatic hydrocarbon group include an alkoxy group having 1 to 4 carbon atoms, an aryl group, an aryloxy group, a hydroxyl group, a carboxy group, an acyl group, an amino group, a halogen atom and the like. Is mentioned. Specific examples of the aliphatic hydrocarbon group having a substituent include a methoxymethyl group and an ethoxymethyl group as an alkoxy-substituted alkyl group, and a benzyl group and the like as an aryl-substituted alkyl group.
In the present invention, the substituent which may be substituted on the aromatic hydrocarbon group includes an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, an aryloxy group, a hydroxyl group, a carboxy group, An acyl group, an amino group, a halogen atom and the like can be mentioned. Specific examples of the aromatic hydrocarbon group having a substituent include an alkyl group-substituted aryl group such as a tolyl group, a dimethylphenyl group, an ethylphenyl group, a propylphenyl group, an n-butylphenyl group, a t-butylphenyl group, Examples of the alkoxy-substituted aryl group include a methoxyphenyl group, an ethoxyphenyl group, an n-butoxyphenyl group, and a t-butoxyphenyl group.
When the aliphatic hydrocarbon group or the aromatic hydrocarbon group has a substituent, the position of the substituent and the number of the substituent are not particularly limited. When it has two or more substituents, they may be the same or different.
　本発明において、炭素数１～１６の２価の飽和脂肪族炭化水素基（アルキル基）または飽和脂環式炭化水素基（シクロアルキル基）としては、メチレン基、エチレン基、プロピレン基、ｎ－ブチレン基、シクロプロピレン基、シクロブチレン基、シクロペンチレン基、シクロヘキシレン基、ノルボルニレン基、アダマンチレン基等が挙げられる。 In the present invention, the divalent saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms (alkyl group) or saturated alicyclic hydrocarbon group (cycloalkyl group) includes methylene, ethylene, propylene, n- Examples thereof include a butylene group, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornylene group, and an adamantylene group.
　本発明において、ハロゲン原子とは、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。 に お い て In the present invention, the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
＜硬化促進剤＞
　本発明は、下記の一般式（１）
Figure JPOXMLDOC01-appb-C000020
 （式中、Ｒ１～Ｒ４は、同一または異なって、炭素数１～１６の置換または非置換の炭化水素基を示し、Ｑはリン原子または窒素原子を示す。）で表されるオニウムカチオンと、
下記の一般式（２）から一般式（５）で表されるフェノール誘導体からなる群から選ばれる少なくとも１種のフェノール誘導体のアニオン残基からなるオニウムフェノラートである。
Figure JPOXMLDOC01-appb-C000021
 （式中、Ｒ５、Ｒ６、Ｒ７は同一または異なって、水素原子、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）、水酸基、またはアミノ基を示す。ａ、ｂ、ｃは同一または異なって、ａ、ｃは０から４のいずれかの整数を示し、ｂは０から３のいずれかの整数を示す。ａ、ｂ、ｃが２以上の整数を示すとき、複数の各Ｒ５、Ｒ６、Ｒ７は同一または異なっていてもよい。また、ｐは０から４の整数を示す。）
Figure JPOXMLDOC01-appb-C000022
 （式中、Ｒ８、Ｒ９、Ｒ１０は同一または異なって、水素原子、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）、水酸基、またはアミノ基を示し、ｄ、ｅ、ｆは同一または異なって、０から４のいずれかの整数を示す。また、ｄ、ｅ、ｆが２以上の整数を示すとき、複数の各Ｒ８、Ｒ９、Ｒ１０は、同一または異なっていてもよい。Ｒ１１は、水素原子、炭素数１～１６の飽和脂肪族炭化水素基（アルキル基）、またはアルキル基もしくはメトキシ基で置換してもよいフェニル基を示す。）
Figure JPOXMLDOC01-appb-C000023
 （式中、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５は同一または異なって、水素原子、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）、水酸基、またはアミノ基を示し、ｇ、ｈ、ｉ、ｊは同一または異なって、０から４のいずれかの整数を示す。また、ｇ、ｈ、ｉ、ｊが２以上の整数を示すとき、複数の各Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５は、同一または異なっていてもよい。Ｘは単結合、炭素数１～１６の２価の飽和脂肪族炭化水素基（アルキル基）もしくは飽和脂環式炭化水素基（シクロアルキル基）、またはフェニレン基を示す。）
Figure JPOXMLDOC01-appb-C000024
 （式中、Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９は同一または異なって、水素原子、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）、水酸基、またはアミノ基を示し、ｋ、ｌ、ｍ、ｎは同一または異なって、０から４のいずれかの整数を示す。また、ｋ、ｌ、ｍ、ｎが２以上の整数を示すとき、複数の各Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９は各々、同一または異なっていてもよい。） <Curing accelerator>
The present invention provides the following general formula (1)
Figure JPOXMLDOC01-appb-C000020
 Wherein R 1 to R 4 are the same or different and each represent a substituted or unsubstituted hydrocarbon group having 1 to 16 carbon atoms, and Q represents a phosphorus atom or a nitrogen atom. When,
An onium phenolate comprising an anionic residue of at least one phenol derivative selected from the group consisting of phenol derivatives represented by the following general formulas (2) to (5).
Figure JPOXMLDOC01-appb-C000021
 (Wherein, R 5 , R 6 and R 7 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group. c is the same or different, a and c each represent an integer of 0 to 4, b represents an integer of 0 to 3. When a, b, and c each represent an integer of 2 or more, R 5 , R 6 , and R 7 may be the same or different, and p represents an integer of 0 to 4.)
Figure JPOXMLDOC01-appb-C000022
 (Wherein, R 8 , R 9 and R 10 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group; f is the same or different and represents an integer of 0 to 4. When d, e, and f each represent an integer of 2 or more, a plurality of R 8 , R 9 , and R 10 are the same or different. R 11 represents a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms (alkyl group), or a phenyl group which may be substituted with an alkyl group or a methoxy group.
Figure JPOXMLDOC01-appb-C000023
 (Wherein, R 12 , R 13 , R 14 and R 15 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group; , H, i, j are the same or different and each represent an integer of 0 to 4. When g, h, i, j represents an integer of 2 or more, a plurality of each of R 12 , R 13 , R 14 and R 15 may be the same or different, and X is a single bond, a divalent saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms (alkyl group) or a saturated alicyclic hydrocarbon group (cycloalkyl group). Group) or a phenylene group.)
Figure JPOXMLDOC01-appb-C000024
 (Wherein, R 16 , R 17 , R 18 and R 19 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group; , L, m, and n are the same or different and each represent an integer of 0 to 4. When k, 1, m, and n represent an integer of 2 or more, a plurality of R 16 , R 17 , R 18 and R 19 may be the same or different.)
《オニウムカチオン》
　一般式（１）のオニウムカチオンにおけるＱは、リン原子または窒素原子である。 《Onium cation》
Q in the onium cation of the general formula (1) is a phosphorus atom or a nitrogen atom.
　一般式（１）のオニウムカチオンにおけるＲ１～Ｒ４は、同一または異なって、炭素数１～１６の置換もしくは非置換の炭化水素基を示す。 R 1 to R 4 in the onium cation of the general formula (1) are the same or different and represent a substituted or unsubstituted hydrocarbon group having 1 to 16 carbon atoms.
　一般式（１）で表されるオニウムカチオンにおいて、Ｒ１～Ｒ４で示される置換基としては、炭素数１～１６の置換もしくは非置換の炭化水素基であり、硬化性の観点から炭素数１～１２が好ましく、炭素数１～６がより好ましい。炭化水素基として前記の置換基の他、具体的にはエチル基、プロピル基、ｎ－ブチル基、オクチル基、ドデシル基、アリル基、シクロヘキシル基、メトキシメチル基、ベンジル基、カルボキシエチル基、フェニル基、４－メチルフェニル基、４－メトキシフェニル基が好ましく、特にｎ－ブチル基、ベンジル基、メトキシメチル基、カルボキシエチル基、フェニル基が好ましい。 In the onium cation represented by the general formula (1), the substituent represented by R 1 to R 4 is a substituted or unsubstituted hydrocarbon group having 1 to 16 carbon atoms. It is preferably from 1 to 12, more preferably from 1 to 6 carbon atoms. As the hydrocarbon group, in addition to the above substituents, specifically, ethyl group, propyl group, n-butyl group, octyl group, dodecyl group, allyl group, cyclohexyl group, methoxymethyl group, benzyl group, carboxyethyl group, phenyl Groups, 4-methylphenyl group and 4-methoxyphenyl group are preferable, and n-butyl group, benzyl group, methoxymethyl group, carboxyethyl group and phenyl group are particularly preferable.
　一般式（１）のオニウムカチオンとしては、テトラブチルホスホニウムカチオン、テトラフェニルホスホニウムカチオン、テトラキス（４－メチルフェニル）ホスホニウムカチオン、テトラキス（４－メトキシフェニル）ホスホニウムカチオン、フェニルトリス（４－メチルフェニル）ホスホニウムカチオン、フェニルトリス（４－メトキシフェニル）ホスホニウムカチオン、フェニルトリブチルホスホニウムカチオン、（４－メチルフェニル）トリフェニルホスホニウムカチオン、（４－メトキシフェニル）トリフェニルホスホニウムカチオン、ブチルトリフェニルホスホニウムカチオン、テトラブチルアンモニウムカチオン、テトラフェニルアンモニウムカチオン、テトラキス（４－メチルフェニル）アンモニウムカチオン、テトラキス（４－メトキシフェニル）アンモニウムカチオン、フェニルトリス（４－メチルフェニル）アンモニウムカチオン、フェニルトリス（４－メトキシフェニル）アンモニウムカチオン、フェニルトリブチルアンモニウムカチオン、（４－メチルフェニル）トリフェニルアンモニウムカチオン、（４－メトキシフェニル）トリフェニルアンモニウムカチオン、ブチルトリフェニルアンモニウムカチオン等が挙げられる。 Examples of the onium cation of the general formula (1) include tetrabutylphosphonium cation, tetraphenylphosphonium cation, tetrakis (4-methylphenyl) phosphonium cation, tetrakis (4-methoxyphenyl) phosphonium cation, and phenyltris (4-methylphenyl) phosphonium Cation, phenyltris (4-methoxyphenyl) phosphonium cation, phenyltributylphosphonium cation, (4-methylphenyl) triphenylphosphonium cation, (4-methoxyphenyl) triphenylphosphonium cation, butyltriphenylphosphonium cation, tetrabutylammonium cation , Tetraphenylammonium cation, tetrakis (4-methylphenyl) ammonium cation, tetrakis (4-methoxyphenyl) ammonium cation, phenyltris (4-methylphenyl) ammonium cation, phenyltris (4-methoxyphenyl) ammonium cation, phenyltributylammonium cation, (4-methylphenyl) triphenylammonium cation, (Methoxyphenyl) triphenylammonium cation, butyltriphenylammonium cation, and the like.
　また、テトラキス（メトキシメチル）ホスホニウムカチオン、テトラキス（カルボキシエチル）ホスホニウムカチオン、テトラベンジルホスホニウムカチオン、フェニルトリス（メトキシメチル）ホスホニウムカチオン、フェニルトリス（カルボキシエチル）ホスホニウムカチオン、フェニルトリベンジルホスホニウムカチオン、（メトキシメチル）トリフェニルホスホニウムカチオン、（カルボキシエチル）トリフェニルホスホニウムカチオン、ベンジルトリフェニルホスホニウムカチオン、テトラキス（メトキシメチル）アンモニウムカチオン、テトラキス（カルボキシエチル）アンモニウムカチオン、テトラベンジルアンモニウムカチオン、フェニルトリス（メトキシメチル）アンモニウムカチオン、フェニルトリス（カルボキシエチル）アンモニウムカチオン、フェニルトリベンジルアンモニウムカチオン、（メトキシメチル）トリフェニルアンモニウムカチオン、（カルボキシエチル）トリフェニルアンモニウムカチオン、ベンジルトリフェニルアンモニウムカチオン等が挙げられる。 Also, tetrakis (methoxymethyl) phosphonium cation, tetrakis (carboxyethyl) phosphonium cation, tetrabenzylphosphonium cation, phenyltris (methoxymethyl) phosphonium cation, phenyltris (carboxyethyl) phosphonium cation, phenyltribenzylphosphonium cation, (methoxymethyl) ) Triphenylphosphonium cation, (carboxyethyl) triphenylphosphonium cation, benzyltriphenylphosphonium cation, tetrakis (methoxymethyl) ammonium cation, tetrakis (carboxyethyl) ammonium cation, tetrabenzylammonium cation, phenyltris (methoxymethyl) ammonium cation , Phenyltris (carboxy Le) ammonium cation, phenyl tri benzyl ammonium cations, (methoxymethyl) triphenyl ammonium cation, (carboxyethyl) triphenyl ammonium cation, benzyl triphenyl ammonium cation or the like.
　具体的にはテトラブチルホスホニウムカチオン、テトラフェニルホスホニウムカチオン、ブチルトリフェニルホスホニウムカチオン、（４－メチルフェニル）トリフェニルホスホニウムカチオン、（４－メトキシフェニル）トリフェニルホスホニウムカチオン、テトラブチルアンモニウムカチオン、テトラフェニルアンモニウムカチオン、ブチルトリフェニルアンモニウムカチオン、（４－メチルフェニル）トリフェニルアンモニウムカチオン、（４－メトキシフェニル）トリフェニルアンモニウムカチオンが好ましい。 Specifically, tetrabutylphosphonium cation, tetraphenylphosphonium cation, butyltriphenylphosphonium cation, (4-methylphenyl) triphenylphosphonium cation, (4-methoxyphenyl) triphenylphosphonium cation, tetrabutylammonium cation, tetraphenylammonium Cations, butyltriphenylammonium cations, (4-methylphenyl) triphenylammonium cations, and (4-methoxyphenyl) triphenylammonium cations are preferred.
　また、（メトキシメチル）トリフェニルホスホニウムカチオン、（カルボキシエチル）トリフェニルホスホニウムカチオン、ベンジルトリフェニルホスホニウムカチオン、（メトキシメチル）トリフェニルアンモニウムカチオン、（カルボキシエチル）トリフェニルアンモニウムカチオン、ベンジルトリフェニルアンモニウムカチオンも好ましい。 Also, (methoxymethyl) triphenylphosphonium cation, (carboxyethyl) triphenylphosphonium cation, benzyltriphenylphosphonium cation, (methoxymethyl) triphenylammonium cation, (carboxyethyl) triphenylammonium cation, and benzyltriphenylammonium cation preferable.
　特にテトラブチルホスホニウムカチオン、テトラフェニルホスホニウムカチオン、テトラブチルアンモニウムカチオン、テトラフェニルアンモニウムカチオン、ブチルトリフェニルホスホニウムカチオン、ベンジルトリフェニルホスホニウムカチオン、メトキシメチルトリフェニルホスホニウムカチオン、（カルボキシエチル）トリフェニルホスホニウムカチオン、ブチルトリフェニルアンモニウムカチオン、ベンジルトリフェニルアンモニウムカチオン、メトキシメチルトリフェニルアンモニウムカチオン、（カルボキシエチル）トリフェニルアンモニウムカチオンがより好ましい。 Particularly, tetrabutylphosphonium cation, tetraphenylphosphonium cation, tetrabutylammonium cation, tetraphenylammonium cation, butyltriphenylphosphonium cation, benzyltriphenylphosphonium cation, methoxymethyltriphenylphosphonium cation, (carboxyethyl) triphenylphosphonium cation, butyl Triphenylammonium cation, benzyltriphenylammonium cation, methoxymethyltriphenylammonium cation, and (carboxyethyl) triphenylammonium cation are more preferred.
《フェノラートアニオン（アニオン残基）》
　フェノール誘導体のフェノール性水酸基から外れるプロトンの箇所としては、得られるフェノラートアニオンが最も安定に存在しうる箇所のプロトンが外れると推定される。分子内水素結合を形成することがあるため、どのフェノール性水酸基からプロトンが外れるかを推定することは困難であるが、ＮＭＲ測定により推定できることがある。 << Phenolate anion (anion residue) >>
It is presumed that the proton at the position where the resulting phenolate anion can be most stably present is removed from the phenolic hydroxyl group of the phenol derivative. Since it may form an intramolecular hydrogen bond, it is difficult to estimate from which phenolic hydroxyl group a proton is released, but it can be estimated by NMR measurement in some cases.
　一般式（２）で表されるフェノラートアニオンにおいてＲ５、Ｒ６、Ｒ７は、同一または異なって、水素原子、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）、水酸基、またはアミノ基を示す。ａ、ｂ、ｃは同一または異なって、ａ、ｃは０から４のいずれかの整数を示し、ｂは０から３のいずれかの整数を示す。ａ、ｂ、ｃが２以上の整数を示すとき、複数の各Ｒ５、Ｒ６、Ｒ７は同一または異なっていてもよい。また、ｐは０から４の整数を示す。 In the phenolate anion represented by the general formula (2), R 5 , R 6 , and R 7 are the same or different and are each a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, Or an amino group. a, b and c are the same or different, a and c each represent an integer of 0 to 4, and b represents an integer of 0 to 3. When a, b, and c represent an integer of 2 or more, each of a plurality of R 5 , R 6 , and R 7 may be the same or different. P represents an integer of 0 to 4.
　一般式（２）のフェノラートアニオンにおけるＲ５、Ｒ６、Ｒ７として、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）については、前記の置換基の他、具体的には、炭素数１～２のメチル基、エチル基、または水酸基が好ましく、特にメチル基または水酸基が好ましい。 As the saturated aliphatic hydrocarbon group (alkyl group) having 1 to 4 carbon atoms as R 5 , R 6 and R 7 in the phenolate anion of the general formula (2), in addition to the above-mentioned substituents, specifically, And a methyl group, an ethyl group or a hydroxyl group having 1 to 2 carbon atoms is preferable, and a methyl group or a hydroxyl group is particularly preferable.
　一般式（２）のフェノラートアニオンにおいて、芳香環に置換されるＲ５、Ｒ６、Ｒ７の置換基の数を示すａ～ｃの整数については、各々、同一または異なってもよく、ａ～ｃが２以上の整数であるときは、複数の各Ｒ５、Ｒ６、Ｒ７は同一または異なってもよく、具体的には０～２の整数であることが好ましい。ａ～ｃの整数が１であるとき、Ｒ５、Ｒ６、Ｒ７として、好ましい置換基はメチル基または水酸基である。ａ～ｃの整数が２であるとき、Ｒ５、Ｒ６、Ｒ７の置換基として、好ましくはメチル基である。 In the phenolate anion of the general formula (2), the integers a to c indicating the number of substituents of R 5 , R 6 , and R 7 substituted on the aromatic ring may be the same or different. When c is an integer of 2 or more, each of a plurality of R 5 , R 6 , and R 7 may be the same or different, and specifically, is preferably an integer of 0 to 2. When the integers a to c are 1, preferred substituents for R 5 , R 6 and R 7 are a methyl group or a hydroxyl group. When the integer of a to c is 2, the substituent of R 5 , R 6 and R 7 is preferably a methyl group.
　Ｒ５、Ｒ６、Ｒ７の置換基の位置としては、芳香環上のいずれの位置でもよいが、Ｒ５、Ｒ６、Ｒ７がアルキル基の場合はメチレン基のメタ位であることが好ましく、Ｒ５、Ｒ６、Ｒ７が水酸基の場合はメチレン基のオルソ位かパラ位であることが好ましく、フェノールを形成する水酸基の位置としては、芳香環上のいずれの位置でもよいが、メチレン基のオルソ位かパラ位であることが好ましい。 The position of the substituent of R 5 , R 6 , and R 7 may be any position on the aromatic ring, but when R 5 , R 6 , or R 7 is an alkyl group, it may be the meta position of the methylene group. Preferably, when R 5 , R 6 , and R 7 are hydroxyl groups, they are preferably in the ortho or para position of the methylene group, and the position of the hydroxyl group forming phenol may be any position on the aromatic ring, It is preferably at the ortho or para position of the methylene group.
　フェノール誘導体の重合度の指標を示すｐとしては、０から４のいずれかの整数を示す。ｐが１のとき、フェノール誘導体はフェノールモノマーの３量体であり、ｐが２のとき、フェノール誘導体はフェノールモノマーの４量体となる。つまり、ｐ＋２がそのフェノール誘導体の重合度である。具体的に、ｐは１または２の整数であることが好ましい。 Ｐ p indicating an index of the degree of polymerization of the phenol derivative is an integer from 0 to 4. When p is 1, the phenol derivative is a phenol monomer trimer, and when p is 2, the phenol derivative is a phenol monomer tetramer. That is, p + 2 is the degree of polymerization of the phenol derivative. Specifically, p is preferably an integer of 1 or 2.
　下記一般式（２’－１）、（２’－２）、（２’－３）、（２’－４）、（２’－５）は、ＮＭＲ測定データから推定される、一般式（２）のフェノラートアニオンとして例示したものである。
Figure JPOXMLDOC01-appb-C000025
 （式中、Ｒ５～Ｒ７、ａ～ｃは、前記と同意である。） The following general formulas (2′-1), (2′-2), (2′-3), (2′-4), and (2′-5) are represented by the general formula ( This is exemplified as the phenolate anion of 2).
Figure JPOXMLDOC01-appb-C000025
 (Wherein, R 5 to R 7 and ac are as defined above.)
　より好適な一般式（２）のフェノラートアニオンとしては、ｐが１または２の整数である上記一般式（２’－２）、（２’－３）が挙げられ、さらに好適な一般式（２）のフェノラートアニオンとしては、Ｒ５、Ｒ６、Ｒ７がメチル基または水酸基となる、下記式（２’－２－１）、（２’－２－２）、（２’－２－３）、（２’－３－１）が挙げられる。
Figure JPOXMLDOC01-appb-C000026
 More preferred phenolate anions of the general formula (2) include the above-mentioned general formulas (2′-2) and (2′-3) where p is an integer of 1 or 2, and more preferred general formula ( As the phenolate anion of 2), the following formulas (2′-2-1), (2′-2-2), and (2′-2) wherein R 5 , R 6 , and R 7 are a methyl group or a hydroxyl group. -3) and (2'-3-1).
Figure JPOXMLDOC01-appb-C000026
　一般式（３）で表されるフェノラートアニオンにおいてＲ８、Ｒ９、Ｒ１０は同一または異なって、水素原子、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）、水酸基、またはアミノ基を示し、ｄ、ｅ、ｆは同一または異なって、０から４のいずれかの整数を示す。また、ｄ、ｅ、ｆが２以上の整数を示すとき、複数の各Ｒ８、Ｒ９、Ｒ１０は、同一または異なっていてもよい。Ｒ１１は、水素原子、炭素数１～１６の飽和脂肪族炭化水素基（アルキル基）、またはアルキル基もしくはメトキシ基で置換してもよいフェニル基を示す置換基である。 In the phenolate anion represented by the general formula (3), R 8 , R 9 , and R 10 are the same or different and are each a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or Represents an amino group; d, e, and f are the same or different and each represents an integer of 0 to 4; When d, e, and f each represent an integer of 2 or more, a plurality of R 8 , R 9 , and R 10 may be the same or different. R 11 is a substituent representing a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms (alkyl group), or a phenyl group which may be substituted with an alkyl group or a methoxy group.
　一般式（３）のフェノラートアニオンにおけるＲ８、Ｒ９、Ｒ１０として、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）については、前記の置換基の他、具体的には、炭素数１～２のメチル基、エチル基、または水酸基が好ましく、特にメチル基または水酸基が好ましい。 As R 8 , R 9 , and R 10 in the phenolate anion of the general formula (3), as the saturated aliphatic hydrocarbon group (alkyl group) having 1 to 4 carbon atoms, specifically, in addition to the above-mentioned substituents, And a methyl group, an ethyl group or a hydroxyl group having 1 to 2 carbon atoms is preferable, and a methyl group or a hydroxyl group is particularly preferable.
　一般式（３）のフェノラートアニオンにおいて、芳香環に置換されるＲ８、Ｒ９、Ｒ１０の置換基の数を示すｄ～ｆの整数については、各々、同一または異なってもよい。ｄ～ｆが２以上の整数であるときは、各Ｒ８、Ｒ９、Ｒ１０は同一または異なってもよく、具体的には０～２の整数であることが好ましい。ｄ～ｆの整数が１であるとき、Ｒ８、Ｒ９、Ｒ１０として、好ましい置換基はメチル基または水酸基である。ｄ～ｆの整数が２であるとき、Ｒ８、Ｒ９、Ｒ１０の置換基として、好ましくはメチル基である。 In the phenolate anion of the general formula (3), the integers of d to f indicating the number of substituents of R 8 , R 9 and R 10 substituted on the aromatic ring may be the same or different. When d to f are integers of 2 or more, each of R 8 , R 9 , and R 10 may be the same or different, and specifically, is preferably an integer of 0 to 2. When the integer of d to f is 1, preferred substituents for R 8 , R 9 and R 10 are a methyl group or a hydroxyl group. When the integer of d to f is 2, the substituent of R 8 , R 9 , and R 10 is preferably a methyl group.
　Ｒ８、Ｒ９、Ｒ１０の炭素数１～４のアルキル基の位置としては、芳香環上のいずれの位置でもよいが、水酸基のオルソ位であることが好ましい。 The position of the alkyl group having 1 to 4 carbon atoms of R 8 , R 9 and R 10 may be any position on the aromatic ring, but is preferably the ortho position of the hydroxyl group.
　一般式（３）のフェノラートアニオンにおけるＲ１１の炭素数１～１６の飽和脂肪族炭化水素基（アルキル基）としては、前記の置換基の他、具体的には、炭素数１～４のアルキル基が好ましい。より具体的にはメチル基またはエチル基であることがより好ましい。 The saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms (alkyl group) represented by R 11 in the phenolate anion of the general formula (3) is, in addition to the above-mentioned substituents, specifically, a C 1 to C 4 alkyl group. Alkyl groups are preferred. More specifically, it is more preferably a methyl group or an ethyl group.
　一般式（３）のフェノラートアニオンにおけるＲ１１のアルキル基またはメトキシ基で置換してもよいフェニル基において、フェニル基を置換してもよいアルキル基としては炭素数１～４のアルキル基であり、具体的にはメチル基が好ましい。したがって、アルキル基またはメトキシ基で置換してもよいフェニル基としては、より具体的には、フェニル基、４－メチルフェニル基、または４－メトキシフェニル基が好ましく、特にフェニル基であることがより好ましい。 In the phenolate anion of the general formula (3), the phenyl group which may be substituted by the alkyl group or the methoxy group of R 11 in the phenolate anion is an alkyl group having 1 to 4 carbon atoms which may be substituted by the phenyl group. Specifically, a methyl group is preferred. Therefore, as the phenyl group which may be substituted with an alkyl group or a methoxy group, more specifically, a phenyl group, a 4-methylphenyl group, or a 4-methoxyphenyl group is preferable, and a phenyl group is more preferable. preferable.
そのため、一般式（３）のフェノラートアニオンにおけるＲ１１としては、具体的に、水素原子、メチル基、エチル基、またはフェニル基が好ましく、特に、水素原子またはメチル基であることが好ましい。 Therefore, specifically, R 11 in the phenolate anion of the general formula (3) is preferably a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, and particularly preferably a hydrogen atom or a methyl group.
　下記一般式（３’）は、ＮＭＲ測定データから推定される、一般式（３）のフェノラートアニオンとして例示したものである。
Figure JPOXMLDOC01-appb-C000027
 （式中、Ｒ８～Ｒ１１、ｄ～ｆは、前記と同意である。） The following general formula (3 ′) is exemplified as the phenolate anion of the general formula (3) estimated from NMR measurement data.
Figure JPOXMLDOC01-appb-C000027
 (Wherein, R 8 to R 11 and d to f have the same meanings as described above.)
　より好適な一般式（３）のフェノラートアニオンとしては、下記一般式（３’－１）、（３’－２）が挙げられる。
Figure JPOXMLDOC01-appb-C000028
 More preferred phenolate anions of the general formula (3) include the following general formulas (3′-1) and (3′-2).
Figure JPOXMLDOC01-appb-C000028
　一般式（４）のフェノラートアニオンにおけるＲ１２、Ｒ１３、Ｒ１４、Ｒ１５は同一または異なって、水素原子、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）、水酸基、またはアミノ基を示し、ｇ、ｈ、ｉ、ｊは同一または異なって、０から４のいずれかの整数を示す。また、ｇ、ｈ、ｉ、ｊが２以上の整数を示すとき、複数の各Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５は、同一または異なっていてもよい。Ｘは単結合、炭素数１～１６の２価の飽和脂肪族炭化水素基もしくは飽和脂環式炭化水素基、またはフェニレン基を示す。 R 12 , R 13 , R 14 and R 15 in the phenolate anion of the general formula (4) are the same or different and are a hydrogen atom, a saturated aliphatic hydrocarbon group (alkyl group) having 1 to 4 carbon atoms, a hydroxyl group, or Represents an amino group; g, h, i, and j are the same or different and each represent an integer of 0 to 4; When g, h, i, and j each represent an integer of 2 or more, a plurality of R 12 , R 13 , R 14 , and R 15 may be the same or different. X represents a single bond, a divalent saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms or a saturated alicyclic hydrocarbon group, or a phenylene group.
　一般式（４）のフェノラートアニオンにおけるＲ１２、Ｒ１３、Ｒ１４、Ｒ１５として、炭素数１～４のアルキル基については、前記の置換基の他、具体的には、炭素数１～２のメチル基、エチル基、または水酸基が好ましく、特にメチル基または水酸基が好ましい。 As the alkyl group having 1 to 4 carbon atoms as R 12 , R 13 , R 14 and R 15 in the phenolate anion of the general formula (4), in addition to the above-mentioned substituents, specifically, 1 to 4 carbon atoms 2 is preferably a methyl group, an ethyl group, or a hydroxyl group, particularly preferably a methyl group or a hydroxyl group.
　一般式（４）のフェノラートアニオンにおいて、芳香環に置換されるＲ１２、Ｒ１３、Ｒ１４、Ｒ１５の置換基の数を示すｇ～ｊの整数については、各々、同一または異なってもよい。ｇ～ｊが２以上の整数であるときは、各Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５は同一または異なってもよく、具体的には０～２の整数であることが好ましい。ｇ～ｊの整数が１であるとき、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５として、好ましい置換基はメチル基または水酸基である。ｇ～ｊの整数が２であるとき、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５の置換基として、好ましくはメチル基である。 In the phenolate anion of the general formula (4), the integers of g to j indicating the number of substituents of R 12 , R 13 , R 14 and R 15 substituted on the aromatic ring may be the same or different. Good. When g to j are an integer of 2 or more, each of R 12 , R 13 , R 14 , and R 15 may be the same or different, and specifically, is preferably an integer of 0 to 2. When the integer of g to j is 1, a preferred substituent for R 12 , R 13 , R 14 and R 15 is a methyl group or a hydroxyl group. When the integer of g to j is 2, the substituent of R 12 , R 13 , R 14 and R 15 is preferably a methyl group.
　Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５の位置としては、芳香環上のいずれの位置でもよいが、水酸基のオルソ位であることが好ましい。 The position of R 12 , R 13 , R 14 , and R 15 may be any position on the aromatic ring, but is preferably the ortho position of the hydroxyl group.
　一般式（４）のフェノラートアニオンにおけるＸで示される炭素数１～１６の２価の飽和脂肪族炭化水素基もしくは飽和脂環式炭化水素基としては、前記の置換基の他、具体的には、炭素数が１～６であることが好ましい。 As the divalent saturated aliphatic hydrocarbon group or saturated alicyclic hydrocarbon group having 1 to 16 carbon atoms represented by X in the phenolate anion of the general formula (4), in addition to the substituents described above, specific examples include Preferably has 1 to 6 carbon atoms.
　そのため、一般式（４）のフェノラートアニオンにおけるＸとしては、具体的には、単結合、つまりビス（４－ヒドロキシフェニル）メチル基２分子が直接結合したもの、メチレン基、シクロヘキシレン基、またはフェニレン基が好ましく、特に単結合またはフェニレン基であることが好ましい。 Therefore, as X in the phenolate anion of the general formula (4), specifically, a single bond, that is, two molecules of a bis (4-hydroxyphenyl) methyl group directly bonded, a methylene group, a cyclohexylene group, or A phenylene group is preferred, and a single bond or a phenylene group is particularly preferred.
　下記一般式（４’）は、ＮＭＲ測定データから推定される、一般式（４）のフェノラートアニオンとして例示したものである。
Figure JPOXMLDOC01-appb-C000029
 （式中、Ｒ１２～Ｒ１５、ｇ～ｊ、Ｘは、前記と同意である。） The following general formula (4 ′) is exemplified as the phenolate anion of the general formula (4) estimated from NMR measurement data.
Figure JPOXMLDOC01-appb-C000029
 (Wherein, R 12 to R 15 , g to j, and X are as defined above.)
　より好適な一般式（４）のフェノラートアニオンとしては、下記式（４’－１）、（４’－２）が挙げられる。
Figure JPOXMLDOC01-appb-C000030
 More preferred phenolate anions of the general formula (4) include the following formulas (4′-1) and (4′-2).
Figure JPOXMLDOC01-appb-C000030
　一般式（５）のフェノラートアニオンにおけるＲ１６、Ｒ１７、Ｒ１８、Ｒ１９は同一または異なって、水素原子、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）、水酸基、アミノ基であり、ｋ、ｌ、ｍ、ｎは同一または異なって、０から４のいずれかの整数を示す。また、ｋ、ｌ、ｍ、ｎが２以上の整数を示すとき、複数の各Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９は各々、同一または異なっていてもよい。 R 16 , R 17 , R 18 , and R 19 in the phenolate anion of the general formula (5) are the same or different and are a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, an amino group. And k, l, m, and n are the same or different and each represents an integer of 0 to 4. When k, l, m, and n each represent an integer of 2 or more, each of a plurality of R 16 , R 17 , R 18 , and R 19 may be the same or different.
　一般式（５）のフェノラートアニオンにおけるＲ１６、Ｒ１７、Ｒ１８、Ｒ１９として、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）については、前記の置換基の他、具体的には、炭素数１～２のメチル基、エチル基、または水酸基が好ましく、特にメチル基または水酸基が好ましい。 As the saturated aliphatic hydrocarbon group (alkyl group) having 1 to 4 carbon atoms as R 16 , R 17 , R 18 and R 19 in the phenolate anion of the general formula (5), in addition to the above substituents, Specifically, a methyl group, an ethyl group, or a hydroxyl group having 1 to 2 carbon atoms is preferable, and a methyl group or a hydroxyl group is particularly preferable.
　一般式（５）のフェノラートアニオンにおいて、芳香環に置換されるＲ１６、Ｒ１７、Ｒ１８、Ｒ１９の置換基の数を示すｋ～ｎの整数については、各々、同一または異なってもよい。ｋ～ｎが２以上の整数であるときは、各Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９は同一または異なってもよく、具体的には０～２の整数であることが好ましい。ｋ～ｎの整数が１であるとき、Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９として、好ましい置換基はメチル基または水酸基である。ｋ～ｎの整数が２であるとき、Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９の置換基として、好ましくはメチル基である。 In the phenolate anion of the general formula (5), the integers of k to n indicating the number of substituents of R 16 , R 17 , R 18 and R 19 substituted on the aromatic ring may be the same or different. Good. When k to n are an integer of 2 or more, each of R 16 , R 17 , R 18 , and R 19 may be the same or different, and specifically, is preferably an integer of 0 to 2. When the integer of k to n is 1, a preferred substituent for R 16 , R 17 , R 18 and R 19 is a methyl group or a hydroxyl group. When the integer of k to n is 2, the substituent of R 16 , R 17 , R 18 and R 19 is preferably a methyl group.
　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９の位置としては、芳香環上のいずれの位置でもよいが、水酸基のオルソ位であることが好ましい。 The position of R 16 , R 17 , R 18 , and R 19 may be any position on the aromatic ring, but is preferably an ortho position of a hydroxyl group.
　下記一般式（５’）は、ＮＭＲ測定データから推定される、一般式（５）のフェノラートアニオンとして例示したものである。
Figure JPOXMLDOC01-appb-C000031
 （式中、Ｒ１６～Ｒ１９、ｋ～ｎは、前記と同意である。） The following general formula (5 ′) is exemplified as the phenolate anion of general formula (5) estimated from NMR measurement data.
Figure JPOXMLDOC01-appb-C000031
 (Wherein, R 16 to R 19 and k to n have the same meanings as described above.)
　より好適な一般式（５）のフェノラートアニオンとしては、下記式（５’－１）が挙げられる。
Figure JPOXMLDOC01-appb-C000032
 A more preferred phenolate anion of the general formula (5) includes the following formula (5′-1).
Figure JPOXMLDOC01-appb-C000032
　上記のオニウムカチオンとフェノール誘導体のアニオン残基との塩は本明細書の記載に基づき、公知の方法により容易に製造できる。 塩 The salt of the above-mentioned onium cation and the anionic residue of the phenol derivative can be easily produced by a known method based on the description of the present specification.
　例えば、フェノール誘導体のアルカリ金属塩を常法で合成（溶媒は、水、メタノール等）した後、そのフェノール誘導体のアルカリ金属塩１モルに対してテトラ置換オニウムハライドを１モル仕込み反応させることにより塩形成する方法等が挙げられる。この場合、テトラ置換オニウムハライドと結晶性フェノール誘導体のアルカリ金属塩をそれぞれ単独もしくは２種類以上を使用して上記塩を形成させてもよい。２種類以上を混合する場合は、２種類以上のテトラ置換オニウムハライドおよび結晶性フェノール誘導体のアルカリ金属塩同士を先に混合した後に、テトラ置換オニウムフェノラートを形成させてもよいし、２種類以上のテトラ置換オニウムフェノラートを混合してもよい。本製法による製造例は、製造例１、７、８、９に記載した。 For example, after synthesizing an alkali metal salt of a phenol derivative by a conventional method (solvent is water, methanol, or the like), reacting 1 mole of the alkali metal salt of the phenol derivative with 1 mole of a tetra-substituted onium halide to cause a reaction. And the like. In this case, the above-mentioned salt may be formed using one or two or more kinds of alkali metal salts of a tetra-substituted onium halide and a crystalline phenol derivative. When two or more kinds are mixed, the tetra-substituted onium phenolate may be formed after two or more kinds of alkali metal salts of the tetra-substituted onium halide and the crystalline phenol derivative are first mixed, or two or more kinds may be formed. May be mixed. Production examples according to this production method are described in Production Examples 1, 7, 8, and 9.
　また、テトラ置換オニウムヒドロキシド１モルに対してフェノール誘導体を１モル用いて中和することにより塩を形成してもよい。本製法による製造例は、製造例２、３、４、５、６に記載した。 塩 Alternatively, a salt may be formed by neutralizing with 1 mol of a phenol derivative per 1 mol of the tetra-substituted onium hydroxide. Production examples according to this production method are described in Production Examples 2, 3, 4, 5, and 6.
　得られた反応物から純度の高い結晶を析出させ、未反応の原料および副生する無機塩を除去すること等を目的に、得られた反応物を水、アルコール系有機溶媒（メタノール、エタノール、プロパノール、ブタノール等）、ケトン系有機溶媒（アセトン、メチルエチルケトン、メチルイソブチルケトン、ジエチルケトン等）、エーテル系有機溶媒（テトラヒドロフラン、ジエチルエーテル、ジブチルエーテル、２－メチルテトラヒドロフラン、シクロペンチルメチルエーテル、ジオキサン等）、無極性溶媒（ベンゼン、トルエン、キシレン、ヘキサン、ヘプタン等）、およびこれらの混合溶媒で洗浄、再結晶精製してもよい。 For the purpose of precipitating high-purity crystals from the obtained reactant and removing unreacted raw materials and by-product inorganic salts, the obtained reactant is treated with water, an alcohol-based organic solvent (methanol, ethanol, Propanol, butanol, etc., ketone organic solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, etc.), ether organic solvents (tetrahydrofuran, diethyl ether, dibutyl ether, 2-methyltetrahydrofuran, cyclopentyl methyl ether, dioxane, etc.), It may be washed with a nonpolar solvent (benzene, toluene, xylene, hexane, heptane, etc.) or a mixed solvent thereof, and purified by recrystallization.
　なお、上記テトラ置換オニウムハライド、テトラ置換オニウムヒドロキシド、フェノール誘導体、および溶媒はいずれも市販されているものを使用してもよい。 The commercially available tetra-substituted onium halide, tetra-substituted onium hydroxide, phenol derivative, and solvent may all be used.
　これらの方法により得られる本発明のオニウム塩は、通常は、オニウムカチオンとフェノール誘導体のアニオン残基との１：１（モル比）塩が主成分であり、一般式（２”－１）～（２”－５）、一般式（３”）、一般式（４”）、一般式（５”）で示される。
Figure JPOXMLDOC01-appb-C000033
 　（式中、Ｑ、Ｒ１～Ｒ７、ａ～ｃは、前記と同意である。）
Figure JPOXMLDOC01-appb-C000034
 　（式中、Ｑ、Ｒ１～Ｒ４、Ｒ８～Ｒ１１、ｄ～ｆは、前記と同意である。）
Figure JPOXMLDOC01-appb-C000035
 　（式中、Ｑ、Ｒ１～Ｒ４、Ｒ１２～Ｒ１５、ｇ～ｊ、Ｘは、前記と同意である。）
Figure JPOXMLDOC01-appb-C000036
 　（式中、Ｑ、Ｒ１～Ｒ４、Ｒ１６～Ｒ１９、ｋ～ｎは、前記と同意である。） The onium salt of the present invention obtained by these methods usually contains a 1: 1 (molar ratio) salt of an onium cation and an anionic residue of a phenol derivative as a main component, and has a general formula (2 ″ -1) to (2 ″ -5), general formula (3 ″), general formula (4 ″), and general formula (5 ″).
Figure JPOXMLDOC01-appb-C000033
 (In the formula, Q, R 1 to R 7 and ac are as defined above.)
Figure JPOXMLDOC01-appb-C000034
 (Wherein, Q, R 1 to R 4 , R 8 to R 11 , and d to f are the same as described above.)
Figure JPOXMLDOC01-appb-C000035
 (In the formula, Q, R 1 to R 4 , R 12 to R 15 , g to j, and X are as defined above.)
Figure JPOXMLDOC01-appb-C000036
 (In the formula, Q, R 1 to R 4 , R 16 to R 19 , and k to n have the same meanings as described above.)
　また、本発明は、一般式（１）で表されるオニウムカチオンと、一般式（２）～（５）で表されるフェノール誘導体のアニオン残基からなるオニウムフェノラート（例えば一般式（２”－１）～（２”－５）、一般式（３”）、一般式（４”）、一般式（５”）で表されるオニウムフェノラート）を少なくとも含む熱硬化性樹脂用硬化促進剤（以下、「本発明の熱硬化性樹脂用硬化促進剤」ということがある）である。 Further, the present invention relates to an onium phenolate comprising an onium cation represented by the general formula (1) and an anionic residue of a phenol derivative represented by the general formulas (2) to (5) (for example, the general formula (2 ") -1) to (2 "-5), a curing accelerator for a thermosetting resin containing at least an onium phenolate represented by the general formula (3"), the general formula (4 "), or the general formula (5")) (Hereinafter may be referred to as “curing accelerator for thermosetting resin of the present invention”).
　本発明の熱硬化性樹脂用硬化促進剤を成分として含有する熱硬化性樹脂系組成物および硬化物は、硬化性、接着性、および耐熱性が良好となる。 (4) The thermosetting resin composition and the cured product containing the curing accelerator for thermosetting resin of the present invention as components have good curability, adhesiveness, and heat resistance.
　さらに、本発明のオニウム塩が硬化剤と均一化し難い場合等は、均一化を容易にすること等を目的として、本発明のオニウム塩をあらかじめ硬化剤と反応させて得たマスターバッチを、熱硬化性樹脂用硬化促進剤として用いてもよい。 Further, when the onium salt of the present invention is difficult to homogenize with the curing agent, for example, for the purpose of facilitating homogenization and the like, a master batch obtained by previously reacting the onium salt of the present invention with the curing agent is heated. It may be used as a curing accelerator for a curable resin.
　本発明の熱硬化性樹脂用硬化促進剤は、本発明のオニウム塩の他に、効果に影響しない限り、熱硬化性樹脂用硬化促進剤に通常使用される溶剤、充填剤、添加剤等をさらに含んでもよい。 The curing accelerator for the thermosetting resin of the present invention, besides the onium salt of the present invention, a solvent, a filler, an additive, etc. which are usually used for the curing accelerator for the thermosetting resin, as long as the effect is not affected. It may further include.
　なお、本発明の熱硬化性樹脂用硬化促進剤は、上記オニウム塩の他に、適宜熱硬化性樹脂の硬化促進剤を併用して使用してもよい。 The curing accelerator for a thermosetting resin of the present invention may be used in combination with a curing accelerator for a thermosetting resin, in addition to the onium salt.
　一般式（２”－１）～（２”－５）の本発明のオニウム塩としては、テトラフェニルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、テトラキス（４－メチルフェニル）ホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、テトラキス（４－メトキシフェニル）ホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、テトラブチルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、フェニルトリス（４－メチルフェニル）ホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、フェニルトリス（４－メトキシフェニル）ホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、フェニルトリブチルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、（４－メチルフェニル）トリフェニルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、（４－メトキシフェニル）トリフェニルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、ブチルトリフェニルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、テトラフェニルアンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、テトラキス（４－メチルフェニル）アンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、テトラキス（４－メトキシフェニル）アンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、テトラブチルアンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、フェニルトリス（４－メチルフェニル）アンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、フェニルトリス（４－メトキシフェニル）アンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、フェニルトリブチルアンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、（４－メチルフェニル）トリフェニルアンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、（４－メトキシフェニル）トリフェニルアンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、ブチルトリフェニルアンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、テトラフェニルホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、テトラキス（４－メチルフェニル）ホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、テトラキス（４－メトキシフェニル）ホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、テトラブチルホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、フェニルトリス（４－メチルフェニル）ホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、フェニルトリス（４－メトキシフェニル）ホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、フェニルトリブチルホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、（４－メチルフェニル）トリフェニルホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、（４－メトキシフェニル）トリフェニルホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、ブチルトリフェニルホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、テトラフェニルアンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、テトラキス（４－メチルフェニル）アンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、テトラキス（４－メトキシフェニル）アンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、テトラブチルアンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、フェニルトリス（４－メチルフェニル）アンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、フェニルトリス（４－メトキシフェニル）アンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、フェニルトリブチルアンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、（４－メチルフェニル）トリフェニルアンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、（４－メトキシフェニル）トリフェニルアンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、ブチルトリフェニルアンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、テトラフェニルホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、テトラキス（４－メチルフェニル）ホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、テトラキス（４－メトキシフェニル）ホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、テトラブチルホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、フェニルトリス（４－メチルフェニル）ホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、フェニルトリス（４－メトキシフェニル）ホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、フェニルトリブチルホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、（４－メチルフェニル）トリフェニルホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、（４－メトキシフェニル）トリフェニルホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、ブチルトリフェニルホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、テトラフェニルアンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、テトラキス（４－メチルフェニル）アンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、テトラキス（４－メトキシフェニル）アンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、テトラブチルアンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、フェニルトリス（４－メチルフェニル）アンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、フェニルトリス（４－メトキシフェニル）アンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、フェニルトリブチルアンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、（４－メトキシフェニル）トリフェニルアンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、ブチルトリフェニルアンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、テトラフェニルホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、テトラキス（４－メチルフェニル）ホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、テトラキス（４－メトキシフェニル）ホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、テトラブチルホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、フェニルトリス（４－メチルフェニル）ホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、フェニルトリス（４－メトキシフェニル）ホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、フェニルトリブチルホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、（４－メチルフェニル）トリフェニルホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、（４－メトキシフェニル）トリフェニルホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、ブチルトリフェニルホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、テトラフェニルアンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、テトラキス（４－メチルフェニル）アンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、テトラキス（４－メトキシフェニル）アンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、テトラブチルアンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、フェニルトリス（４－メチルフェニル）アンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、フェニルトリス（４－メトキシフェニル）アンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、フェニルトリブチルアンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、（４－メチルフェニル）トリフェニルアンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、（４－メトキシフェニル）トリフェニルアンモニウム２－［３－（２－ヒドロキシ－５－メチ
ルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、ブチルトリフェニルアンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート等が挙げられる。 Examples of the onium salts of the present invention represented by the general formulas (2 ″ -1) to (2 ″ -5) include tetraphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, tetrakis (4-methylphenyl) phosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, tetrakis (4-methoxyphenyl) phosphonium 2,6-bis (2-hydroxy-5-methyl Benzyl) -4-methylphenolate, tetrabutylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, phenyltris (4-methylphenyl) phosphonium 2,6-bis (2 -Hydroxy-5-methylbenzyl) -4-methylphenolate, phenyltris (4-methoxyphenyl) Phosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, phenyltributylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, (4 -Methylphenyl) triphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, (4-methoxyphenyl) triphenylphosphonium 2,6-bis (2-hydroxy-5- Methylbenzyl) -4-methylphenolate, butyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, tetraphenylammonium 2,6-bis (2-hydroxy-5 -Methylbenzyl) -4-methylphenolate, tetrakis (4- Tylphenyl) ammonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, tetrakis (4-methoxyphenyl) ammonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4 -Methylphenolate, tetrabutylammonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, phenyltris (4-methylphenyl) ammonium 2,6-bis (2-hydroxy-5 -Methylbenzyl) -4-methylphenolate, phenyltris (4-methoxyphenyl) ammonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, phenyltributylammonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methyl Phenolate, (4-methylphenyl) triphenylammonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, (4-methoxyphenyl) triphenylammonium 2,6-bis (2- (Hydroxy-5-methylbenzyl) -4-methylphenolate, butyltriphenylammonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, tetraphenylphosphonium 2,6-bis (4 -Hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, tetrakis (4-methylphenyl) phosphonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, tetrakis (4-methoxyphenyl) phosphonium 2,6-bis (4-h Roxy-3,5-dimethylbenzyl) -4-methylphenolate, tetrabutylphosphonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, phenyltris (4-methylphenyl ) Phosphonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, phenyltris (4-methoxyphenyl) phosphonium 2,6-bis (4-hydroxy-3,5-dimethyl Benzyl) -4-methylphenolate, phenyltributylphosphonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, (4-methylphenyl) triphenylphosphonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenol , (4-methoxyphenyl) triphenylphosphonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, butyltriphenylphosphonium 2,6-bis (4-hydroxy-3, 5-dimethylbenzyl) -4-methylphenolate, tetraphenylammonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, tetrakis (4-methylphenyl) ammonium 2,6 -Bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, tetrakis (4-methoxyphenyl) ammonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methyl Phenolate, tetrabutylammonium 2,6-bis (4-hydroxy-3,5 -Dimethylbenzyl) -4-methylphenolate, phenyltris (4-methylphenyl) ammonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, phenyltris (4-methoxy Phenyl) ammonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, phenyltributylammonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4- Methylphenolate, (4-methylphenyl) triphenylammonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, (4-methoxyphenyl) triphenylammonium 2,6- Bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenyl Nolate, butyltriphenylammonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, tetraphenylphosphonium 2,6-bis (2,4-dihydroxybenzyl) -4-methyl Phenolate, tetrakis (4-methylphenyl) phosphonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, tetrakis (4-methoxyphenyl) phosphonium 2,6-bis (2,4-dihydroxy Benzyl) -4-methylphenolate, tetrabutylphosphonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, phenyltris (4-methylphenyl) phosphonium 2,6-bis (2,4 -Dihydroxybenzyl) -4-methylphenolate, Tris (4-methoxyphenyl) phosphonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, phenyltributylphosphonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate , (4-methylphenyl) triphenylphosphonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, (4-methoxyphenyl) triphenylphosphonium 2,6-bis (2,4-dihydroxy Benzyl) -4-methylphenolate, butyltriphenylphosphonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, tetraphenylammonium 2,6-bis (2,4-dihydroxybenzyl)- 4-methylphenolate, tetrakis (4-methyl Phenyl) ammonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, tetrakis (4-methoxyphenyl) ammonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate , Tetrabutylammonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, phenyltris (4-methylphenyl) ammonium 2,6-bis (2,4-dihydroxybenzyl) -4-methyl Phenolate, phenyltris (4-methoxyphenyl) ammonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, phenyltributylammonium 2,6-bis (2,4-dihydroxybenzyl) -4 -Methylphenolate, (4-methoxyphenyl) to Phenylammonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, butyltriphenylammonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, tetraphenylphosphonium 2 -[3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, tetrakis (4-methylphenyl) phosphonium 2- [ 3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, tetrakis (4-methoxyphenyl) phosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5- Tylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, tetrabutylphosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2 -Hydroxy-5-methylbenzyl) phenolate, phenyltris (4-methylphenyl) phosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2- (Hydroxy-5-methylbenzyl) phenolate, phenyltris (4-methoxyphenyl) phosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy -5-methylbenzyl) phenolate, phenyltributylphosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, (4-methylphenyl) triphenylphosphonium 2- [3- ( 2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, (4-methoxyphenyl) triphenylphosphonium 2- [3- (2 -Hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, butyltriphenylphosphonium 2- [3- (2-hydroxy-5-methyl Benzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methyl Benzyl) phenolate, tetraphenylammonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, tetrakis (4 -Methylphenyl) ammonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, tetrakis (4-methoxy Phenyl) ammonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, tetrabutylammonium 2- [3 -(2-hydroxy-5-methylbenzyl) -2-hydroxy-5- Tylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, phenyltris (4-methylphenyl) ammonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl ] -6- (2-Hydroxy-5-methylbenzyl) phenolate, phenyltris (4-methoxyphenyl) ammonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, phenyltributylammonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy -5-methylbenzyl) phenolate, (4-methylphenyl) triphenyl Ammonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, (4-methoxyphenyl) triphenylammonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, butyltriphenylammonium 2- [3- ( 2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate and the like.
　また、テトラキス（メトキシメチル）ホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、テトラキス（カルボキシエチル）ホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、テトラベンジルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、フェニルトリス（メトキシメチル）ホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、フェニルトリス（カルボキシエチル）ホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、フェニルトリベンジルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、（メトキシメチル）トリフェニルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、（カルボキシエチル）トリフェニルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、ベンジルトリフェニルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、テトラキス（メトキシメチル）アンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、テトラキス（カルボキシエチル）アンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、テトラベンジルアンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、フェニルトリス（メトキシメチル）アンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、フェニルトリス（カルボキシエチル）アンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、フェニルトリベンジルアンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、（メトキシメチル）トリフェニルアンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、（カルボキシエチル）トリフェニルアンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、ベンジルトリフェニルアンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート、テトラキス（メトキシメチル）ホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、テトラキス（カルボキシエチル）ホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、テトラベンジルホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、フェニルトリス（メトキシメチル）ホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、フェニルトリス（カルボキシエチル）ホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、フェニルトリベンジルホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、（メトキシメチル）トリフェニルホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、（カルボキシエチル）トリフェニルホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、ベンジルトリフェニルホスホニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、テトラキス（メトキシメチル）アンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、テトラキス（カルボキシエチル）アンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、テトラベンジルアンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、フェニルトリス（メトキシメチル）アンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、フェニルトリス（カルボキシエチル）アンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、フェニルトリベンジルアンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、（メトキシメチル）トリフェニルアンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、（カルボキシエチル）トリフェニルアンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、ベンジルトリフェニルアンモニウム２，６－ビス（４－ヒドロキシ－３，５－ジメチルベンジル）－４－メチルフェノラート、テトラキス（メトキシメチル）ホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、テトラキス（カルボキシエチル）ホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、テトラベンジルホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、フェニルトリス（メトキシメチル）ホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、フェニルトリス（カルボキシエチル）ホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、フェニルトリベンジルホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、（メトキシメチル）トリフェニルホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、（カルボキシエチル）トリフェニルホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、ベンジルトリフェニルホスホニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、テトラキス（メトキシメチル）アンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、テトラキス（カルボキシエチル）アンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、テトラベンジルアンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、フェニルトリス（メトキシメチル）アンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、フェニルトリス（カルボキシエチル）アンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、フェニルトリベンジルアンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、（４－メチルフェニル）トリフェニルアンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、（メトキシメチル）トリフェニルアンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、（カルボキシエチル）トリフェニルアンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、ベンジルトリフェニルアンモニウム２，６－ビス（２，４－ジヒドロキシベンジル）－４－メチルフェノラート、テトラキス（メトキシメチル）ホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、テトラキス（カルボキシエチル）ホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、テトラベンジルホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、フェニルトリス（メトキシメチル）ホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、フェニルトリス（カルボキシエチル）ホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、フェニルトリベンジルホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、（メトキシメチル）トリフェニルホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、（カルボキシエチル）トリフェニルホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、ベンジルトリフェニルホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、テトラキス（メトキシメチル）アンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、テトラキス（カルボキシエチル）アンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、テトラベンジルアンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、フェニルトリス（メトキシメチル）アンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、フェニルトリス（カルボキシエチル）アンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、フェニルトリベンジルアンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、（メトキシメチル）トリフェニルアンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、（カルボキシエチル）トリフェニルアンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート、ベンジルトリフェニルアンモニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート等が挙げられる。 Also, tetrakis (methoxymethyl) phosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, tetrakis (carboxyethyl) phosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) ) -4-Methylphenolate, tetrabenzylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, phenyltris (methoxymethyl) phosphonium 2,6-bis (2-hydroxy- 5-methylbenzyl) -4-methylphenolate, phenyltris (carboxyethyl) phosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, phenyltribenzylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl -4-methylphenolate, (methoxymethyl) triphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, (carboxyethyl) triphenylphosphonium 2,6-bis (2 -Hydroxy-5-methylbenzyl) -4-methylphenolate, benzyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, tetrakis (methoxymethyl) ammonium 2,6 -Bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, tetrakis (carboxyethyl) ammonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, tetrabenzylammonium 2,6-bis (2-hydroxy-5 Methylbenzyl) -4-methylphenolate, phenyltris (methoxymethyl) ammonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, phenyltris (carboxyethyl) ammonium 2,6- Bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, phenyltribenzylammonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, (methoxymethyl) triphenyl Ammonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, (carboxyethyl) triphenylammonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylpheno Benzyltriphenylammonium 2, 6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate, tetrakis (methoxymethyl) phosphonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, Tetrakis (carboxyethyl) phosphonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, tetrabenzylphosphonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, phenyltris (methoxymethyl) phosphonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, phenyltris (carboxyethyl) phosphonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methyl Enolate, phenyltribenzylphosphonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, (methoxymethyl) triphenylphosphonium 2,6-bis (4-hydroxy-3,5 -Dimethylbenzyl) -4-methylphenolate, (carboxyethyl) triphenylphosphonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, benzyltriphenylphosphonium 2,6- Bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, tetrakis (methoxymethyl) ammonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, Tetrakis (carboxyethyl) ammonium 2,6-bi (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, tetrabenzylammonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, phenyltris (methoxy Methyl) ammonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, phenyltris (carboxyethyl) ammonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) ) -4-Methylphenolate, phenyltribenzylammonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, (methoxymethyl) triphenylammonium 2,6-bis (4 -Hydroxy-3,5-dimethylbenzyl) -4-methylphenol , (Carboxyethyl) triphenylammonium 2,6-bis (4-hydroxy-3,5-dimethylbenzyl) -4-methylphenolate, benzyltriphenylammonium 2,6-bis (4-hydroxy-3,5 -Dimethylbenzyl) -4-methylphenolate, tetrakis (methoxymethyl) phosphonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, tetrakis (carboxyethyl) phosphonium 2,6-bis (2 , 4-dihydroxybenzyl) -4-methylphenolate, tetrabenzylphosphonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, phenyltris (methoxymethyl) phosphonium 2,6-bis (2 , 4-dihydroxybenzyl) -4-methylphen Phenyltris (carboxyethyl) phosphonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, phenyltribenzylphosphonium 2,6-bis (2,4-dihydroxybenzyl) -4-methyl Phenolate, (methoxymethyl) triphenylphosphonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, (carboxyethyl) triphenylphosphonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, benzyltriphenylphosphonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, tetrakis (methoxymethyl) ammonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, Trakis (carboxyethyl) ammonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, tetrabenzylammonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, phenyl Tris (methoxymethyl) ammonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, phenyltris (carboxyethyl) ammonium 2,6-bis (2,4-dihydroxybenzyl) -4-methyl Phenolate, phenyltribenzylammonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, (4-methylphenyl) triphenylammonium 2,6-bis (2,4-dihydroxybenzyl)- 4-methylphenolate, (methoxymeth Tyl) triphenylammonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, (carboxyethyl) triphenylammonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylpheno Benzyltriphenylammonium 2,6-bis (2,4-dihydroxybenzyl) -4-methylphenolate, tetrakis (methoxymethyl) phosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2- Hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, tetrakis (carboxyethyl) phosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5- Methylbenzyl] -6- (2-hydroxy-5-methylben Phenolate, tetrabenzylphosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, phenyltris ( Methoxymethyl) phosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, phenyltris (carboxyethyl) Phosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, phenyltribenzylphosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy- -Methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, (methoxymethyl) triphenylphosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl ] -6- (2-Hydroxy-5-methylbenzyl) phenolate, (carboxyethyl) triphenylphosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6 -(2-hydroxy-5-methylbenzyl) phenolate, benzyltriphenylphosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy- 5-methylbenzyl) phenolate, tetrakis (methoxymethyl) ammonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, tetrakis (carboxyethyl) ammonium 2- [3 -(2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, tetrabenzylammonium 2- [3- (2-hydroxy-5 -Methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, phenyltris (methoxymethyl) ammonium 2- [3- (2-hydroxy-5-methylbenzyl) ) -2-Hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) (Zyl) phenolate, phenyltris (carboxyethyl) ammonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate Phenyltribenzylammonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, (methoxymethyl) tri Phenylammonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, (carboxyethyl) triphenylammonium 2 -[3- (2-hydroxy-5-methylbenzyl) 2-hydroxy-5-methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate, benzyltriphenylammonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5- Methylbenzyl] -6- (2-hydroxy-5-methylbenzyl) phenolate and the like.
　一般式（３”）の本発明のオニウム塩としては、テトラフェニルホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、テトラキス（４－メチルフェニル）ホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、テトラキス（４－メトキシフェニル）ホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、テトラブチルホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、フェニルトリス（４－メチルフェニル）ホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、フェニルトリス（４－メトキシフェニル）ホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、フェニルトリブチルホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、（４－メチルフェニル）トリフェニルホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、（４－メトキシフェニル）トリフェニルホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、ブチルトリフェニルホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、テトラフェニルアンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、テトラキス（４－メチルフェニル）アンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、テトラキス（４－メトキシフェニル）アンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、テトラブチルアンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、フェニルトリス（４－メチルフェニル）アンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、フェニルトリス（４－メトキシフェニル）アンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、フェニルトリブチルアンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、（４－メチルフェニル）トリフェニルアンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、（４－メトキシフェニル）トリフェニルアンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、ブチルトリフェニルアンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、テトラフェニルホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、テトラキス（４－メチルフェニル）ホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、テトラキス（４－メトキシフェニル）ホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、テトラブチルホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリス（４－メチルフェニル）ホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリス（４－メトキシフェニル）ホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリブチルホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、（４－メチルフェニル）トリフェニルホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、（４－メトキシフェニル）トリフェニルホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、ブチルトリフェニルホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、テトラフェニルアンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、テトラキス（４－メチルフェニル）アンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、テトラキス（４－メトキシフェニル）アンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、テトラブチルアンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリス（４－メチルフェニル）アンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリス（４－メトキシフェニル）アンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリブチルアンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、（４－メチルフェニル）トリフェニルアンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、（４－メトキシフェニル）トリフェニルアンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、ブチルトリフェニルアンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート等が挙げられる。 Examples of the onium salt of the present invention represented by the general formula (3 ″) include tetraphenylphosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate and tetrakis (4-methylphenyl) phosphonium 4- [bis (4-hydroxyphenyl) Methyl] phenolate, tetrakis (4-methoxyphenyl) phosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, tetrabutylphosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, phenyltris (4-methylphenyl ) Phosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, phenyltris (4-methoxyphenyl) phosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, phenyltributylphosphonium 4- Bis (4-hydroxyphenyl) methyl] phenolate, (4-methylphenyl) triphenylphosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, (4-methoxyphenyl) triphenylphosphonium 4- [bis (4- (Hydroxyphenyl) methyl] phenolate, butyltriphenylphosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, tetraphenylammonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, tetrakis (4-methylphenyl) ammonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, tetrakis (4-methoxyphenyl) ammonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, tetrabutylammonium -[Bis (4-hydroxyphenyl) methyl] phenolate, phenyltris (4-methylphenyl) ammonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, phenyltris (4-methoxyphenyl) ammonium 4- [bis ( 4-hydroxyphenyl) methyl] phenolate, phenyltributylammonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, (4-methylphenyl) triphenylammonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, ( 4-methoxyphenyl) triphenylammonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, butyltriphenylammonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, tetraphen Nylphosphonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, tetrakis (4-methylphenyl) phosphonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, tetrakis (4- Methoxyphenyl) phosphonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, tetrabutylphosphonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, phenyltris (4-methylphenyl ) Phosphonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, phenyltris (4-methoxyphenyl) phosphonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, phenyltributylphosphonium 4- [1,1 Bis (4-hydroxyphenyl) ethyl] phenolate, (4-methylphenyl) triphenylphosphonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, (4-methoxyphenyl) triphenylphosphonium 4- [ 1,1-bis (4-hydroxyphenyl) ethyl] phenolate, butyltriphenylphosphonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, tetraphenylammonium 4- [1,1-bis (4 -Hydroxyphenyl) ethyl] phenolate, tetrakis (4-methylphenyl) ammonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, tetrakis (4-methoxyphenyl) ammonium 4- [1,1-bis (4-hydroxyphenyl Ethyl] phenolate, tetrabutylammonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, phenyltris (4-methylphenyl) ammonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] Phenolate, phenyltris (4-methoxyphenyl) ammonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, phenyltributylammonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, (4-methylphenyl) triphenylammonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, (4-methoxyphenyl) triphenylammonium 4- [1,1-bis (4-hydroxyphenyl) Ethyl] phenolate, Tyltriphenylammonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate;
　また、テトラキス（メトキシメチル）ホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、テトラキス（カルボキシエチル）ホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、テトラベンジルホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、フェニルトリス（メトキシメチル）ホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、フェニルトリス（カルボキシエチル）ホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、フェニルトリベンジルホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、（メトキシメチル）トリフェニルホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、（カルボキシエチル）トリフェニルホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、ベンジルトリフェニルホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、テトラキス（メトキシメチル）アンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、テトラキス（カルボキシエチル）アンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、テトラベンジルアンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、フェニルトリス（メトキシメチル）アンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、フェニルトリス（カルボキシエチル）アンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、フェニルトリベンジルアンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、（メトキシメチル）トリフェニルアンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、（カルボキシエチル）トリフェニルアンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、ベンジルトリフェニルアンモニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート、テトラキス（メトキシメチル）ホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、テトラキス（カルボキシエチル）ホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、テトラベンジルホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリス（メトキシメチル）ホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリス（カルボキシエチル）ホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリベンジルホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、（メトキシメチル）トリフェニルホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、（カルボキシエチル）トリフェニルホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、ベンジルトリフェニルホスホニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、テトラキス（メトキシメチル）アンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、テトラキス（カルボキシエチル）アンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、テトラベンジルアンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリス（メトキシメチル）アンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリス（カルボキシエチル）アンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリベンジルアンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、（メトキシメチル）トリフェニルアンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、（カルボキシエチル）トリフェニルアンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート、ベンジルトリフェニルアンモニウム４－［１，１－ビス（４－ヒドロキシフェニル）エチル］フェノラート等が挙げられる。 Further, tetrakis (methoxymethyl) phosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, tetrakis (carboxyethyl) phosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, tetrabenzylphosphonium 4- [bis ( 4-hydroxyphenyl) methyl] phenolate, phenyltris (methoxymethyl) phosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, phenyltris (carboxyethyl) phosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate Phenyltribenzylphosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, (methoxymethyl) triphenylphosphonium 4- [bis (4-hydroxyphenyl) meth Phenolate, (carboxyethyl) triphenylphosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, benzyltriphenylphosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, tetrakis (methoxymethyl) ammonium 4 -[Bis (4-hydroxyphenyl) methyl] phenolate, tetrakis (carboxyethyl) ammonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, tetrabenzylammonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, Phenyltris (methoxymethyl) ammonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, phenyltris (carboxyethyl) ammonium 4- [bis (4-hydroxy Phenyl) methyl] phenolate, phenyltribenzylammonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, (methoxymethyl) triphenylammonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, (carboxyethyl) triol Phenylammonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, benzyltriphenylammonium 4- [bis (4-hydroxyphenyl) methyl] phenolate, tetrakis (methoxymethyl) phosphonium 4- [1,1-bis (4 -Hydroxyphenyl) ethyl] phenolate, tetrakis (carboxyethyl) phosphonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, tetrabenzylphosphonium 4- [1,1 -Bis (4-hydroxyphenyl) ethyl] phenolate, phenyltris (methoxymethyl) phosphonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, phenyltris (carboxyethyl) phosphonium 4- [1,1 -Bis (4-hydroxyphenyl) ethyl] phenolate, phenyltribenzylphosphonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, (methoxymethyl) triphenylphosphonium 4- [1,1-bis ( 4-hydroxyphenyl) ethyl] phenolate, (carboxyethyl) triphenylphosphonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, benzyltriphenylphosphonium 4- [1,1-bis (4-hydroxy Phenyl Ethyl] phenolate, tetrakis (methoxymethyl) ammonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, tetrakis (carboxyethyl) ammonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] Phenolate, tetrabenzylammonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, phenyltris (methoxymethyl) ammonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, phenyltris (Carboxyethyl) ammonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, phenyltribenzylammonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, (methoxymethyl Triphenylammonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, (carboxyethyl) triphenylammonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate, benzyltriphenylammonium 4- [1,1-bis (4-hydroxyphenyl) ethyl] phenolate and the like.
　一般式（４”）の本発明のオニウム塩としては、テトラフェニルホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、テトラキス（４－メチルフェニル）ホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、テトラキス（４－メトキシフェニル）ホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、テトラブチルホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリス（４－メチルフェニル）ホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリス（４－メトキシフェニル）ホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリブチルホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、（４－メチルフェニル）トリフェニルホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、（４－メトキシフェニル）トリフェニルホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、ブチルトリフェニルホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、テトラフェニルアンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、テトラキス（４－メチルフェニル）アンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、テトラキス（４－メトキシフェニル）アンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、テトラブチルアンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリス（４－メチルフェニル）アンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリス（４－メトキシフェニル）アンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリブチルアンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、（４－メチルフェニル）トリフェニルアンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、（４－メトキシフェニル）トリフェニルアンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、ブチルトリフェニルアンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、テトラフェニルホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、テトラキス（４－メチルフェニル）ホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、テトラキス（４－メトキシフェニル）ホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、テトラブチルホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、フェニルトリス（４－メチルフェニル）ホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、フェニルトリス（４－メトキシフェニル）ホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、フェニルトリブチルホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、（４－メチルフェニル）トリフェニルホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、（４－メトキシフェニル）トリフェニルホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、ブチルトリフェニルホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、テトラフェニルアンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、テトラキス（４－メチルフェニル）アンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、テトラキス（４－メトキシフェニル）アンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、テトラブチルアンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、フェニルトリス（４－メチルフェニル）アンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、フェニルトリス（４－メトキシフェニル）アンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、フェニルトリブチルアンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、（４－メチルフェニル）トリフェニルアンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、（４－メトキシフェニル）トリフェニルアンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、ブチルトリフェニルアンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート等が挙げられる。 Examples of the onium salt of the present invention represented by the general formula (4 ″) include tetraphenylphosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate and tetrakis (4-methylphenyl) phosphonium 4- [1 , 2,2-Tris (4-hydroxyphenyl) ethyl] phenolate, tetrakis (4-methoxyphenyl) phosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, tetrabutylphosphonium 4- [ 1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, phenyltris (4-methylphenyl) phosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, phenyltris (4 -Methoxyphenyl) phosphonium 4- [1,2,2-tri (4-hydroxyphenyl) ethyl] phenolate, phenyltributylphosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, (4-methylphenyl) triphenylphosphonium 4- [1,2,2 -Tris (4-hydroxyphenyl) ethyl] phenolate, (4-methoxyphenyl) triphenylphosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, butyltriphenylphosphonium 4- [1, 2,2-Tris (4-hydroxyphenyl) ethyl] phenolate, tetraphenylammonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, tetrakis (4-methylphenyl) ammonium 4- [1 , 2,2-Tris (4-H Roxyphenyl) ethyl] phenolate, tetrakis (4-methoxyphenyl) ammonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, tetrabutylammonium 4- [1,2,2-tris (4 -Hydroxyphenyl) ethyl] phenolate, phenyltris (4-methylphenyl) ammonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, phenyltris (4-methoxyphenyl) ammonium 4- [1 , 2,2-Tris (4-hydroxyphenyl) ethyl] phenolate, phenyltributylammonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, (4-methylphenyl) triphenylammonium 4- [1,2,2-Tris (4-hydroxyphenyl) ethyl] phenolate, (4-methoxyphenyl) triphenylammonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, butyltriphenylammonium 4- [1,2,2 2-tris (4-hydroxyphenyl) ethyl] phenolate, tetraphenylphosphonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, tetrakis ( 4-methylphenyl) phosphonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, tetrakis (4-methoxyphenyl) phosphonium 4- {α -(4-hydroxyphenyl) -4- [1,1-bi (4-hydroxyphenyl) methyl] benzyl} phenolate, tetrabutylphosphonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, phenyltris ( 4-methylphenyl) phosphonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, phenyltris (4-methoxyphenyl) phosphonium 4- { α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, phenyltributylphosphonium 4- {α- (4-hydroxyphenyl) -4- [1,1 -Bis (4-hydroxyphenyl) methyl] benzyl} phenolate, ( 4-methylphenyl) triphenylphosphonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, (4-methoxyphenyl) triphenylphosphonium 4 -{Α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, butyltriphenylphosphonium 4- {α- (4-hydroxyphenyl) -4- [ 1,1-bis (4-hydroxyphenyl) methyl] benzyl {phenolate, tetraphenylammonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} Phenolate, tetrakis (4-methylphenyl) ammonium 4- {α- (4-hydro (Xyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, tetrakis (4-methoxyphenyl) ammonium 4- {α- (4-hydroxyphenyl) -4- [1,1- Bis (4-hydroxyphenyl) methyl] benzyl} phenolate, tetrabutylammonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, phenyltris (4-methylphenyl) ammonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, phenyltris (4-methoxyphenyl) ammonium 4- ｛Α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydrido) [Xyphenyl) methyl] benzyl} phenolate, phenyltributylammonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, (4-methylphenyl) triol Phenylammonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, (4-methoxyphenyl) triphenylammonium 4- {α- (4 -Hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, butyltriphenylammonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis ( 4-hydroxyphenyl) methyl] benzyl} phenolate and the like
　また、テトラキス（メトキシメチル）ホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、テトラキス（カルボキシエチル）ホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、テトラベンジルホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリス（メトキシメチル）ホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリス（カルボキシエチル）ホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリベンジルホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、（メトキシメチル）トリフェニルホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、（カルボキシエチル）トリフェニルホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、ベンジルトリフェニルホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、テトラキス（メトキシメチル）アンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、テトラキス（カルボキシエチル）アンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、テトラベンジルアンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリス（メトキシメチル）アンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリス（カルボキシエチル）アンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、フェニルトリベンジルアンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、（メトキシメチル）トリフェニルアンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、（カルボキシエチル）トリフェニルアンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、ベンジルトリフェニルアンモニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート、テトラキス（メトキシメチル）ホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、テトラキス（カルボキシエチル）ホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、テトラベンジルホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、フェニルトリス（メトキシメチル）ホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、フェニルトリス（カルボキシエチル）ホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、フェニルトリベンジルホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、（メトキシメチル）トリフェニルホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、（カルボキシエチル）トリフェニルホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、ベンジルトリフェニルホスホニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、テトラキス（メトキシメチル）アンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、テトラキス（カルボキシエチル）アンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、テトラベンジルアンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、フェニルトリス（メトキシメチル）アンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、フェニルトリス（カルボキシエチル）アンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、フェニルトリベンジルアンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、（メトキシメチル）トリフェニルアンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、（カルボキシエチル）トリフェニルアンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート、ベンジルトリフェニルアンモニウム４－｛α－（４－ヒドロキシフェニル）－４－［１，１－ビス（４－ヒドロキシフェニル）メチル］ベンジル｝フェノラート等が挙げられる。 Also, tetrakis (methoxymethyl) phosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, tetrakis (carboxyethyl) phosphonium 4- [1,2,2-tris (4-hydroxyphenyl) Ethyl] phenolate, tetrabenzylphosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, phenyltris (methoxymethyl) phosphonium 4- [1,2,2-tris (4-hydroxyphenyl) Ethyl] phenolate, phenyltris (carboxyethyl) phosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, phenyltribenzylphosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ) Ethyl] phenol , (Methoxymethyl) triphenylphosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, (carboxyethyl) triphenylphosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ) Ethyl] phenolate, benzyltriphenylphosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, tetrakis (methoxymethyl) ammonium 4- [1,2,2-tris (4-hydroxyphenyl) ) Ethyl] phenolate, tetrakis (carboxyethyl) ammonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, tetrabenzylammonium 4- [1,2,2-tris (4-hydroxyphenyl) Ethyl] phenolate, Fe Tris (methoxymethyl) ammonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, phenyltris (carboxyethyl) ammonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl Phenolate, phenyltribenzylammonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, (methoxymethyl) triphenylammonium 4- [1,2,2-tris (4-hydroxyphenyl) Ethyl] phenolate, (carboxyethyl) triphenylammonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate, benzyltriphenylammonium 4- [1,2,2-tris (4-hydroxyphenyl) ) Ethyl] phenolate, Tetrakis (methoxymethyl) phosphonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, tetrakis (carboxyethyl) phosphonium 4- {α- ( 4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, tetrabenzylphosphonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis ( 4-hydroxyphenyl) methyl] benzyl} phenolate, phenyltris (methoxymethyl) phosphonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, Phenyltris (carboxyethyl) phosphonium 4- {α- (4- (Hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, phenyltribenzylphosphonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4 -Hydroxyphenyl) methyl] benzyl} phenolate, (methoxymethyl) triphenylphosphonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, ( Carboxyethyl) triphenylphosphonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, benzyltriphenylphosphonium 4- {α- (4- Hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) ) Methyl] benzyl} phenolate, tetrakis (methoxymethyl) ammonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, tetrakis (carboxyethyl) Ammonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, tetrabenzylammonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, phenyltris (methoxymethyl) ammonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) ) Methyl] benzyl diphenolate, phenyltris (carboxy) Tyl) ammonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, phenyltribenzylammonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, (methoxymethyl) triphenylammonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4 -Hydroxyphenyl) methyl] benzyl} phenolate, (carboxyethyl) triphenylammonium 4- {α- (4-hydroxyphenyl) -4- [1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate, benzyl Triphenylammonium 4- {α- (4-hydroxyphenyl) -4- [ , 1,1-bis (4-hydroxyphenyl) methyl] benzyl} phenolate and the like.
　一般式（５”）の本発明のオニウム塩としては、下記一般式（５”－１）が挙げられる。
Figure JPOXMLDOC01-appb-C000037
 （式中、Ｑ、Ｒ１～Ｒ４は、前記と同意である。） The onium salt of the present invention represented by the general formula (5 ″) includes the following general formula (5 ″ -1).
Figure JPOXMLDOC01-appb-C000037
 (Wherein, Q and R 1 to R 4 are as defined above.)
　また、本発明は、本発明の熱硬化性樹脂用硬化促進剤と、熱硬化性樹脂とを少なくとも含む、熱硬化性樹脂系組成物である（以下、「本発明の単独硬化型熱硬化性樹脂系組成物」ということがある）。さらなる本発明は、さらに熱硬化性樹脂用硬化剤を含む、熱硬化性樹脂系組成物である。以下、これらを「本発明の熱硬化性樹脂系組成物」ということがある。 Further, the present invention is a thermosetting resin-based composition comprising at least the curing accelerator for a thermosetting resin of the present invention and a thermosetting resin (hereinafter, referred to as a “single-curing thermosetting resin of the present invention”). Resin-based composition "). A further aspect of the present invention is a thermosetting resin composition further including a curing agent for a thermosetting resin. Hereinafter, these may be referred to as “the thermosetting resin composition of the present invention”.
　本発明の熱硬化性樹脂系組成物の成分である熱硬化性樹脂の好ましい例であるエポキシ樹脂、マレイミド樹脂、シアネート樹脂、イソシアネート樹脂、および熱硬化性樹脂用硬化剤について次に説明する。 エ ポ キ シ Epoxy resins, maleimide resins, cyanate resins, isocyanate resins, and curing agents for thermosetting resins, which are preferable examples of the thermosetting resin that is a component of the thermosetting resin composition of the present invention, will be described below.
＜エポキシ樹脂＞
　エポキシ樹脂としては、特に限定されず、１分子中に２個以上のエポキシ基を有する汎用的なエポキシ樹脂を用いることが可能であり、例えば、フェノール、クレゾール、キシレノール、カテコール、レゾルシン、ビスフェノールＡ、ビスフェノールＦ等のフェノール類および／またはナフトール、ジヒドロキシナフタレン等のナフトール類とホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド、サリチルアルデヒド等のアルデヒド基を有する化合物とを酸性触媒の存在下で縮合または共縮合させて得られるノボラック樹脂をエポキシ化したフェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂；ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、アルキル置換または非置換のビフェノール、スチルベン系フェノール類等をエポキシ化したビスフェノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、スチルベン型エポキシ樹脂；フェノール類および／またはナフトール類とジメトキシパラキシレンやビス（メトキシメチル）ビフェニルから合成されるフェノールアラルキル樹脂、ナフトールアラルキル樹脂、ビフェニルアラルキル樹脂等をエポキシ化したフェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂；ブタンジオール、ポリエチレングリコール、ポリプロピレングリコール等のアルコール類のグリシジルエーテル型エポキシ樹脂；フタル酸、イソフタル酸、テトラヒドロフタル酸等のカルボン酸類のグリシジルエステル型エポキシ樹脂；アニリン、イソシアヌル酸等の窒素原子に結合した活性水素をグリシジル基で置換したグリシジル型またはメチルグリシジル型エポキシ樹脂；分子内のオレフィン結合をエポキシ化して得られるビニルシクロヘキセンジエポキシド、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、２－（３，４－エポキシ）シクロヘキシル－５，５－スピロ（３，４－エポキシ）シクロヘキサン－ｍ－ジオキサン等の脂環型エポキシ樹脂；パラキシリレンおよび／またはメタキシリレン変性フェノール樹脂のグリシジルエーテル；テルペン変性フェノール樹脂のグリシジルエーテル；フェノール類および／またはナフトール類とジシクロペンタジエンから合成される、ジシクロペンタジエン変性フェノール樹脂、ジシクロペンタジエン型ナフトール樹脂のグリシジルエーテル；シクロペンタジエン変性フェノール樹脂のグリシジルエーテル；多環芳香環変性フェノール樹脂のグリシジルエーテル；ナフタレン環含有フェノール樹脂のグリシジルエーテル；ハロゲン化フェノールノボラック型エポキシ樹脂；ハイドロキノン型エポキシ樹脂；トリメチロールプロパン型エポキシ樹脂；オレフィン結合を過酢酸等の過酸で酸化して得られる線状脂肪族エポキシ樹脂；ジフェニルメタン型エポキシ樹脂；硫黄原子含有エポキシ樹脂等が挙げられる。 <Epoxy resin>
The epoxy resin is not particularly limited, and a general-purpose epoxy resin having two or more epoxy groups in one molecule can be used. For example, phenol, cresol, xylenol, catechol, resorcin, bisphenol A, A phenol such as bisphenol F and / or a naphthol such as naphthol and dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde are condensed or co-condensed in the presence of an acidic catalyst. Phenol novolak type epoxy resin obtained by epoxidizing the obtained novolak resin, orthocresol novolak type epoxy resin; bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or non-substituted Bisphenol-type epoxy resin, biphenyl-type epoxy resin, stilbene-type epoxy resin obtained by epoxidizing substituted biphenol, stilbene-based phenols, etc .; synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl Phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin obtained by epoxidizing phenol aralkyl resin, naphthol aralkyl resin, biphenyl aralkyl resin, etc .; glycidyl ether type of alcohols such as butanediol, polyethylene glycol and polypropylene glycol Epoxy resin; glycidyl ester type epoxy resin of carboxylic acids such as phthalic acid, isophthalic acid and tetrahydrophthalic acid Glycidyl-type or methylglycidyl-type epoxy resin in which active hydrogen bonded to a nitrogen atom such as aniline or isocyanuric acid is substituted with a glycidyl group; vinylcyclohexene diepoxide, 3,4-epoxycyclohexyl obtained by epoxidizing an olefin bond in a molecule Alicyclic epoxy resins such as methyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane; paraxylylene and / or Or a glycidyl ether of a metaxylylene-modified phenol resin; a glycidyl ether of a terpene-modified phenol resin; a dicyclopentadiene-modified phenol resin synthesized from phenols and / or naphthols and dicyclopentadiene Glycidyl ether of dicyclopentadiene type naphthol resin; glycidyl ether of cyclopentadiene-modified phenol resin; glycidyl ether of polycyclic aromatic ring-modified phenol resin; glycidyl ether of phenol resin containing naphthalene ring; halogenated phenol novolak epoxy resin; hydroquinone type Epoxy resin; trimethylolpropane-type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid; diphenylmethane-type epoxy resin; sulfur atom-containing epoxy resin.
　これらのエポキシ樹脂は、単独で、また２種類以上を混合してもよく、有姿のまま使用してもよく、適宜溶剤や添加材等を添加してもよく、市販品を使用してもよい。 These epoxy resins may be used alone or as a mixture of two or more kinds, may be used as they are, may be appropriately added with a solvent or an additive, or may be a commercially available product. Good.
＜マレイミド樹脂＞
　マレイミド樹脂としては、特に限定されず、１分子中に２個以上のマレイミド基を有する汎用的なマレイミド樹脂を用いることが可能であり、例えば、４，４’－ビスマレイミドジフェニルメタン、Ｎ，Ｎ’－１，３－フェニレンジマレイミド、２，２’－ビス［４－（４－マレイミドフェノキシ）フェニル］プロパン、３，３’－ジメチル－５，５’－ジエチル－４，４’－ジフェニルメタンビスマレイミド、４－メチル－１，３－フェニレンビスマレイミド、１，６’－ビスマレイミド－（２，２，４－トリメチル）ヘキサン、ポリフェニルメタンマレイミド等が挙げられる。 <Maleimide resin>
The maleimide resin is not particularly limited, and a general-purpose maleimide resin having two or more maleimide groups in one molecule can be used. For example, 4,4′-bismaleimidediphenylmethane, N, N ′ 1,3-phenylenedimaleimide, 2,2'-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide , 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, polyphenylmethanemaleimide and the like.
　これらのマレイミド樹脂は、単独で、また２種類以上を混合してもよく、有姿のまま使用してもよく、適宜溶媒や添加材等を添加してもよく、市販品を使用してもよい。 These maleimide resins may be used alone or as a mixture of two or more kinds, may be used as they are, may be appropriately added with a solvent or an additive, or may be a commercially available product. Good.
＜シアネート樹脂＞
　シアネート樹脂としては、特に限定されず、１分子中に２個以上のシアネート基を有する汎用的なシアネート樹脂を用いることが可能であり、例えば、１，３－ジシアナトベンゼン、１，４－ジシアナトベンゼン、１，３，５－トリシアナトベンゼン、ビス（３，５－ジメチル－４－シアナトフェニル）メタン、１，３－ジシアナトナフタレン、１，４－ジシアナトナフタレン、１，６－ジシアナトナフタレン、１，８－ジシアナトナフタレン、２，６－ジシアナトナフタレン、２，７－ジシアナトナフタレン、１，３，６－トリシアナトナフタレン、４，４’－ジシアナトビフェニル、ビス（４－シアナトフェニル）メタン、２，２’－ビス（４－シアナトフェニル）プロパン、ビス（４－シアナトフェニル）エーテル、ビス（４－シアナトフェニル）チオエーテル、ビス（４－シアナトフェニル）スルホン、２，２’－ビス（４－シアナトフェニル）プロパン、ビス（３，５－ジメチル－４－シアナトフェニル）メタン、ノボラック樹脂をシアネート化したフェノールノボラック型シアネート樹脂等が挙げられる。 <Cyanate resin>
The cyanate resin is not particularly limited, and a general-purpose cyanate resin having two or more cyanate groups in one molecule can be used. For example, 1,3-dicyanatobenzene, Anatobenzene, 1,3,5-tricyanatobenzene, bis (3,5-dimethyl-4-cyanatophenyl) methane, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-disi Anatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4′-dicyanatobiphenyl, bis (4- Cyanatophenyl) methane, 2,2′-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ether, bis (4-cyanato Enyl) thioether, bis (4-cyanatophenyl) sulfone, 2,2′-bis (4-cyanatophenyl) propane, bis (3,5-dimethyl-4-cyanatophenyl) methane, cyanate novolak resin Phenol novolak type cyanate resin and the like.
　これらのシアネート樹脂は、単独で、また２種類以上を混合してもよく、有姿のまま使用してもよく、適宜溶媒や添加材等を添加してもよく、市販品を使用してもよい。 These cyanate resins may be used alone or as a mixture of two or more kinds, may be used as they are, may be appropriately added with a solvent or an additive, or may be a commercially available product. Good.
＜イソシアネート樹脂＞
　イソシアネート樹脂としては、特に限定されず、１分子中に２個以上のイソシアネート基を有する汎用的なイソシアネート樹脂を用いることが可能であり、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート等のポリイソシアネートと、ポリプロピレングリコール、ポリテトラメチレングリコール等のポリオールとの反応で得られる末端イソシアネート基オリゴマーの末端イソシアネート基を、フェノール類、アルコール類等でブロックしたイソシアネート樹脂等が挙げられる。 <Isocyanate resin>
The isocyanate resin is not particularly limited, and a general-purpose isocyanate resin having two or more isocyanate groups in one molecule can be used. For example, polyisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and polypropylene Isocyanate resins in which terminal isocyanate groups of terminal oligomers of isocyanate groups obtained by reaction with a polyol such as glycol or polytetramethylene glycol are blocked with phenols, alcohols, and the like.
　これらのイソシアネート樹脂は、単独で、また２種類以上を混合してもよく、有姿のまま使用してもよく、適宜溶媒や添加材等を添加してもよく、市販品を使用してもよい。 These isocyanate resins may be used alone or as a mixture of two or more kinds, may be used as they are, may be appropriately added with a solvent or an additive, or may be a commercially available product. Good.
＜硬化剤＞
　熱硬化性樹脂用硬化剤としては、フェノール樹脂系硬化剤、アミン系硬化剤、酸無水物系硬化剤、ベンゾオキサジン系硬化剤、ジシアンジアミド等が挙げられる。また、熱硬化性樹脂系組成物の主剤として用いる熱硬化性樹脂以外の熱硬化性樹脂を、熱硬化性樹脂用硬化剤として使用してもよい。 <Curing agent>
Examples of the curing agent for a thermosetting resin include a phenol resin-based curing agent, an amine-based curing agent, an acid anhydride-based curing agent, a benzoxazine-based curing agent, and dicyandiamide. Further, a thermosetting resin other than the thermosetting resin used as a main component of the thermosetting resin composition may be used as a curing agent for the thermosetting resin.
　フェノール樹脂系硬化剤としては、特に限定されず、一般に硬化剤として使用される１分子中に２個以上のフェノール性水酸基を有する汎用的なフェノール樹脂を用いることが可能であり、例えば、カテコール、レゾルシン、ヒドロキノン、ビスフェノールＡ、ビスフェノールＦ、置換または非置換のビフェノール等の１分子中に２個以上のフェノール性水酸基を有する化合物；フェノール、クレゾール、キシレノール、カテコール、レゾルシン、ヒドロキノン、ビスフェノールＡ、ビスフェノールＦ、フェニルフェノール、アミノフェノール等のフェノール類および／またはナフトール、ジヒドロキシナフタレン等のナフトール類とホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ベンズアルデヒド、サリチルアルデヒド等から合成されるノボラック型フェノール樹脂；フェノール類および／またはナフトール類とジメトキシパラキシレンやビス（メトキシメチル）ビフェニルから合成されるフェノールアラルキル樹脂、ナフトールアラルキル樹脂、ビフェニルアラルキル樹脂等のアラルキル型フェノール樹脂；パラキシリレンおよび／またはメタキシリレン変性フェノール樹脂；メラミン変性フェノール樹脂；テルペン変性フェノール樹脂；フェノール類および／またはナフトール類とジシクロペンタジエンから合成される、ジシクロペンタジエン型フェノール樹脂、ジシクロペンタジエン型ナフトール樹脂；シクロペンタジエン変性フェノール樹脂；多環芳香環変性フェノール樹脂；ビフェニル型フェノール樹脂；トリフェニルメタン型フェノール樹脂等が挙げられる。 The phenolic resin-based curing agent is not particularly limited, and a general-purpose phenolic resin having two or more phenolic hydroxyl groups in one molecule, which is generally used as a curing agent, can be used. For example, catechol, Compounds having two or more phenolic hydroxyl groups in one molecule such as resorcin, hydroquinone, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F And phenols such as phenylphenol and aminophenol and / or naphthols such as naphthol and dihydroxynaphthalene and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde Novolak-type phenolic resin synthesized from phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl; aralkyl-type phenolic resins such as naphthol aralkyl resin and biphenylaralkyl resin; paraxylylene And / or meta-xylylene-modified phenol resin; melamine-modified phenol resin; terpene-modified phenol resin; dicyclopentadiene-type phenol resin, dicyclopentadiene-type naphthol resin synthesized from phenols and / or naphthols and dicyclopentadiene; cyclopentadiene Modified phenol resin; polycyclic aromatic ring modified phenol resin; biphenyl phenol resin; triphenylmethane phenol resin, etc. It is below.
　アミン系硬化剤としては、特に限定されず、汎用的な芳香族アミン、脂肪族アミン等を用いることが可能であり、例えば、トリエチレンテトラアミン、テトラエチレンペンタミン、ｍ－キシレンジアミン、トリメチルヘキサメチレンジアミン、２－メチルペンタメチレンジアミン等の脂肪族ポリアミン、イソフォロンジアミン、１，３－ビスアミノメチルシクロヘキサン、ビス（４－アミノシクロヘキシル）メタン、ノルボルネンジアミン、１，２－ジアミノシクロヘキサン等の脂環式ポリアミン、Ｎ－アミノエチルピペラジン、１，４－ビス（２－アミノ－２－メチルプロピル）ピペラジン等のピペラジン型のポリアミン、ジエチルトルエンジアミン、ジメチルチオトルエンジアミン、４，４’－ジアミノ－３，３’－ジエチルジフェニルメタン、ビス（メチルチオ）トルエンジアミン、ジアミノジフェニルメタン、ｍ－フェニレンジアミン、ジアミノジフェニルスルホン、トリメチレンビス（４－アミノベンゾエート）、ポリテトラメチレンオキシド－ジ－ｐ－アミノベンゾエート、ポリオキシテトラメチレンビス（ｐ－アミノベンゾエート）等が挙げられる。 The amine-based curing agent is not particularly limited, and general-purpose aromatic amines, aliphatic amines, and the like can be used. Examples thereof include triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, and trimethylhexaamine. Aliphatic polyamines such as methylenediamine and 2-methylpentamethylenediamine, alicyclic rings such as isophoronediamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, and 1,2-diaminocyclohexane Formulas polyamines, piperazine-type polyamines such as N-aminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, diethyltoluenediamine, dimethylthiotoluenediamine, 4,4′-diamino-3, 3'-diethyldiphenyl Methane, bis (methylthio) toluenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, trimethylenebis (4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate, polyoxytetramethylenebis (p -Aminobenzoate) and the like.
　酸無水物系硬化剤としては、特に限定されず、汎用的な酸無水物を用いることが可能であり、例えば、ヘキサヒドロフタル酸無水物、３－メチルヘキサヒドロフタル酸無水物、４－メチルヘキサヒドロフタル酸無水物、１－メチルノルボルナン－２，３－ジカルボン酸無水物、５－メチルノルボルナン－２，３－ジカルボン酸無水物、ノルボルナン－２，３－ジカルボン酸無水物、１－メチルナジック酸無水物、５－メチルナジック酸無水物、ナジック酸無水物、フタル酸無水物、テトラヒドロフタル酸無水物、３－メチルテトラヒドロフタル酸無水物、４－メチルテトラヒドロフタル酸無水物、およびドデセニルコハク酸無水物等が挙げられる。 The acid anhydride-based curing agent is not particularly limited, and a general-purpose acid anhydride can be used. For example, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methyl Hexahydrophthalic anhydride, 1-methylnorbornane-2,3-dicarboxylic anhydride, 5-methylnorbornane-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, 1-methylnadic Acid anhydride, 5-methylnadic anhydride, nadic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, and dodecenyl succinic anhydride Objects and the like.
　ベンゾオキサジン系硬化剤としては、特に限定されず、汎用的なベンゾオキサジン樹脂を用いることが可能であり、例えばビスフェノールＦとホルムアルデヒドとアニリンを反応させて得られるＦ－ａ型ベンゾオキサジン樹脂、ジアミノジフェニルメタンとホルムアルデヒドとフェノールを反応させて得られるＰ－ｄ型ベンゾオキサジン樹脂等が挙げられる。
　これらの硬化剤は、単独で、または２種類以上を混合して使用することができ、有姿でそのまま使用してもよく、適宜溶剤や添加材等を添加し、硬化剤組成物として使用することもでき、市販品を使用してもよい。 The benzoxazine-based curing agent is not particularly limited, and a general-purpose benzoxazine resin can be used. For example, an Fa type benzoxazine resin obtained by reacting bisphenol F with formaldehyde and aniline, diaminodiphenylmethane Pd-type benzoxazine resin obtained by reacting phenol with formaldehyde and phenol.
These hardeners can be used alone or as a mixture of two or more, and may be used as they are, and may be used as a hardener composition by appropriately adding a solvent or an additive. Alternatively, a commercially available product may be used.
＜熱硬化性樹脂系組成物＞
　また、本発明の熱硬化性樹脂系組成物は、本発明の熱硬化性樹脂用硬化促進剤、熱硬化性樹脂、および／または、熱硬化性樹脂用硬化剤の他に、効果に影響しない限り、熱硬化性樹脂系組成物に通常使用される溶剤、充填剤、添加剤等をさらに含んでもよい。
　熱硬化性樹脂系組成物は、線膨張率を小さくするために、公知の各種無機充填剤を含有することができる。無機充填剤としては、例えば、溶融シリカ、結晶シリカ、アルミナ、窒化アルミニウム等が挙げられる。これらの無機充填剤は、シランカップリング剤等のカップリング剤で表面処理してもよい。 <Thermosetting resin composition>
In addition, the thermosetting resin-based composition of the present invention does not affect the effect, in addition to the curing accelerator for thermosetting resin, the thermosetting resin, and / or the curing agent for thermosetting resin of the present invention. As long as it is included, it may further contain a solvent, a filler, an additive, and the like which are usually used in the thermosetting resin composition.
The thermosetting resin composition can contain various known inorganic fillers in order to reduce the coefficient of linear expansion. Examples of the inorganic filler include fused silica, crystalline silica, alumina, aluminum nitride, and the like. These inorganic fillers may be surface-treated with a coupling agent such as a silane coupling agent.
　その他、熱硬化性樹脂系組成物に、イオントラップ剤、離型剤、カーボンブラック等の顔料等を添加してもよく、熱硬化性樹脂以外の樹脂を含むこともできる。 In addition, an ion trapping agent, a release agent, a pigment such as carbon black, or the like may be added to the thermosetting resin-based composition, and a resin other than the thermosetting resin may be included.
　熱硬化性樹脂系組成物中の本発明のオニウム塩の含有量は、０．５重量部より少ないと、組成物の硬化力を十分に発揮できない場合があり、１０重量部より多いと、組成物の貯蔵安定性が悪くなる場合があるため、熱硬化性樹脂１００重量部に対して０．５～１０重量部であることが好ましく、硬化性をより厳密に考慮すれば、かかる含有量を０．７～５重量部とすることが更に好ましい。さらに熱硬化性樹脂用硬化剤を使用する場合、硬化剤の含有量は、熱硬化性樹脂中の反応性基当量（例えばエポキシ樹脂であれば、樹脂中のエポキシ当量）と、硬化剤の当量との当量比を考慮して、一般的には、反応性基当量と硬化剤の当量との当量比が１．０：０．９～１．０：１．２となるようにする。 When the content of the onium salt of the present invention in the thermosetting resin-based composition is less than 0.5 part by weight, the curing power of the composition may not be sufficiently exhibited. Since the storage stability of the product may be deteriorated, the content is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the thermosetting resin. More preferably, the amount is 0.7 to 5 parts by weight. When a thermosetting resin curing agent is used, the content of the curing agent is determined by the reactive group equivalent in the thermosetting resin (for example, in the case of an epoxy resin, the epoxy equivalent in the resin) and the equivalent of the curing agent. In general, the equivalent ratio of the reactive group equivalent to the curing agent equivalent is set to 1.0: 0.9 to 1.0: 1.2 in consideration of the equivalent ratio of
　本発明の熱硬化性樹脂系組成物をプリプレグに用いる場合、各成分が有機溶媒中に溶解または分散されたワニスの状態とすることが好ましい。 場合 When the thermosetting resin composition of the present invention is used for a prepreg, it is preferable that each component be in a varnish state in which the components are dissolved or dispersed in an organic solvent.
　ワニスを製造する場合に用いる有機溶媒としては、例えば、メタノール、エタノール、プロパノール、ブタノール、メチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のアルコール系溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート等のエステル系溶媒、テトラヒドロフラン等のエーテル系溶媒、トルエン、キシレン、メシチレン等の芳香族炭化水素系溶媒、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン、ジメチルスルホキシド等の非プロトン性極性溶媒等が挙げられる。これらの有機溶媒は、単独で、また２種類以上を混合してもよく、市販品を使用してもよい。 Examples of the organic solvent used in producing the varnish include, for example, alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Solvent, butyl acetate, ester solvents such as propylene glycol monomethyl ether acetate, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene, xylene and mesitylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide And other aprotic polar solvents. These organic solvents may be used alone or in combination of two or more, and commercially available products may be used.
　熱硬化性樹脂系組成物の調製方法は特に制限されず、前記各成分を均一に混合することにより調製できる。好ましい調製方法として、熱硬化性樹脂と本発明のオニウム塩とを温度２０～１５０℃程度で均一に攪拌混合する方法を挙げることができ、場合によっては上記ワニスの製造に用いられる溶媒として例示された溶媒を用いてもよい。また、熱硬化性樹脂用硬化剤を加える場合、硬化剤と硬化促進剤の混合物を加熱後、冷却し、続いて熱硬化性樹脂と混合し、加熱後、冷却することが好ましい。 (4) The method for preparing the thermosetting resin-based composition is not particularly limited, and the composition can be prepared by uniformly mixing the above components. As a preferable preparation method, a method of uniformly stirring and mixing the thermosetting resin and the onium salt of the present invention at a temperature of about 20 to 150 ° C. can be mentioned, and in some cases, a solvent used in the production of the varnish is exemplified. May be used. When a curing agent for a thermosetting resin is added, it is preferable that the mixture of the curing agent and the curing accelerator is heated and then cooled, then mixed with the thermosetting resin, heated, and cooled.
　硬化剤と硬化促進剤の混合物を加熱することにより、硬化剤の粘度を低下させ、撹拌・混合を容易にし、硬化剤と硬化促進剤が均一に分散される。 加熱 By heating the mixture of the curing agent and the curing accelerator, the viscosity of the curing agent is reduced, stirring and mixing are facilitated, and the curing agent and the curing accelerator are uniformly dispersed.
　硬化剤と硬化促進剤の混合物は熱硬化性樹脂と混合する前に、予め冷却することにより正確に計量でき、取り扱いが容易になる。 混合 Before the mixture of the curing agent and the curing accelerator is mixed with the thermosetting resin, it can be accurately measured by cooling in advance, and the handling becomes easy.
　硬化促進剤が硬化剤に均一化し難い場合は、硬化促進剤を硬化剤の一部に高濃度で加熱溶解後、冷却して得られるマスターバッチを硬化促進剤として用いてもよい。このマスターバッチは、硬化剤への溶解性が比較的良好となる。 When it is difficult to make the curing accelerator uniform in the curing agent, a master batch obtained by heating and dissolving the curing accelerator in a part of the curing agent at a high concentration and then cooling may be used as the curing accelerator. This masterbatch has relatively good solubility in the curing agent.
　また、硬化剤、硬化促進剤、および熱硬化性樹脂の各成分は、各混合工程において一度に混合してもよく、または複数回に分けて少しずつ混合してもよい。また、上記溶剤や添加剤、無機充填剤等を混合する場合も、同様に、任意の時期に一度または複数回に分けて混合することができる。 硬化 The components of the curing agent, the curing accelerator, and the thermosetting resin may be mixed at once in each mixing step, or may be mixed a plurality of times little by little. Also, when the above-mentioned solvent, additive, inorganic filler, and the like are mixed, they can be similarly mixed once or at a plurality of times at any time.
　なお、硬化剤と硬化促進剤との混合や熱硬化性樹脂との混合の際は、均一に攪拌・混合することを容易とするため、ロールやニーダー等の混練機等を用いてもよい。 When mixing the curing agent with the curing accelerator or the thermosetting resin, a kneader such as a roll or a kneader may be used to facilitate uniform stirring and mixing.
　本発明の熱硬化性樹脂系組成物は、高い触媒活性を発揮し短時間で硬化させることが可能である。 熱 The thermosetting resin composition of the present invention exhibits high catalytic activity and can be cured in a short time.
　熱硬化性樹脂系組成物の硬化性は、常法の硬化性評価方法により測定・評価することができる。例えば、ＪＩＳ　Ｋ　６９１０、ＥＩＭＳ　Ｔ－９０１に準拠したゲル化時間測定法、ＪＩＳ　Ｋ　６３００－２に準拠したトルク計測法により測定・評価することができる。本発明では、ＪＩＳ　Ｋ　６３００－２に準拠したトルク計測法により、硬化性を評価した。 硬化 The curability of the thermosetting resin composition can be measured and evaluated by a conventional method for evaluating curability. For example, it can be measured and evaluated by a gel time measurement method based on JIS K 6910 and EIMS T-901 and a torque measurement method based on JIS K 6300-2. In the present invention, the curability was evaluated by a torque measurement method based on JIS K6300-2.
＜熱硬化性樹脂系硬化物＞
　本発明において熱硬化性樹脂系硬化物とは、熱硬化性樹脂系組成物を、熱硬化性樹脂系組成物に応じた特定の条件下で加熱することによって熱硬化性樹脂の流動性がなくなり、硬化した固形物のことをいう。以下、本発明の熱硬化性樹脂系組成物を硬化した固形物を「本発明の熱硬化性樹脂系硬化物」ということがある。 <Thermosetting resin-based cured product>
In the present invention, the thermosetting resin-based cured product, the thermosetting resin-based composition, the fluidity of the thermosetting resin is lost by heating under specific conditions according to the thermosetting resin-based composition , A cured solid. Hereinafter, the solid obtained by curing the thermosetting resin composition of the present invention may be referred to as “the thermosetting resin-based cured product of the present invention”.
　本発明の熱硬化性樹脂系硬化物は、上記した本発明の熱硬化性樹脂系組成物を、通常の熱硬化性樹脂系組成物の硬化の条件下で加熱することで得ることができる。通常硬化温度１００～２５０℃程度で硬化時間３０秒～１５時間加熱により得ることができ、適宜条件を変更することも可能である。 The thermosetting resin-based cured product of the present invention can be obtained by heating the above-described thermosetting resin-based composition of the present invention under ordinary curing conditions of the thermosetting resin-based composition. Usually, it can be obtained by heating at a curing temperature of about 100 to 250 ° C. for a curing time of 30 seconds to 15 hours, and the conditions can be appropriately changed.
　本発明の熱硬化性樹脂系硬化物は、熱硬化性樹脂系硬化物に含まれる熱硬化性樹脂用硬化促進剤が、自身のフェノール性水酸基により硬化に組み込まれるため、熱硬化性樹脂用硬化促進剤は硬化物中で不純物として耐熱性や接着性に悪影響を及ぼさない。そのため、本発明の熱硬化性樹脂系硬化物は、耐熱性や接着性に優れる。 In the thermosetting resin-based cured product of the present invention, the curing accelerator for the thermosetting resin contained in the thermosetting resin-based cured product is incorporated into the curing by its own phenolic hydroxyl group. Accelerators do not adversely affect heat resistance and adhesion as impurities in the cured product. Therefore, the thermosetting resin-based cured product of the present invention is excellent in heat resistance and adhesiveness.
　熱硬化性樹脂系硬化物の接着性は、常法の接着性方法により測定・評価することができる。例えば、ＪＩＳ　Ｋ　５６００に準拠したクロスカット法による評価方法、ＪＩＳ　Ｋ　６８５０に準拠した引張せん断接着強さによる評価方法、ＪＩＳ　Ｋ　６８５４に準拠したはく離接着強さによる評価方法等が挙げられる。本発明では、ＪＩＳ　Ｋ　５６００に準拠したクロスカット法による評価方法により、接着性を評価した。 接着 The adhesiveness of the thermosetting resin-based cured product can be measured and evaluated by an ordinary adhesive method. For example, an evaluation method based on a cross-cut method according to JIS @ K # 5600, an evaluation method based on a tensile shear adhesive strength based on JIS @ K # 6850, an evaluation method based on a peel adhesive strength based on JIS @ K # 6854, and the like can be given. In the present invention, the adhesiveness was evaluated by an evaluation method using a cross cut method based on JIS K5600.
　熱硬化性樹脂系硬化物の耐熱性は、常法の耐熱性方法により測定・評価することができる。例えば、ＪＩＳ　Ｋ　７２４４に準拠した動的機械特性（動的粘弾性ともいう）による評価方法、ＪＩＳ　Ｋ　７１９７に準拠した熱機械分析による評価方法、ＪＩＳ　Ｋ　７１２１に準拠した示差走査熱分析による評価方法等が挙げられる。本発明では、ＪＩＳ　Ｋ　７２４４に準拠した動的機械特性（動的粘弾性ともいう）により、耐熱性を評価した。 耐熱 The heat resistance of the thermosetting resin-based cured product can be measured and evaluated by a conventional heat resistance method. For example, an evaluation method based on dynamic mechanical properties (also referred to as dynamic viscoelasticity) according to JIS K7244, an evaluation method based on thermomechanical analysis based on JIS K7197, and an evaluation method based on differential scanning calorimetry according to JIS K7121 And the like. In the present invention, heat resistance was evaluated based on dynamic mechanical properties (also referred to as dynamic viscoelasticity) in accordance with JIS {K} 7244.
　以下に本発明の熱硬化性樹脂系組成物を実施例および試験例により詳細に説明するが、本発明はこれらに限定されるものではない。 熱 The thermosetting resin composition of the present invention will be described in detail below with reference to examples and test examples, but the present invention is not limited to these examples.
［１Ｈ－ＮＭＲ測定］　
　結晶１０ｍｇを約０．５ｍｌの重ＤＭＳＯまたは重メタノールに溶かし、φ５ｍｍの試料管に入れ、（株）ＪＥＯＬ　ＲＥＳＯＮＡＮＣＥ社製ＪＮＭ－ＥＣＳ４００で測定した。シフト値は、ＤＭＳＯ（δ＝２．４９ｐｐｍ）またはＴＭＳ（δ＝０ｐｐｍ）を基準とした。 [ 1 H-NMR measurement]
10 mg of the crystal was dissolved in about 0.5 ml of heavy DMSO or heavy methanol, placed in a φ5 mm sample tube, and measured with JNM-ECS400 manufactured by JEOL RESONANCE CO., LTD. The shift values were based on DMSO (δ = 2.49 ppm) or TMS (δ = 0 ppm).
［３１Ｐ－ＮＭＲ測定］　
　結晶１０ｍｇを約０．５ｍｌの重ＤＭＳＯまたは重メタノールに溶かし、φ５ｍｍの試料管に入れ、（株）ＪＥＯＬ　ＲＥＳＯＮＡＮＣＥ社製ＪＮＭ－ＥＣＳ４００で測定した。シフト値は、リン酸（δ＝０ｐｐｍ）を基準とした。 [ 31 P-NMR measurement]
10 mg of the crystal was dissolved in about 0.5 ml of heavy DMSO or heavy methanol, placed in a φ5 mm sample tube, and measured with JNM-ECS400 manufactured by JEOL RESONANCE CO., LTD. The shift values were based on phosphoric acid (δ = 0 ppm).
［ＩＲ測定］　
　ブルカー・オプティクス（株）社製ＡＬＰＨＡを用い、ＡＴＲ法で測定した。 [IR measurement]
It was measured by ATR method using ALPHA manufactured by Bruker Optics Co., Ltd.
＜製造例１＞
　２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノール７０重量部をメタノール６４０重量部に６０℃下溶解させ、これに水酸化ナトリウム８重量部を加え、６０℃で反応させた。次いで、テトラフェニルホスホニウムブロミド８４重量部と反応させ、反応混合物中で生成した結晶を濾取することにより、白色粉末状生成物を１１６重量部得た。
　融点：１１３～１１５℃
　１Ｈ－ＮＭＲ（測定溶媒：重ＤＭＳＯ）　σ（ｐｐｍ）：
１３．９１（２Ｈ，　ｓ）、８．００－７．９０（４Ｈ，　ｍ）、７．８６－７．６６（１６Ｈ，　ｍ）、６．９５－６．８０（２Ｈ，　ｍ）、６．７０－６．６０（４Ｈ，　ｍ）、６．４５－６．３５（２Ｈ，　ｍ）、３．５４（４Ｈ，　ｓ）、２．１０（６Ｈ，　ｓ）、２．０７（３Ｈ，　ｓ）
　３１Ｐ－ＮＭＲ（測定溶媒：重ＤＭＳＯ）　σ（ｐｐｍ）：２３．３
　また、得られた生成物のＩＲスペクトルデータを図１に示す。
　これらのデータから、得られた生成物は式（２”－２－１）で示される目的のテトラフェニルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート（以下、「ＴＰＰ－３ＰＣ」という。）であると推定され、収率８４％と算出された。
Figure JPOXMLDOC01-appb-C000038
 　（式中、Ｐｈは、フェニル基を示す。） <Production Example 1>
70 parts by weight of 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol was dissolved in 640 parts by weight of methanol at 60 ° C., and 8 parts by weight of sodium hydroxide was added thereto. I let it. Then, it was reacted with 84 parts by weight of tetraphenylphosphonium bromide, and the crystals formed in the reaction mixture were collected by filtration to obtain 116 parts by weight of a white powdery product.
Melting point: 113-115 ° C
1 H-NMR (measurement solvent: heavy DMSO) σ (ppm):
13.91 (2H, s), 8.00-7.90 (4H, m), 7.86-7.66 (16H, m), 6.95-6.80 (2H, m), 6. 70-6.60 (4H, m), 6.45-6.35 (2H, m), 3.54 (4H, s), 2.10 (6H, s), 2.07 (3H, s)
31 P-NMR (measurement solvent: heavy DMSO) σ (ppm): 23.3
FIG. 1 shows IR spectrum data of the obtained product.
From these data, the obtained product was obtained from the target tetraphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate (formula (2 ″ -2-1)) Hereinafter, referred to as “TPP-3PC”), and the yield was calculated to be 84%.
Figure JPOXMLDOC01-appb-C000038
 (In the formula, Ph represents a phenyl group.)
＜製造例２＞
　２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノール７０重量部をアセトン４８０重量部に溶解させ、これにテトラブチルホスホニウムヒドロキシドの４０重量％水溶液１３８重量部を加えて中和し、得られた反応混合物から減圧蒸留法を用いて脱水して得た残渣をメチルイソブチルケトン４８０重量部に仕込み、析出した結晶を濾取することにより、白色粉末状生成物を１０９重量部得た。
　融点：２１７～２１９℃
　１Ｈ－ＮＭＲ（測定溶媒：重ＤＭＳＯ）　σ（ｐｐｍ）：
１３．９１（２Ｈ，　ｓ）、６．９０－６．８５（２Ｈ，　ｍ）、６．７０－６．６５（４Ｈ，　ｍ）、６．４５－６．４０（２Ｈ，　ｍ）、３．５５（４Ｈ，　ｓ）、２．２０－２．１０（８Ｈ，　ｍ）、２．１２（６Ｈ，　ｓ）、２．０５（３Ｈ，　ｓ）、１．５０－１．３５（１６Ｈ，　ｍ）、０．９１（１２Ｈ，　ｔ）
　３１Ｐ－ＮＭＲ（測定溶媒：重ＤＭＳＯ）　σ（ｐｐｍ）：３４．７
　また、得られた生成物のＩＲスペクトルデータを図２に示す。
　これらのデータから、得られた生成物は式（２”－２－２）で示されるテトラブチルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート（以下、「ＴＢＰ－３ＰＣ」という。）であると推定され、収率９０％と算出された。
Figure JPOXMLDOC01-appb-C000039
 （式中、Ｂｕは、ブチル基を示す。） <Production Example 2>
70 parts by weight of 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol were dissolved in 480 parts by weight of acetone, and 138 parts by weight of a 40% by weight aqueous solution of tetrabutylphosphonium hydroxide was added thereto. Neutralized, the residue obtained by dehydrating the obtained reaction mixture using a vacuum distillation method is charged into 480 parts by weight of methyl isobutyl ketone, and the precipitated crystals are collected by filtration to give a white powdery product in an amount of 109 parts by weight. I got a copy.
Melting point: 217-219 ° C
1 H-NMR (measurement solvent: heavy DMSO) σ (ppm):
13.91 (2H, s), 6.90-6.85 (2H, m), 6.70-6.65 (4H, m), 6.45-6.40 (2H, m), 3. 55 (4H, s), 2.20-2.10 (8H, m), 2.12 (6H, s), 2.05 (3H, s), 1.50-1.35 (16H, m) , 0.91 (12H, t)
31 P-NMR (measurement solvent: heavy DMSO) σ (ppm): 34.7
FIG. 2 shows IR spectrum data of the obtained product.
Based on these data, the obtained product was identified as tetrabutylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate (hereinafter, referred to as formula (2 ″ -2-2)). "TBP-3PC"), and the yield was calculated to be 90%.
Figure JPOXMLDOC01-appb-C000039
 (In the formula, Bu represents a butyl group.)
＜製造例３＞
　２，２’－メチレンビス［６－（２－ヒドロキシ－５－メチルベンジル）－ｐ－クレゾール］９４重量部をアセトン４８０重量部に溶解させ、これにテトラブチルホスホニウムヒドロキシドの４０重量％水溶液１３８重量部を加えて中和し、得られた反応混合物から減圧蒸留法を用いて脱水して得た残渣をヘキサン４８０重量部に仕込み、析出した結晶を濾取することにより、白色粉末状生成物を１３０重量部得た。
　融点：１９７～２００℃
　１Ｈ－ＮＭＲ（測定溶媒：重ＤＭＳＯ）　σ（ｐｐｍ）：
１２．７４（３Ｈ，　ｓ）、６．９０－６．５０（１０Ｈ，　ｍ）、３．７０－３．５０（６Ｈ，　ｍ）、２．２０－２．１０（１４Ｈ，　ｍ）、２．０５（６Ｈ，　ｓ）、１．５０－１．３５（１６Ｈ，　ｍ）、０．９１（１２Ｈ，　ｔ）
　３１Ｐ－ＮＭＲ（測定溶媒：重ＤＭＳＯ）　σ（ｐｐｍ）：３４．７
　また、得られた生成物のＩＲスペクトルデータを図３に示す。
　これらのデータから、得られた生成物は式（２”－３－１）で示されるテトラブチルホスホニウム２－［３－（２－ヒドロキシ－５－メチルベンジル）－２－ヒドロキシ－５－メチルベンジル］－６－（２－ヒドロキシ－５－メチルベンジル）フェノラート（以下、「ＴＢＰ－４ＰＣ」という。）であると推定され、収率８９％と算出された。
Figure JPOXMLDOC01-appb-C000040
 （式中、Ｂｕは、ブチル基を示す。） <Production Example 3>
94 parts by weight of 2,2'-methylenebis [6- (2-hydroxy-5-methylbenzyl) -p-cresol] are dissolved in 480 parts by weight of acetone, and 138 parts by weight of a 40% by weight aqueous solution of tetrabutylphosphonium hydroxide is added thereto. The residue obtained by dehydration from the resulting reaction mixture using a vacuum distillation method was charged into 480 parts by weight of hexane, and the precipitated crystals were collected by filtration to obtain a white powdery product. 130 parts by weight were obtained.
Melting point: 197-200 ° C
1 H-NMR (measurement solvent: heavy DMSO) σ (ppm):
12.74 (3H, s), 6.90-6.50 (10H, m), 3.70-3.50 (6H, m), 2.20-2.10 (14H, m), 2. 05 (6H, s), 1.50-1.35 (16H, m), 0.91 (12H, t)
31 P-NMR (measurement solvent: heavy DMSO) σ (ppm): 34.7
FIG. 3 shows IR spectrum data of the obtained product.
From these data, the obtained product was represented by tetrabutylphosphonium 2- [3- (2-hydroxy-5-methylbenzyl) -2-hydroxy-5-methylbenzyl represented by the formula (2 ″ -3-1): ] -6- (2-hydroxy-5-methylbenzyl) phenolate (hereinafter referred to as "TBP-4PC"), and the yield was calculated to be 89%.
Figure JPOXMLDOC01-appb-C000040
 (In the formula, Bu represents a butyl group.)
＜製造例４＞
　２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノール７０重量部に代えて、トリス（４－ヒドロキシフェニル）メタン５８重量部使用した以外は、製造例２と同様にして白色粉末状生成物を１０６重量部得た。
　融点：室温から２８０℃までの範囲では融解しなかった。
　１Ｈ－ＮＭＲ（測定溶媒：重メタノール）　σ（ｐｐｍ）：
６．８４－６．７８（６Ｈ，　ｍ）、６．６４－６．５８（６Ｈ，　ｍ）、５．１６（１Ｈ，　ｓ）、２．２０－２．１０（８Ｈ，　ｍ）、１．６０－１．４０（１６Ｈ，　ｍ）、０．９９（１２Ｈ，　ｔ）
　３１Ｐ－ＮＭＲ（測定溶媒：重メタノール）　σ（ｐｐｍ）：３４．３
　また、得られた生成物のＩＲスペクトルデータを図４に示す。
　これらのデータから、得られた生成物は式（３”－１）で示されるテトラブチルホスホニウム４－［ビス（４－ヒドロキシフェニル）メチル］フェノラート（以下、「ＴＢＰ－ＴＰＭ」という。）であると推定され、収率９６％と算出された。
Figure JPOXMLDOC01-appb-C000041
 （式中、Ｂｕは、ブチル基を示す。） <Production Example 4>
Same as Production Example 2 except that 58 parts by weight of tris (4-hydroxyphenyl) methane was used instead of 70 parts by weight of 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol 106 parts by weight of a white powdery product were obtained.
Melting point: No melting in the range from room temperature to 280 ° C.
1 H-NMR (measurement solvent: heavy methanol) σ (ppm):
6.84-6.78 (6H, m), 6.64-6.58 (6H, m), 5.16 (1H, s), 2.20-2.10 (8H, m), 1. 60-1.40 (16H, m), 0.99 (12H, t)
31 P-NMR (measurement solvent: heavy methanol) σ (ppm): 34.3
FIG. 4 shows IR spectrum data of the obtained product.
From these data, the obtained product is tetrabutylphosphonium 4- [bis (4-hydroxyphenyl) methyl] phenolate represented by the formula (3 ″ -1) (hereinafter, referred to as “TBP-TPM”). And the yield was calculated to be 96%.
Figure JPOXMLDOC01-appb-C000041
 (In the formula, Bu represents a butyl group.)
＜製造例５＞
　１，１，２，２－テトラキス（４－ヒドロキシフェニル）エタン８０重量部をメタノール６４０重量部に６０℃下溶解させ、これにテトラブチルホスホニウムヒドロキシドの４０重量％水溶液１３８重量部を加え、６０℃で反応させた。反応混合物中で生成した結晶を濾取することにより、白色粉末状生成物を１２６重量部得た。
　融点：室温から２８０℃までの範囲では融解しなかった。
　１Ｈ－ＮＭＲ（測定溶媒：重ＤＭＳＯ）　σ（ｐｐｍ）：
６．９０－６．８０（８Ｈ，　ｍ）、６．３５－６．２０（８Ｈ，　ｍ）、４．３９（２Ｈ，　ｓ）、２．２０－２．１０（８Ｈ，　ｍ）、１．５０－１．３５（１６Ｈ，　ｍ）、０．９１（１２Ｈ，　ｔ）
　３１Ｐ－ＮＭＲ（測定溶媒：重ＤＭＳＯ）　σ（ｐｐｍ）：３４．７
　また、得られた生成物のＩＲスペクトルデータを図５に示す。
　これらのデータから、得られた生成物は式（４”－１）で示されるテトラブチルホスホニウム４－［１，２，２－トリス（４－ヒドロキシフェニル）エチル］フェノラート（以下、「ＴＢＰ－ＴＰＥ」という。）であると推定され、収率９６％と算出された。
Figure JPOXMLDOC01-appb-C000042
 （式中、Ｂｕは、ブチル基を示す。） <Production Example 5>
80 parts by weight of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane was dissolved in 640 parts by weight of methanol at 60 ° C., and 138 parts by weight of a 40% by weight aqueous solution of tetrabutylphosphonium hydroxide was added thereto. The reaction was carried out at ℃. The crystals formed in the reaction mixture were collected by filtration to obtain 126 parts by weight of a white powdery product.
Melting point: No melting in the range from room temperature to 280 ° C.
1 H-NMR (measurement solvent: heavy DMSO) σ (ppm):
6.90-6.80 (8H, m), 6.35-6.20 (8H, m), 4.39 (2H, s), 2.20-2.10 (8H, m), 1. 50-1.35 (16H, m), 0.91 (12H, t)
31 P-NMR (measurement solvent: heavy DMSO) σ (ppm): 34.7
FIG. 5 shows IR spectrum data of the obtained product.
From these data, the obtained product was identified as tetrabutylphosphonium 4- [1,2,2-tris (4-hydroxyphenyl) ethyl] phenolate (hereinafter referred to as “TBP-TPE”) represented by the formula (4 ″ -1). "), And the yield was calculated to be 96%.
Figure JPOXMLDOC01-appb-C000042
 (In the formula, Bu represents a butyl group.)
＜製造例６＞
　２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノール７０重量部をアセトン４８０重量部に溶解させ、これにテトラブチルアンモニウムヒドロキシドの４０重量％水溶液１３０重量部を加えて中和し、得られた反応混合物から減圧蒸留法を用いてアセトンを除去して得た残渣を脱イオン水４８０重量部に仕込み、析出した結晶を濾取することにより、白色粉末状生成物を１１３重量部得た。
　融点：１９４～１９６℃
　１Ｈ－ＮＭＲ（測定溶媒：重ＤＭＳＯ）　σ（ｐｐｍ）：
１３．７４（２Ｈ，　ｓ）、６．９０－６．８５（２Ｈ，　ｍ）、６．７０－６．６５（４Ｈ，　ｍ）、６．４５－６．４０（２Ｈ，　ｍ）、３．５６（４Ｈ，　ｓ）、３．２０－３．００（８Ｈ，　ｍ）、２．１２（６Ｈ，　ｓ）、２．０５（３Ｈ，　ｓ）、１．６０－１．４５（８Ｈ，　ｍ）、１．３５－１．２０（８Ｈ，　ｍ）、０．９３（１２Ｈ，　ｔ）
　また、得られた生成物のＩＲスペクトルデータを図６に示す。
　これらのデータから、得られた生成物は式（２”－２－１－Ｎ）で示されるテトラブチルアンモニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート（以下、「ＴＢＡ－３ＰＣ」という。）であると推定され、収率９６％と算出された。
Figure JPOXMLDOC01-appb-C000043
 （式中、Ｂｕは、ブチル基を示す。）
＜製造例７＞
　２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノール７０重量部をメタノール１６０重量部に６０℃下溶解させ、これに水酸化ナトリウム８重量部を加え、６０℃で反応させた。次いで、ブチルトリフェニルホスホニウムブロミド８０重量部と反応させ、反応液を得た。反応液を水８００重量部の中に投入し、生成した結晶を濾取することにより、白色粉末状生成物を１３０重量部得た。
　融点：なし
　１Ｈ－ＮＭＲ（測定溶媒：重ＤＭＳＯ）　σ（ｐｐｍ）：
１３．４３（２Ｈ，　ｓ）、７．９２－７．８４（３Ｈ，　ｍ）、７．８４－７．７０（１２Ｈ，　ｍ）、６．９０－６．８５（２Ｈ，　ｍ）、６．７２－６．６３（４Ｈ，　ｍ）、６．５５－６．４０（２Ｈ，　ｍ）、３．６５－３．４５（６Ｈ，　ｍ）、２．１１（６Ｈ，　ｓ）、２．０４（３Ｈ，　ｓ）、１．５５－１．４０（４Ｈ，　ｍ）、０．８９（３Ｈ，　ｔ）
　３１Ｐ－ＮＭＲ（測定溶媒：重ＤＭＳＯ）　σ（ｐｐｍ）：２５．０
　また、得られた生成物のＩＲスペクトルデータを図７に示す。
　これらのデータから、得られた生成物は式（２”－２－３）で示される目的のブチルトリフェニルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート（以下、「ＴＰＰＢ－３ＰＣ」という。）であると推定され、収率９８％と算出された。
Figure JPOXMLDOC01-appb-C000044
 　（式中、Ｐｈはフェニル基を示し、Ｂｕはブチル基を示す。）
＜製造例８＞
　ブチルトリフェニルホスホニウムブロミド８０重量部に代えて、ベンジルトリフェニルホスホニウムクロリド７８重量部使用した以外は、製造例７と同様にして白色粉末状生成物を１２８重量部得た。
　融点：なし
　１Ｈ－ＮＭＲ（測定溶媒：重ＤＭＳＯ）　σ（ｐｐｍ）：
１３．６１（２Ｈ，　ｓ）、７．９２－７．８４（３Ｈ，　ｍ）、７．８０－７．６０（１２Ｈ，　ｍ）、７．３５－７．１８（３Ｈ，　ｍ）、７．００－６．９３（２Ｈ，　ｍ）、６．９０－６．８５（２Ｈ，　ｍ）、６．７２－６．６３（４Ｈ，　ｍ）、６．４８－６．３８（２Ｈ，　ｍ）、５．２０－５．０５（２Ｈ，　ｄ）、３．５５（４Ｈ，　ｓ）、２．１１（６Ｈ，　ｓ）、２．０４（３Ｈ，　ｓ）
　３１Ｐ－ＮＭＲ（測定溶媒：重ＤＭＳＯ）　σ（ｐｐｍ）：２４．１
　また、得られた生成物のＩＲスペクトルデータを図８に示す。
　これらのデータから、得られた生成物は式（２”－２－４）で示される目的のベンジルトリフェニルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート（以下、「ＴＰＰＺ－３ＰＣ」という。）であると推定され、収率９１％と算出された。
Figure JPOXMLDOC01-appb-C000045
 　（式中、Ｐｈはフェニル基を示し、Ｂｎはベンジル基を示す。）
＜製造例９＞
　ブチルトリフェニルホスホニウムブロミド８０重量部に代えて、メトキシメチルトリフェニルホスホニウムクロリド６９重量部使用した以外は、製造例７と同様にして白色粉末状生成物を１２０重量部得た。
　融点：なし
　１Ｈ－ＮＭＲ（測定溶媒：重ＤＭＳＯ）　σ（ｐｐｍ）：
１３．５６（２Ｈ，　ｓ）、７．９６－７．８６（３Ｈ，　ｍ）、７．８４－７．７０（１２Ｈ，　ｍ）、６．９２－６．８６（２Ｈ，　ｍ）、６．７２－６．６４（４Ｈ，　ｍ）、６．４８－６．４０（２Ｈ，　ｍ）、５．６２－５．５４（２Ｈ，　ｄ）、３．５７（４Ｈ，　ｓ）、３．４７（３Ｈ，　ｓ）、２．１１（６Ｈ，　ｓ）、２．０５（３Ｈ，　ｓ）
　３１Ｐ－ＮＭＲ（測定溶媒：重ＤＭＳＯ）　σ（ｐｐｍ）：１８．３
　また、得られた生成物のＩＲスペクトルデータを図９に示す。
　これらのデータから、得られた生成物は式（２”－２－５）で示される目的のメトキシメチルトリフェニルホスホニウム２，６－ビス（２－ヒドロキシ－５－メチルベンジル）－４－メチルフェノラート（以下、「ＴＰＰＭＯ－３ＰＣ」という。）であると推定され、収率９１％と算出された。
Figure JPOXMLDOC01-appb-C000046
 　（式中、Ｐｈはフェニル基を示す。） <Production Example 6>
70 parts by weight of 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol were dissolved in 480 parts by weight of acetone, and 130 parts by weight of a 40% by weight aqueous solution of tetrabutylammonium hydroxide was added thereto. The residue obtained by neutralizing and removing acetone from the obtained reaction mixture by using a vacuum distillation method is charged into 480 parts by weight of deionized water, and the precipitated crystals are collected by filtration to obtain a white powdery product. 113 parts by weight were obtained.
Melting point: 194-196 ° C
1 H-NMR (measurement solvent: heavy DMSO) σ (ppm):
13.74 (2H, s), 6.90-6.85 (2H, m), 6.70-6.65 (4H, m), 6.45-6.40 (2H, m), 3. 56 (4H, s), 3.20-3.00 (8H, m), 2.12 (6H, s), 2.05 (3H, s), 1.60-1.45 (8H, m) , 1.35-1.20 (8H, m), 0.93 (12H, t)
FIG. 6 shows IR spectrum data of the obtained product.
From these data, the obtained product was identified as tetrabutylammonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate represented by the formula (2 ″ -2-1-N) ( Hereinafter, referred to as “TBA-3PC”), and the yield was calculated to be 96%.
Figure JPOXMLDOC01-appb-C000043
 (In the formula, Bu represents a butyl group.)
<Production Example 7>
70 parts by weight of 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol was dissolved in 160 parts by weight of methanol at 60 ° C., and 8 parts by weight of sodium hydroxide was added thereto, followed by reaction at 60 ° C. I let it. Next, it was reacted with 80 parts by weight of butyltriphenylphosphonium bromide to obtain a reaction solution. The reaction solution was poured into 800 parts by weight of water, and the generated crystals were collected by filtration to obtain 130 parts by weight of a white powdery product.
Melting point: none
1 H-NMR (measurement solvent: heavy DMSO) σ (ppm):
13.43 (2H, s), 7.92-7.84 (3H, m), 7.84-7.70 (12H, m), 6.90-6.85 (2H, m), 6. 72-6.63 (4H, m), 6.55-6.40 (2H, m), 3.65-3.45 (6H, m), 2.11 (6H, s), 2.04 ( 3H, s), 1.55-1.40 (4H, m), 0.89 (3H, t)
31 P-NMR (measurement solvent: heavy DMSO) σ (ppm): 25.0
FIG. 7 shows IR spectrum data of the obtained product.
From these data, the obtained product is the target butyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate of the formula (2 ″ -2-3) (Hereinafter, referred to as “TPPB-3PC”), and the yield was calculated to be 98%.
Figure JPOXMLDOC01-appb-C000044
 (In the formula, Ph represents a phenyl group, and Bu represents a butyl group.)
<Production Example 8>
128 parts by weight of a white powdery product was obtained in the same manner as in Production Example 7, except that 78 parts by weight of benzyltriphenylphosphonium chloride was used instead of 80 parts by weight of butyltriphenylphosphonium bromide.
Melting point: none
1 H-NMR (measurement solvent: heavy DMSO) σ (ppm):
13.61 (2H, s), 7.92-7.84 (3H, m), 7.80-7.60 (12H, m), 7.35-7.18 (3H, m), 7. 00-6.93 (2H, m), 6.90-6.85 (2H, m), 6.72-6.63 (4H, m), 6.48-6.38 (2H, m), 5.20-5.05 (2H, d), 3.55 (4H, s), 2.11 (6H, s), 2.04 (3H, s)
31 P-NMR (measurement solvent: heavy DMSO) σ (ppm): 24.1
FIG. 8 shows IR spectrum data of the obtained product.
From these data, the obtained product was the target benzyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenolate represented by the formula (2 ″ -2-4) (Hereinafter, referred to as “TPPZ-3PC”), and the yield was calculated to be 91%.
Figure JPOXMLDOC01-appb-C000045
 (In the formula, Ph represents a phenyl group, and Bn represents a benzyl group.)
<Production Example 9>
120 parts by weight of a white powdery product was obtained in the same manner as in Production Example 7, except that 69 parts by weight of methoxymethyltriphenylphosphonium chloride was used instead of 80 parts by weight of butyltriphenylphosphonium bromide.
Melting point: none
1 H-NMR (measurement solvent: heavy DMSO) σ (ppm):
13.56 (2H, s), 7.96-7.86 (3H, m), 7.84-7.70 (12H, m), 6.92-6.86 (2H, m), 6. 72-6.64 (4H, m), 6.48-6.40 (2H, m), 5.62-5.54 (2H, d), 3.57 (4H, s), 3.47 ( 3H, s), 2.11 (6H, s), 2.05 (3H, s)
31 P-NMR (measurement solvent: heavy DMSO) σ (ppm): 18.3
FIG. 9 shows IR spectrum data of the obtained product.
From these data, the obtained product was the target methoxymethyltriphenylphosphonium 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylpheno represented by the formula (2 ″ -2-5). (Hereinafter referred to as “TPPMO-3PC”), and the yield was calculated to be 91%.
Figure JPOXMLDOC01-appb-C000046
 (In the formula, Ph represents a phenyl group.)
＜比較製造例１＞
　特許文献３の記載に基づいて、フェノール樹脂系硬化剤のフェノライトＴＤ－２１３１（水酸基当量１０４、ＤＩＣ社製）６２重量部をアセトン８０重量部に溶解させ、これにテトラブチルホスホニウムヒドロキシドの４０重量％水溶液６９重量部を加えて中和し、得られた反応混合物を減圧下、１７０℃で減圧濃縮を行ない、溶媒を系外に排出した。得られた黄色透明溶融物を冷却、粉砕し、テトラブチルホスホニウム－フェノライトＴＤ－２１３１塩（以下「ＴＢＰ－ＴＤ２１３１」という。）を８８重量部得た。 <Comparative Production Example 1>
On the basis of the description in Patent Document 3, 62 parts by weight of a phenolic resin-based curing agent, phenolite TD-2131 (hydroxyl equivalent: 104, manufactured by DIC) are dissolved in 80 parts by weight of acetone, and 40 parts of tetrabutylphosphonium hydroxide is added thereto. The resulting reaction mixture was concentrated under reduced pressure at 170 ° C. under reduced pressure, and the solvent was discharged out of the system. The resulting yellow transparent melt was cooled and pulverized to obtain 88 parts by weight of tetrabutylphosphonium-phenolite TD-2131 salt (hereinafter referred to as “TBP-TD2131”).
＜実施例１＞
　フェノール樹脂系硬化剤のＭＥＨＣ－７８５１Ｍ（水酸基当量２１４、明和化成社製）３０３重量部に、ＴＰＰ－３ＰＣを１１．７重量部加え、１５０℃加熱下で２分間攪拌・混合した後、室温まで冷却した。これにエポキシ樹脂のＮＣ－３０００（エポキシ当量２７４、日本化薬社製）４００重量部を加え、１２０℃加熱下で２分間攪拌・混合した後、室温まで冷却し熱硬化性樹脂系組成物（エポキシ当量と水酸基当量の当量比１．０：１．０）を得た。
　また、得られた熱硬化性樹脂系組成物を１５０℃８ｈ加熱硬化させることにより、熱硬化性樹脂系硬化物を得た。 <Example 1>
To 303 parts by weight of a phenolic resin-based curing agent, MEHC-7851M (hydroxyl equivalent 214, manufactured by Meiwa Kasei Co., Ltd.), 11.7 parts by weight of TPP-3PC is added, and the mixture is stirred and mixed at 150 ° C. for 2 minutes, and then cooled to room temperature. Cool. 400 parts by weight of an epoxy resin NC-3000 (epoxy equivalent: 274, manufactured by Nippon Kayaku Co., Ltd.) was added thereto, and the mixture was stirred and mixed under heating at 120 ° C. for 2 minutes, and then cooled to room temperature to obtain a thermosetting resin composition ( The equivalent ratio of epoxy equivalent to hydroxyl equivalent was 1.0: 1.0).
The obtained thermosetting resin composition was heated and cured at 150 ° C. for 8 hours to obtain a thermosetting resin-based cured product.
＜実施例２＞
　ＴＰＰ－３ＰＣ１１．７重量部に代えて、ＴＢＰ－３ＰＣ１０．３重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物および熱硬化性樹脂系硬化物を得た。 <Example 2>
A thermosetting resin composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1, except that 10.3 parts by weight of TBP-3PC was used instead of 11.7 parts by weight of TPP-3PC.
＜実施例３＞
　ＴＰＰ－３ＰＣ１１．７重量部に代えて、ＴＢＰ－４ＰＣ１２．４重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物および熱硬化性樹脂系硬化物を得た。 <Example 3>
A thermosetting resin composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1, except that 12.4 parts by weight of TBP-4PC was used instead of 11.7 parts by weight of TPP-3PC.
＜実施例４＞
　ＴＰＰ－３ＰＣ１１．７重量部に代えて、ＴＢＰ－ＴＰＭ９．４重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物および熱硬化性樹脂系硬化物を得た。 <Example 4>
A thermosetting resin composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1 except that 9.4 parts by weight of TBP-TPM was used instead of 11.7 parts by weight of TPP-3PC.
＜実施例５＞
　ＴＰＰ－３ＰＣ１１．７重量部に代えて、ＴＢＰ－ＴＰＥ１１．２重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物および熱硬化性樹脂系硬化物を得た。 <Example 5>
A thermosetting resin composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1, except that 11.2 parts by weight of TBP-TPE was used instead of 11.7 parts by weight of TPP-3PC.
＜実施例６＞
　ＴＰＰ－３ＰＣ１１．７重量部に代えて、ＴＢＡ－３ＰＣ１０．０重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物および熱硬化性樹脂系硬化物を得た。
＜実施例７＞
　ＴＰＰ－３ＰＣ１１．７重量部に代えて、ＴＰＰＢ－３ＰＣ１１．３重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物および熱硬化性樹脂系硬化物を得た。
＜実施例８＞
　ＴＰＰ－３ＰＣ１１．７重量部に代えて、ＴＰＰＺ－３ＰＣ１１．９重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物および熱硬化性樹脂系硬化物を得た。
＜実施例９＞
　ＴＰＰ－３ＰＣ１１．７重量部に代えて、ＴＰＰＭＯ－３ＰＣ１１．１重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物および熱硬化性樹脂系硬化物を得た。 <Example 6>
A thermosetting resin composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1, except that 10.0 parts by weight of TBA-3PC was used instead of 11.7 parts by weight of TPP-3PC.
<Example 7>
A thermosetting resin composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1 except that 11.3 parts by weight of TPP-3PC was used instead of 11.7 parts by weight of TPP-3PC.
<Example 8>
A thermosetting resin-based composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1 except that 11.9 parts by weight of TPP-3PC was used instead of 11.7 parts by weight of TPP-3PC.
<Example 9>
A thermosetting resin composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1, except that 11.1 parts by weight of TPP-3PC was used instead of 11.7 parts by weight of TPP-3PC.
＜比較例１＞
　ＴＰＰ－３ＰＣ１１．７重量部に代えて、トリフェニルホスフィン（以下「ＴＰＰ」という。）を４．２重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物および熱硬化性樹脂系硬化物を得た。 <Comparative Example 1>
A thermosetting resin composition and a thermosetting resin were prepared in the same manner as in Example 1 except that 4.2 parts by weight of triphenylphosphine (hereinafter referred to as “TPP”) was used instead of 11.7 parts by weight of TPP-3PC. A cured resin-based cured product was obtained.
＜比較例２＞
　ＴＰＰ－３ＰＣ１１．７重量部に代えて、トリス（４－メチルフェニル）ホスフィン（以下「ＴＰＴＰ」という。）を４．９重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物および熱硬化性樹脂系硬化物を得た。 <Comparative Example 2>
A thermosetting resin system was prepared in the same manner as in Example 1 except that 4.9 parts by weight of tris (4-methylphenyl) phosphine (hereinafter, referred to as “TPTP”) was used instead of 11.7 parts by weight of TPP-3PC. A composition and a thermosetting resin-based cured product were obtained.
＜比較例３＞
　ＴＰＰ－３ＰＣ１１．７重量部に代えて、特許文献１に記載のビス（テトラブチルホスホニウム）ピロメリテート（以下「ＢＴＢＰ－ピロメリテート」という。）を７．３重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物および熱硬化性樹脂系硬化物を得た。 <Comparative Example 3>
Same as Example 1 except that 7.3 parts by weight of bis (tetrabutylphosphonium) pyromellitate (hereinafter referred to as “BTBP-pyromellitate”) described in Patent Document 1 was used instead of 11.7 parts by weight of TPP-3PC. Thus, a thermosetting resin composition and a thermosetting resin-based cured product were obtained.
＜比較例４＞
　ＴＰＰ－３ＰＣ１１．７重量部に代えて、２－エチル－４－メチルイミダゾール（以下「２Ｅ４ＭＺ」という。）を４．７重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物および熱硬化性樹脂系硬化物を得た。 <Comparative Example 4>
A thermosetting resin system was prepared in the same manner as in Example 1 except that 4.7 parts by weight of 2-ethyl-4-methylimidazole (hereinafter referred to as "2E4MZ") was used instead of 11.7 parts by weight of TPP-3PC. A composition and a thermosetting resin-based cured product were obtained.
＜比較例５＞
　ＴＰＰ－３ＰＣ１１．７重量部に代えて、特許文献２に記載のテトラブチルホスホニウムビスフェノールＡ塩（以下「ＴＢＰ－ＢＰＡ」という。）を１２．２重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物および熱硬化性樹脂系硬化物を得た。 <Comparative Example 5>
In the same manner as in Example 1 except that instead of 11.7 parts by weight of TPP-3PC, 12.2 parts by weight of tetrabutylphosphonium bisphenol A salt (hereinafter referred to as “TBP-BPA”) described in Patent Document 2 was used. Thus, a thermosetting resin composition and a thermosetting resin-based cured product were obtained.
＜比較例６＞
　ＴＰＰ－３ＰＣ１１．７重量部に代えて、ＴＢＰ－ＴＤ２１３１を１５．０重量部使用した以外は、実施例１と同様にして熱硬化性樹脂系組成物および熱硬化性樹脂系硬化物を得た。 <Comparative Example 6>
A thermosetting resin composition and a thermosetting resin-based cured product were obtained in the same manner as in Example 1 except that 15.0 parts by weight of TBP-TD2131 was used instead of 11.7 parts by weight of TPP-3PC. .
［硬化性評価］
　得られた熱硬化性樹脂系組成物を、ＪＳＲトレーディング（株）社製キュラストメーター７Ｐを用い、温度１７５℃、振幅角度±１°にて、トルク計測法による硬化性評価を行った。
　なお、硬化性の指標として、ＪＩＳ　Ｋ　６３００－２に準じ、ｔｃ（１０）、ｔｃ（９０）、およびｔｃ（Δ８０）を評価した。ここで、ｔｃ（１０）、ｔｃ（９０）、およびｔｃ（Δ８０）は表１の定義による。
Figure JPOXMLDOC01-appb-T000047
 　つまり、ｔｃ（Δ８０）が小さいほど、硬化性が良好ということができる。 [Curability evaluation]
The curability of the obtained thermosetting resin composition was evaluated by a torque measurement method at a temperature of 175 ° C. and an amplitude angle of ± 1 ° using a Curastometer 7P manufactured by JSR Trading Co., Ltd.
In addition, tc (10), tc (90), and tc (Δ80) were evaluated as indices of curability according to JIS K 6300-2. Here, tc (10), tc (90), and tc (Δ80) are as defined in Table 1.
Figure JPOXMLDOC01-appb-T000047
 That is, it can be said that the smaller the tc (Δ80), the better the curability.
［接着性評価］
　得られた熱硬化性樹脂系組成物を、バーコーターを使用して膜厚４０～６０μｍになるように、銅基板上に塗布し、対流式オーブンにて１５０℃８ｈ硬化させて、接着性試験用硬化物を作製した。
　得られた接着性試験用硬化物を使用して、クロスカット試験（ＪＩＳ　　Ｋ　５６００準拠）を行い、同規格の判定基準に従い、接着性を分類０～５までの６段階にて判定した。分類値が小さい方が優れる。 [Adhesion evaluation]
The resulting thermosetting resin-based composition was applied on a copper substrate using a bar coater so as to have a film thickness of 40 to 60 μm, and cured at 150 ° C. for 8 hours in a convection oven to conduct an adhesion test. A cured product was prepared.
A cross cut test (according to JIS K 5600) was performed using the obtained cured product for an adhesiveness test, and the adhesiveness was determined in six steps of classifications 0 to 5 according to the criteria of the same standard. The smaller the classification value, the better.
［耐熱性評価］　
　得られた熱硬化性樹脂系硬化物を、ＳＩＩナノテクノロジー（株）社製ＤＭＳ６１００を用い、昇温５℃／分、周波数１Ｈｚ、曲げモードにて、ＪＩＳ　Ｋ　７２４４に準拠する動的機械特性（動的粘弾性ともいう）による耐熱性評価を行った。
　なお、耐熱性の指標であるガラス転移温度（Ｔｇ）は、貯蔵弾性率と損失弾性率の比である損失正接（ｔａｎδ）のピーク温度とした。 [Heat resistance evaluation]
The obtained thermosetting resin-based cured product was subjected to dynamic mechanical properties according to JIS K 7244 at a temperature rise of 5 ° C./min, a frequency of 1 Hz, and a bending mode using DMS6100 manufactured by SII Nano Technology Co., Ltd. (Also referred to as dynamic viscoelasticity).
The glass transition temperature (Tg), which is an index of heat resistance, was defined as the peak temperature of the loss tangent (tan δ), which is the ratio between the storage elastic modulus and the loss elastic modulus.
　また、結果を表２－１～２，表３に示した。 結果 The results are shown in Tables 2-1 to 2 and Table 3.
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000050
　表２－１，２－２に示すように、本発明のオニウム塩を配合した熱硬化性樹脂系組成物および硬化物は、ｔｃ（Δ８０）が２以下であり、かつ接着性が区分１以下であり、かつガラス転移温度が１４９℃以上であり、いずれも、硬化性、接着性、および耐熱性が共に優れる結果を示した。 As shown in Tables 2-1 and 2-2, the thermosetting resin composition and the cured product containing the onium salt of the present invention have tc (Δ80) of 2 or less and adhesiveness of 1 or less. And the glass transition temperature was 149 ° C. or higher, and all showed excellent results in curability, adhesiveness, and heat resistance.
　表３に示すように、従来の硬化促進剤を用いた場合、接着性と、硬化性および耐熱性はトレードオフの関係になりやすく、比較例１、２のホスフィンは、接着性に優れるが、硬化性、耐熱性が劣り、比較例３のホスホニウムカルボキシレートは硬化性にやや優れ、耐熱性、接着性が劣った。比較例４のイミダゾールは硬化性および耐熱性に比較的優れるが、接着性が劣る結果となった。また、比較例５、６のホスホニウムフェノラートは、耐熱性に優れるが、接着性を含め、他の性能を満足させることはできなかった。 As shown in Table 3, when a conventional curing accelerator is used, the adhesiveness, the curability and the heat resistance tend to be in a trade-off relationship, and the phosphines of Comparative Examples 1 and 2 are excellent in the adhesiveness. The curability and heat resistance were inferior, and the phosphonium carboxylate of Comparative Example 3 was slightly superior in curability and inferior in heat resistance and adhesiveness. The imidazole of Comparative Example 4 was relatively excellent in curability and heat resistance, but resulted in poor adhesion. Further, the phosphonium phenolates of Comparative Examples 5 and 6 were excellent in heat resistance, but could not satisfy other performances including adhesiveness.
　本発明のオニウム塩を配合した熱硬化性樹脂系組成物および硬化物は、従来の硬化促進剤を用いた場合に比べ、硬化性、接着性および耐熱性が良好となるため有用である。 熱 The thermosetting resin composition and the cured product containing the onium salt of the present invention are useful because they have better curability, adhesiveness and heat resistance than the case where a conventional curing accelerator is used.
　本発明の熱硬化性樹脂系組成物および硬化物は、硬化性、接着性および耐熱性を同時に満たすことが可能であるため、例えば、各種の小型の電気・電子部品や半導体部品の樹脂封止に有用である。 Since the thermosetting resin composition and the cured product of the present invention can simultaneously satisfy curability, adhesiveness and heat resistance, for example, resin sealing of various small electric / electronic parts and semiconductor parts Useful for

Claims (15)

  1. 　下記の一般式（１）
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１～Ｒ４は、同一または異なって、炭素数１～１６の置換または非置換の炭化水素基を示し、Ｑはリン原子または窒素原子を示す。）で表されるオニウムカチオンと、
    下記の一般式（２）から一般式（５）で表されるフェノール誘導体からなる群から選ばれる少なくとも１種のフェノール誘導体のアニオン残基からなるオニウムフェノラート。
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ５、Ｒ６、Ｒ７は同一または異なって、水素原子、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）、水酸基、またはアミノ基を示す。ａ、ｂ、ｃは同一または異なって、ａ、ｃは０から４のいずれかの整数を示し、ｂは０から３のいずれかの整数を示す。また、ａ、ｂ、ｃが２以上の整数を示すとき、複数の各Ｒ５、Ｒ６、Ｒ７は、同一または異なっていてもよい。また、ｐは０から４の整数を示す。）
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ８、Ｒ９、Ｒ１０は同一または異なって、水素原子、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）、水酸基、またはアミノ基を示し、ｄ、ｅ、ｆは同一または異なって、０から４のいずれかの整数を示す。また、ｄ、ｅ、ｆが２以上の整数を示すとき、複数の各Ｒ８、Ｒ９、Ｒ１０は、同一または異なっていてもよい。Ｒ１１は、水素原子、炭素数１～１６の飽和脂肪族炭化水素基（アルキル基）、またはアルキル基もしくはメトキシ基で置換してもよいフェニル基を示す。）
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５は同一または異なって、水素原子、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）、水酸基、またはアミノ基を示し、ｇ、ｈ、ｉ、ｊは同一または異なって、０から４のいずれかの整数を示す。また、ｇ、ｈ、ｉ、ｊが２以上の整数を示すとき、複数の各Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５は、同一または異なっていてもよい。Ｘは単結合、炭素数１～１６の２価の飽和脂肪族炭化水素基（アルキル基）もしくは飽和脂環式炭化水素基（シクロアルキル基）、またはフェニレン基を示す。）
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９は同一または異なって、水素原子、炭素数１～４の飽和脂肪族炭化水素基（アルキル基）、水酸基、またはアミノ基を示し、ｋ、ｌ、ｍ、ｎは同一または異なって、０から４のいずれかの整数を示す。また、ｋ、ｌ、ｍ、ｎが２以上の整数を示すとき、複数の各Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９は、同一または異なっていてもよい。）     The following general formula (1)
    Figure JPOXMLDOC01-appb-C000001
     Wherein R 1 to R 4 are the same or different and each represent a substituted or unsubstituted hydrocarbon group having 1 to 16 carbon atoms, and Q represents a phosphorus atom or a nitrogen atom. When,
    An onium phenolate comprising an anionic residue of at least one phenol derivative selected from the group consisting of phenol derivatives represented by the following general formulas (2) to (5).
    Figure JPOXMLDOC01-appb-C000002
     (Wherein, R 5 , R 6 and R 7 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group. c is the same or different, a and c each represent an integer of 0 to 4, b represents an integer of 0 to 3. When a, b, and c each represent an integer of 2 or more, , A plurality of R 5 , R 6 and R 7 may be the same or different, and p represents an integer of 0 to 4.)
    Figure JPOXMLDOC01-appb-C000003
     (Wherein, R 8 , R 9 and R 10 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group; f is the same or different and represents an integer of 0 to 4. When d, e, and f each represent an integer of 2 or more, a plurality of R 8 , R 9 , and R 10 are the same or different. R 11 represents a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms (alkyl group), or a phenyl group which may be substituted with an alkyl group or a methoxy group.
    Figure JPOXMLDOC01-appb-C000004
     (Wherein, R 12 , R 13 , R 14 and R 15 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group; , H, i, j are the same or different and each represent an integer of 0 to 4. When g, h, i, j represents an integer of 2 or more, a plurality of each of R 12 , R 13 , R 14 and R 15 may be the same or different, and X is a single bond, a divalent saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms (alkyl group) or a saturated alicyclic hydrocarbon group (cycloalkyl group). Group) or a phenylene group.)
    Figure JPOXMLDOC01-appb-C000005
     (Wherein, R 16 , R 17 , R 18 and R 19 are the same or different and each represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms (alkyl group), a hydroxyl group, or an amino group; , L, m, and n are the same or different and each represent an integer of 0 to 4. When k, 1, m, and n represent an integer of 2 or more, a plurality of R 16 , R 17 , R 18 and R 19 may be the same or different.)
  2. 　前記一般式（１）において、Ｒ１～Ｒ４が、同一または異なって、ブチル基、フェニル基、４－メチルフェニル基、４－メトキシフェニル基、ベンジル基、メトキシメチル基、およびカルボキシエチル基から選ばれる置換基である請求項１に記載のオニウムフェノラート。 In the general formula (1), R 1 to R 4 are the same or different from each other and are selected from a butyl group, a phenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, a benzyl group, a methoxymethyl group, and a carboxyethyl group. The onium phenolate according to claim 1, which is a substituent selected.
  3. 　前記一般式（１）において、Ｒ１～Ｒ４が全てフェニル基である請求項１に記載のテトラフェニルオニウムフェノラート。 2. The tetraphenylonium phenolate according to claim 1, wherein in the general formula (1), R 1 to R 4 are all phenyl groups.
  4. 　前記一般式（１）において、Ｒ１～Ｒ４が全てブチル基である請求項１に記載のテトラブチルオニウムフェノラート。 The tetrabutylonium phenolate according to claim 1, wherein in the general formula (1), R 1 to R 4 are all butyl groups.
  5. 　前記一般式（２）が下記式（２ａ）～（２ｄ）からなる群から選ばれる１種のフェノール誘導体であることを特徴とする請求項１～４のいずれかに記載のオニウムフェノラート。
    Figure JPOXMLDOC01-appb-C000006
         The onium phenolate according to claim 1, wherein the general formula (2) is one kind of phenol derivative selected from the group consisting of the following formulas (2a) to (2d).
    Figure JPOXMLDOC01-appb-C000006
  6. 　前記一般式（３）が下記式（３ａ）または下記式（３ｂ）のいずれか１種のフェノール誘導体であることを特徴とする請求項１～４のいずれかに記載のオニウムフェノラート。
    Figure JPOXMLDOC01-appb-C000007
         The onium phenolate according to any one of claims 1 to 4, wherein the general formula (3) is a phenol derivative of any one of the following formulas (3a) and (3b).
    Figure JPOXMLDOC01-appb-C000007
  7. 　前記一般式（４）が下記式（４ａ）または下記式（４ｂ）のいずれか１種のフェノール誘導体であることを特徴とする請求項１～４のいずれかに記載のオニウムフェノラート。
    Figure JPOXMLDOC01-appb-C000008
         The onium phenolate according to any one of claims 1 to 4, wherein the general formula (4) is a phenol derivative of any one of the following formulas (4a) and (4b).
    Figure JPOXMLDOC01-appb-C000008
  8. 　前記一般式（５）が下記式（５ａ）のフェノール誘導体であることを特徴とする請求項１～４のいずれかに記載のオニウムフェノラート。
    Figure JPOXMLDOC01-appb-C000009
         The onium phenolate according to any one of claims 1 to 4, wherein the general formula (5) is a phenol derivative represented by the following formula (5a).
    Figure JPOXMLDOC01-appb-C000009
  9. 　請求項１～８のいずれかに記載のオニウムフェノラートを少なくとも含む、熱硬化性樹脂用硬化促進剤。 A curing accelerator for a thermosetting resin, comprising at least the onium phenolate according to any one of claims 1 to 8.
  10. 　請求項９に記載の熱硬化性樹脂用硬化促進剤と、熱硬化性樹脂とを少なくとも含む、熱硬化性樹脂系組成物。 A thermosetting resin-based composition comprising at least the thermosetting resin curing accelerator according to claim 9 and a thermosetting resin.
  11. 　前記熱硬化性樹脂が、エポキシ樹脂、マレイミド樹脂、シアネート樹脂、およびイソシアネート樹脂から選ばれる１種または２種以上の熱硬化性樹脂である、請求項１０に記載の熱硬化性樹脂系組成物。 The thermosetting resin composition according to claim 10, wherein the thermosetting resin is one or more thermosetting resins selected from an epoxy resin, a maleimide resin, a cyanate resin, and an isocyanate resin.
  12. 　さらに熱硬化性樹脂用硬化剤を含む、請求項１０または請求項１１に記載の熱硬化性樹脂系組成物。 The thermosetting resin composition according to claim 10 or 11, further comprising a thermosetting resin curing agent.
  13. 　前記熱硬化性樹脂用硬化剤が、フェノール樹脂、ポリアミン、酸無水物、およびベンゾオキサジンから選ばれる１種または２種以上の熱硬化性樹脂用硬化剤である、請求項１２に記載の熱硬化性樹脂系組成物。 The heat curing according to claim 12, wherein the curing agent for a thermosetting resin is one or more curing agents for a thermosetting resin selected from a phenol resin, a polyamine, an acid anhydride, and benzoxazine. Resin-based composition.
  14. 　請求項１２または請求項１３に記載の熱硬化性樹脂系組成物であって、熱硬化性樹脂用硬化促進剤が、前記熱硬化性樹脂用硬化促進剤と前記熱硬化性樹脂用硬化剤の一部と反応させたマスターバッチである、熱硬化性樹脂系組成物。 The thermosetting resin-based composition according to claim 12 or 13, wherein the thermosetting resin curing accelerator is composed of the thermosetting resin curing accelerator and the thermosetting resin curing agent. A thermosetting resin composition which is a master batch reacted with a part.
  15. 　請求項１０～１４のいずれかに記載の熱硬化性樹脂系組成物を硬化して得られる熱硬化性樹脂系硬化物。
          A cured thermosetting resin obtained by curing the thermosetting resin composition according to any one of claims 10 to 14.
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JP2000086867A (en) * 1998-09-14 2000-03-28 Sumitomo Bakelite Co Ltd Epoxy resin composition and semiconductor device
JP2000273155A (en) * 1999-03-25 2000-10-03 Sumitomo Bakelite Co Ltd Semiconductor sealing epoxy resin molding material and semiconductor device using the same
JP2001151863A (en) * 1999-11-25 2001-06-05 Matsushita Electric Works Ltd Epoxy resin composition for semiconductor sealing use
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