WO2014024663A1 - Curing agent composition and epoxy resin composition containing same - Google Patents

Curing agent composition and epoxy resin composition containing same Download PDF

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Publication number
WO2014024663A1
WO2014024663A1 PCT/JP2013/069624 JP2013069624W WO2014024663A1 WO 2014024663 A1 WO2014024663 A1 WO 2014024663A1 JP 2013069624 W JP2013069624 W JP 2013069624W WO 2014024663 A1 WO2014024663 A1 WO 2014024663A1
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group
epoxy resin
curing agent
formula
resin composition
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PCT/JP2013/069624
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French (fr)
Japanese (ja)
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つばさ 伊藤
石川　和憲
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横浜ゴム株式会社
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Priority to CN201380040681.8A priority Critical patent/CN104507999A/en
Priority to JP2013553726A priority patent/JPWO2014024663A1/en
Priority to KR20157003241A priority patent/KR20150042199A/en
Publication of WO2014024663A1 publication Critical patent/WO2014024663A1/en

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    • 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
    • C08G59/40—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 curing agents used
    • C08G59/66—Mercaptans
    • 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
    • C08G59/687—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 containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/375—Thiols containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a curing agent composition and an epoxy resin composition containing the same.
  • cationic polymerization initiators such as sulfonium salt compounds are known as curing agents for epoxy resins (for example, Patent Document 1).
  • JP 2011-168574 A Japanese Patent No. 35639797
  • Patent Document 2 discloses a stabilization method using a predetermined alkylphenyl sulfide compound.
  • the present inventors made a curing agent composition containing an alkylphenyl sulfide-based compound disclosed in Patent Document 2 and a cationic polymerization initiator that is a sulfonium salt compound.
  • the epoxy resin composition used as the curing agent was examined, it was found that the storage stability was insufficient.
  • This invention is made
  • the present inventors have intensively studied to achieve the above object. As a result, when a curing agent composition in which a predetermined compound is blended with a cationic polymerization initiator that is a sulfonium salt compound is used as a curing agent for the epoxy resin composition, the storage stability of the epoxy resin composition is excellent.
  • the present invention was completed.
  • the present invention provides the following (I) to (V).
  • (I) A curing agent composition comprising a cationic polymerization initiator that is a sulfonium salt compound and a stabilizer that is a compound represented by the following formula (1).
  • R 1 represents a hydroxy group, a carboxy group, or a group represented by the following formula (2)
  • R 2 represents an alkyl group having 1 to 6 carbon atoms
  • R 3 represents Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, provided that when R 3 represents a hydrogen atom, R 1 represents a carboxy group.
  • R 4 represents an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group which may have a substituent.
  • R 5 represents a hydroxy group or a group represented by any of the following formulas (4) to (7)
  • R 6 represents an alkyl group having 1 to 6 carbon atoms
  • 7 represents an unsaturated hydrocarbon group which may have a substituent
  • X represents a non-nucleophilic anionic group.
  • each R 8 independently represents an aromatic or aliphatic hydrocarbon group which may have a substituent which may contain a hetero atom.
  • the present invention when used as a curing agent for an epoxy resin composition, it is possible to provide a curing agent composition that improves the storage stability of the epoxy resin composition.
  • curing agent composition of this invention is a hardening
  • Such an epoxy resin composition containing the curing agent composition of the present invention and an epoxy resin is excellent in storage stability. At this time, the curability is not impaired. This is because, for example, in the case where the stabilizer is a compound represented by the formula (1A) described later, a methyl group that is an electron-combining group is introduced at the ortho position, so that the nucleophilicity of the sulfide. It is considered that the storage stability is improved.
  • the stabilizer when the stabilizer is a compound represented by the formula (1B) described later, in addition to the nucleophilicity of the sulfide, it may have a structure in which the carbonyl oxygen of the carboxy group is coordinated to the sulfonium salt. Therefore, it is considered that the storage stability is improved by these effects.
  • curing agent composition of this invention is demonstrated in detail.
  • (Cationic polymerization initiator) Although it will not specifically limit if it is a sulfonium salt compound as a cationic polymerization initiator contained in the hardening
  • R 5 represents a hydroxy group or a group represented by any of the following formulas (4) to (7)
  • R 6 represents an alkyl group having 1 to 6 carbon atoms
  • R 7 Represents an unsaturated hydrocarbon group which may have a substituent
  • X represents a non-nucleophilic anionic group.
  • each R 8 independently represents an aromatic or aliphatic hydrocarbon group which may have a substituent which may contain a hetero atom.
  • a hetero atom an oxygen atom, a sulfur atom, a nitrogen atom, etc. are illustrated.
  • R 8 in the formulas (4) to (7) can be selected from various substituents from the viewpoint of adjusting the curability of the epoxy resin composition, and is not particularly limited, but includes a hetero atom represented by R 8.
  • the aromatic hydrocarbon group which may have a substituent may be carbon such as phenyl group, naphthyl group, biphenylenyl group, fluorenyl group, anthryl group, p-toluenesulfonyl group (tosyl group), etc.
  • arylaryl groups such as benzyl group and phenylethyl group; arylalkenyl groups such as styryl group and cinnamyl group; and the like.
  • examples of the aliphatic hydrocarbon group which may have a substituent which may include a hetero atom represented by R 8 include, for example, a saturated group having 1 to 12 carbon atoms such as an alkyl group, an alkenyl group and an alkynyl group.
  • an unsaturated chain hydrocarbon group and specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, Isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, 2-ethylhexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, vinyl, allyl, isopropenyl, A —CH ⁇ CH— (CH 2 ) 8 — group, an ethynyl group and the like can be mentioned.
  • an aromatic hydrocarbon group which may have a substituent which may contain a hetero atom is preferable because the curability of the epoxy resin composition is excellent.
  • An aryl group having 6 to 18 carbon atoms is more preferable, and a p-toluenesulfonyl group is more preferable.
  • the group represented by R 5 in formula (3) is not particularly limited as long as it is a hydroxy group or a group represented by any one of formulas (4) to (7), but the curability of the epoxy resin composition is excellent. Therefore, a hydroxy group or a group represented by the formula (6) is preferable.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R 6 in the formula (3) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Among them, a methyl group and an ethyl group are preferable.
  • Examples of the unsaturated hydrocarbon group which may have a substituent represented by R 7 in formula (3) include an aromatic hydrocarbon group which may have a substituent, and specific examples thereof.
  • an aryl group having 6 to 18 carbon atoms such as a phenyl group, a naphthyl group, a biphenylenyl group, a fluorenyl group, an anthryl group, a p-toluenesulfonyl group (tosyl group); an arylalkyl group such as a benzyl group or a phenylethyl group;
  • Arylalkenyl groups such as a styryl group and a cinnamyl group;
  • the group represented by R 7 is preferably an aryl group or arylalkenyl group having 6 to 18 carbon atoms, and more preferably a naphthyl group or a styryl group, because the epoxy resin composition has excellent curability.
  • non-nucleophilic anionic group represented by X in the formula (3) examples include tetrakis (pentafluorophenyl) borate represented by the following formula (8), SbF 6 , BF 4 , PF 6 , AsF 6 , SbCl 4, and the like.
  • tetrakis (pentafluorophenyl) borate SbF 6 , BF 4 , and PF 6 are preferred, and tetrakis (pentafluorophenyl) borate is more preferred because of the excellent curability of the epoxy resin composition.
  • the sulfonium salt compounds represented by the following formulas (3A) to (3D) can be preferably exemplified.
  • the stabilizer contained in the curing agent composition of the present invention is a compound represented by the following formula (1). Such a stabilizer contributes to the storage stability of the epoxy resin composition in combination with the cationic polymerization initiator described above.
  • R 1 represents a hydroxy group, a carboxy group, or a group represented by the following formula (2)
  • R 2 represents an alkyl group having 1 to 6 carbon atoms
  • R 3 represents A hydrogen atom or an alkyl group having 1 to 6 carbon atoms is shown. However, when R 3 represents a hydrogen atom, R 1 represents a carboxy group.
  • R 4 represents an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group which may have a substituent.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R 4 in the formula (2) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Among them, a methyl group and an ethyl group are preferable.
  • examples of the aromatic hydrocarbon group which may have a substituent represented by R 4 in the formula (2) include a phenyl group, a naphthyl group, a biphenylenyl group, a fluorenyl group, an anthryl group, and p-toluenesulfonyl.
  • Aryl groups having 6 to 18 carbon atoms such as a group (tosyl group); arylalkyl groups such as benzyl group and phenylethyl group; arylalkenyl groups such as styryl group and cinnamyl group;
  • R ⁇ 1 > in Formula (1) shows, a hydroxy group and a carboxy group are preferable from the reason that the storage stability of an epoxy resin composition is more excellent.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R 2 in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Among them, a methyl group and an ethyl group are preferable.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R 3 in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Among them, a methyl group and an ethyl group are preferable.
  • the group represented by R 3 in the formula (1) is not particularly limited as long as it is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, but for the reason that the storage stability of the epoxy resin composition is more excellent, 1-6 alkyl groups are preferred.
  • a compound represented by the formula (1) as described above a compound represented by the following formula (1A) or (1B) can be preferably exemplified.
  • the content of such a stabilizer is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, based on the above-described cationic polymerization initiator, and 0.05 More preferably, it is ⁇ 10% by mass. If content of a stabilizer is this range, in the epoxy resin composition using the hardening
  • the method for producing the curing agent composition of the present invention is not particularly limited.
  • the manufacturing method of the epoxy resin composition of this invention mentioned later may serve as the manufacturing method of the hardening
  • Epoxy resin composition ⁇ Epoxy resin composition> Next, the epoxy resin composition of the present invention will be described.
  • the epoxy resin composition of this invention will not be specifically limited if it contains an epoxy resin and the hardening
  • the content of the curing agent composition of the present invention is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin. . If content of the hardening
  • Epoxy resin The epoxy resin contained in the epoxy resin composition of the present invention is not particularly limited as long as it has two or more epoxy groups, and conventionally known ones can be used, for example, bisphenol A type epoxy resin, Bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, diaminodiphenylmethane type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, hydrogenated bisphenol A type epoxy resin, water Bisphenol F type epoxy resin, hydrogenated biphenol type epoxy resin, polyalkylene glycol type epoxy resin, alicyclic epoxy resin, and the like may be used, and these may be used alone or in combination of two or more. Good.
  • a commercial item can be used as such an epoxy resin.
  • examples of the bisphenol A type epoxy resin include Epicoat 828 (manufactured by JER) and EP4100E (manufactured by ADEKA).
  • examples of the polyalkylene glycol type epoxy resin include EP4000S and EP4010S (both are ADEKA).
  • examples of the alicyclic epoxy resin include Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd.).
  • the epoxy resin composition of the present invention is, as necessary, for example, a filler, a reaction retarding agent, an antioxidant, an antioxidant, a pigment (dye), a plasticizer, as long as the object of the present invention is not impaired.
  • Various additives such as a thixotropic agent, an ultraviolet absorber, a flame retardant, a solvent, a surfactant (including a leveling agent), a dispersant, a dehydrating agent, an adhesion imparting agent, and an antistatic agent can be contained.
  • the method for producing the epoxy resin composition of the present invention is not particularly limited.
  • the epoxy resin, the curing agent composition of the present invention, and an additive that can be used as necessary are used under reduced pressure or under an inert atmosphere.
  • the manufacturing method of the epoxy resin composition of this invention may serve as the manufacturing method of the hardening
  • the epoxy resin composition of the present invention is excellent in storage stability, it can be a one-component type.
  • the epoxy resin composition of the present invention is a one-pack type, the epoxy resin composition of the present invention can be placed in a container, hermetically sealed and stored at room temperature or lower (for example, ⁇ 20 to 25 ° C.).
  • the epoxy resin composition of the present invention can be cured by heating for a short time under heating conditions.
  • the heating temperature is preferably 60 to 250 ° C., and more preferably 60 to 200 ° C. from the viewpoint of shortening the curing time in production.
  • adherends to which the epoxy resin composition of the present invention can be used include glass materials, plastic materials, metals, and organic-inorganic composite materials. Although it does not specifically limit as a use of the epoxy resin composition of this invention, For example, a sealing material, a laminated board, an adhesive agent, a sealing material, a coating material etc. are mentioned.
  • the epoxy resin composition of the present invention can be cured at a low temperature in a short time, thereby reducing the internal stress that occurs during curing. For example, it can be used in the field of electronic materials such as anisotropic conductive films. Can be suitably used.
  • ⁇ Preparation of epoxy resin composition Preparation of a curing agent composition by blending each component so as to have the composition shown in Table 1 below (unit: parts by mass) and uniformly mixing with a stirrer (conditioning mixer MX-20, manufactured by Sinky Corporation) In addition, an epoxy resin composition was prepared.
  • the Yasuda-type gel time tester is a device that rotates the rotor in a test tube containing a sample in an oil bath, and when the gelation proceeds and a certain torque is applied, the rotor is dropped by the magnetic coupling mechanism and the timer is stopped. .
  • Epoxy resin 1 bisphenol A type epoxy resin (EP4100E, manufactured by ADEKA)
  • Cationic polymerization initiator 1 sulfonium salt compound represented by the formula (3A) prepared as follows First, 4.59 g of 4-methylthiophenol and 5 g of cinnamilk chloride were mixed with 1: 1 of methanol and methylcyclohexane. The reaction was carried out in a mixed solvent at room temperature for 24 hours to obtain a chloride intermediate.
  • Cationic polymerization initiator 2 sulfonium salt compound represented by the formula (3B) prepared as follows First, 10 g of 1- (chloromethyl) naphthalene and 7.9 g of 4-methylthiophenol were mixed in methanol at room temperature. Reaction was performed for 24 hours to obtain a chloride intermediate. Next, 10 g of the obtained chloride intermediate was mixed with 220.16 g of an aqueous sodium salt solution of tetrakis (pentafluorophenyl) borate (solid content 10%) to obtain an intermediate.
  • Cationic polymerization initiator 3 Sulphonium salt compound represented by the formula (3C) prepared as follows First, 10 g of 1- (chloromethyl) naphthalene and 7.9 g of 4-methylthiophenol were mixed in methanol at room temperature. Reaction was performed for 24 hours to obtain a chloride intermediate. Next, 10 g of the obtained chloride intermediate was mixed with 220.16 g of an aqueous sodium salt solution (solid content: 10%) of tetrakis (pentafluorophenyl) borate to obtain a sulfonium salt compound represented by the formula (3C). .
  • Cationic polymerization initiator 4 sulfonium salt compound represented by the formula (3D) (SI60L, manufactured by Sanshin Chemical Co., Ltd.)
  • Stabilizer 1 Compound represented by formula (1A) (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Stabilizer 2 Compound represented by formula (1B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • -Stabilizer 3 Compound represented by the following formula (Z) (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Examples 1 to 8 using Stabilizer 1 or Stabilizer 2 have a lower rate of increase in viscosity than Comparative Examples 1 to 3 which do not use them, and storage. It was found to be excellent in stability. In addition, Examples 1 to 8 had the same gel time as Comparative Examples 1 to 3, and the curability was not impaired.
  • the stabilizer 3 is a stabilizer disclosed in Patent Document 2
  • the comparative example 4 using the stabilizer 3 has, for example, a lower viscosity increase rate than the comparative example 1 that does not include the stabilizer. However, it was found that the rate of increase in viscosity was high compared to other examples, and the storage stability was insufficient.
  • the stabilizer 1 which is a compound represented by the formula (1A) has a sulfide nucleophilicity increased due to the introduction of a methyl group which is an electron-donating group at the ortho position, and storage stability. It is thought that the property improved.
  • the stabilizer 2 which is a compound represented by the formula (1B) can take a structure in which the carbonyl oxygen of the carboxy group is coordinated to the sulfonium salt in addition to the nucleophilicity of the sulfide. It is considered that the storage stability was improved by the effect of.

Abstract

Provided is a curing agent composition which improves the storage stability of an epoxy resin composition if used as a curing agent for the epoxy resin composition. This curing agent composition contains a cationic polymerization initiator that is composed of a sulfonium salt compound and a stabilizer that is composed of a compound represented by formula (1). (In formula (1), R1 represents a hydroxy group, a carboxy group or a group represented by formula (2); R2 represents an alkyl group having 1-6 carbon atoms; and R3 represents a hydrogen atom or an alkyl group having 1-6 carbon atoms. In this connection, in cases where R3 represents a hydrogen atom, R1 represents a carboxy group.) R4O－ (2) (In formula (2), R4 represents an alkyl group having 1-6 carbon atoms or an optionally substituted aromatic hydrocarbon group.)

Description

硬化剤組成物およびこれを含有するエポキシ樹脂組成物Curing agent composition and epoxy resin composition containing the same
　本発明は、硬化剤組成物およびこれを含有するエポキシ樹脂組成物に関する。 The present invention relates to a curing agent composition and an epoxy resin composition containing the same.
　従来、エポキシ樹脂の硬化剤として、スルホニウム塩化合物などのカチオン重合開始剤が知られている（例えば、特許文献１）。 Conventionally, cationic polymerization initiators such as sulfonium salt compounds are known as curing agents for epoxy resins (for example, Patent Document 1).
特開２０１１－１６８５７４号公報JP 2011-168574 A 特許第３５６６３９７号公報Japanese Patent No. 35639797
　本発明者らが、特許文献１に記載されたカチオン重合開始剤を硬化剤として含むエポキシ樹脂組成物について検討したところ、硬化性は比較的良好であるものの、貯蔵安定性に劣ることが分かった。 When the present inventors examined the epoxy resin composition which contains the cationic polymerization initiator described in patent document 1 as a hardening | curing agent, although curability was comparatively favorable, it turned out that it is inferior to storage stability. .
　ここで、例えば、特許文献２には、所定のアルキルフェニルスルフィド系化合物を用いた安定化方法が開示されている。
　しかしながら、本発明者らが、特許文献２に開示されたアルキルフェニルスルフィド系化合物と、スルホニウム塩化合物であるカチオン重合開始剤とを含有する硬化剤組成物を作成し、作成した硬化剤組成物を硬化剤として用いたエポキシ樹脂組成物について検討したところ、貯蔵安定性が不十分であることが分かった。 Here, for example, Patent Document 2 discloses a stabilization method using a predetermined alkylphenyl sulfide compound.
However, the present inventors made a curing agent composition containing an alkylphenyl sulfide-based compound disclosed in Patent Document 2 and a cationic polymerization initiator that is a sulfonium salt compound. When the epoxy resin composition used as the curing agent was examined, it was found that the storage stability was insufficient.
　本発明は、以上の点を鑑みてなされたものであり、エポキシ樹脂組成物の硬化剤として使用された場合に、該エポキシ樹脂組成物の貯蔵安定性を良好にする硬化剤組成物を提供することを目的とする。 This invention is made | formed in view of the above point, and when used as a hardening | curing agent of an epoxy resin composition, the hardening | curing agent composition which makes the storage stability of this epoxy resin composition favorable is provided. For the purpose.
　本発明者らは、上記目的を達成するために鋭意検討を行なった。その結果、エポキシ樹脂組成物の硬化剤として、スルホニウム塩化合物であるカチオン重合開始剤に所定の化合物を配合した硬化剤組成物を使用した場合に、該エポキシ樹脂組成物の貯蔵安定性が優れることを見出し、本発明を完成させた。 The present inventors have intensively studied to achieve the above object. As a result, when a curing agent composition in which a predetermined compound is blended with a cationic polymerization initiator that is a sulfonium salt compound is used as a curing agent for the epoxy resin composition, the storage stability of the epoxy resin composition is excellent. The present invention was completed.
　すなわち、本発明は、以下の（Ｉ）～（Ｖ）を提供する。
　（Ｉ）スルホニウム塩化合物であるカチオン重合開始剤と、下記式（１）で表される化合物である安定剤と、を含有する硬化剤組成物。 That is, the present invention provides the following (I) to (V).
(I) A curing agent composition comprising a cationic polymerization initiator that is a sulfonium salt compound and a stabilizer that is a compound represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
（式（１）中、Ｒ1は、ヒドロキシ基、カルボキシ基、または、下記式（２）で表される基を示し、Ｒ2は、炭素数１～６のアルキル基を示し、Ｒ3は、水素原子または炭素数１～６のアルキル基を示す。ただし、Ｒ3が水素原子を示すときは、Ｒ1はカルボキシ基を示す。） (In the formula (1), R 1 represents a hydroxy group, a carboxy group, or a group represented by the following formula (2), R 2 represents an alkyl group having 1 to 6 carbon atoms, and R 3 represents Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, provided that when R 3 represents a hydrogen atom, R 1 represents a carboxy group.)
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
（式（２）中、Ｒ4は、炭素数１～６のアルキル基、または、置換基を有していてもよい芳香族炭化水素基を示す。） (In the formula (2), R 4 represents an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group which may have a substituent.)
　（ＩＩ）上記安定剤の含有量が、上記カチオン重合開始剤に対して、０．００１～２０質量％である、上記（Ｉ）に記載の硬化剤組成物。 (II) The curing agent composition according to (I), wherein the content of the stabilizer is 0.001 to 20% by mass with respect to the cationic polymerization initiator.
　（ＩＩＩ）上記カチオン重合開始剤が、下記式（３）で表されるスルホニウム塩化合物である、上記（Ｉ）または（ＩＩ）に記載の硬化剤組成物。 (III) The curing agent composition according to (I) or (II), wherein the cationic polymerization initiator is a sulfonium salt compound represented by the following formula (3).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
（式（３）中、Ｒ5は、ヒドロキシ基または下記式（４）～（７）のいずれかで表される基を示し、Ｒ6は、炭素数１～６のアルキル基を示し、Ｒ7は、置換基を有していてもよい不飽和炭化水素基を示し、Ｘは、非求核性アニオン性基を示す。） (In the formula (3), R 5 represents a hydroxy group or a group represented by any of the following formulas (4) to (7), R 6 represents an alkyl group having 1 to 6 carbon atoms, 7 represents an unsaturated hydrocarbon group which may have a substituent, and X represents a non-nucleophilic anionic group.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
（式（４）～（７）中、Ｒ8は、それぞれ独立に、ヘテロ原子を含んでいてもよい置換基を有していてもよい芳香族または脂肪族炭化水素基を示す。） (In formulas (4) to (7), each R 8 independently represents an aromatic or aliphatic hydrocarbon group which may have a substituent which may contain a hetero atom.)
　（ＩＶ）エポキシ樹脂と、上記（Ｉ）～（ＩＩＩ）のいずれかに記載の硬化剤組成物とを含有する、エポキシ樹脂組成物。 (IV) An epoxy resin composition containing an epoxy resin and the curing agent composition according to any one of (I) to (III) above.
　（Ｖ）上記硬化剤組成物の含有量が、上記エポキシ樹脂１００質量部に対して、０．１～２０質量部である、上記（ＩＶ）に記載のエポキシ樹脂組成物。 (V) The epoxy resin composition according to (IV), wherein the content of the curing agent composition is 0.1 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin.
　本発明によれば、エポキシ樹脂組成物の硬化剤として使用された場合に、該エポキシ樹脂組成物の貯蔵安定性を良好にする硬化剤組成物を提供することができる。 According to the present invention, when used as a curing agent for an epoxy resin composition, it is possible to provide a curing agent composition that improves the storage stability of the epoxy resin composition.
＜硬化剤組成物＞
　本発明の硬化剤組成物は、スルホニウム塩化合物であるカチオン重合開始剤と、上記式（１）で表される化合物である安定剤と、を含有する硬化剤組成物である。このような本発明の硬化剤組成物と、エポキシ樹脂とを含有するエポキシ樹脂組成物においては、貯蔵安定性に優れる。また、このとき、硬化性が損なわれることもない。
　これは、例えば、安定剤が後述する式（１Ａ）で表される化合物である場合においては、オルト位に電子共与性基であるメチル基が導入されていることにより、スルフィドの求核性が高まり、貯蔵安定性が向上するものと考えられる。
　また、例えば、安定剤が後述する式（１Ｂ）で表される化合物である場合においては、スルフィドの求核性の他に、カルボキシ基のカルボニル酸素がスルホニウム塩に配位する構造をとることができるため、これらの効果により貯蔵安定性が向上するものと考えられる。
　以下、本発明の硬化剤組成物に含有される各成分について、詳細に説明する。 <Curing agent composition>
The hardening | curing agent composition of this invention is a hardening | curing agent composition containing the cationic polymerization initiator which is a sulfonium salt compound, and the stabilizer which is a compound represented by the said Formula (1). Such an epoxy resin composition containing the curing agent composition of the present invention and an epoxy resin is excellent in storage stability. At this time, the curability is not impaired.
This is because, for example, in the case where the stabilizer is a compound represented by the formula (1A) described later, a methyl group that is an electron-combining group is introduced at the ortho position, so that the nucleophilicity of the sulfide. It is considered that the storage stability is improved.
Further, for example, when the stabilizer is a compound represented by the formula (1B) described later, in addition to the nucleophilicity of the sulfide, it may have a structure in which the carbonyl oxygen of the carboxy group is coordinated to the sulfonium salt. Therefore, it is considered that the storage stability is improved by these effects.
Hereinafter, each component contained in the hardening | curing agent composition of this invention is demonstrated in detail.
（カチオン重合開始剤）
　本発明の硬化剤組成物に含有されるカチオン重合開始剤としては、スルホニウム塩化合物であれば特に限定されないが、例えば、下記式（３）で表されるスルホニウム塩化合物が挙げられる。 (Cationic polymerization initiator)
Although it will not specifically limit if it is a sulfonium salt compound as a cationic polymerization initiator contained in the hardening | curing agent composition of this invention, For example, the sulfonium salt compound represented by following formula (3) is mentioned.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式（３）中、Ｒ5は、ヒドロキシ基または下記式（４）～（７）のいずれかで表される基を示し、Ｒ6は、炭素数１～６のアルキル基を示し、Ｒ7は、置換基を有していてもよい不飽和炭化水素基を示し、Ｘは、非求核性アニオン性基を示す。 In the formula (3), R 5 represents a hydroxy group or a group represented by any of the following formulas (4) to (7), R 6 represents an alkyl group having 1 to 6 carbon atoms, R 7 Represents an unsaturated hydrocarbon group which may have a substituent, and X represents a non-nucleophilic anionic group.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　式（４）～（７）中、Ｒ8は、それぞれ独立に、ヘテロ原子を含んでいてもよい置換基を有していてもよい芳香族または脂肪族炭化水素基を示す。なお、ヘテロ原子としては、酸素原子、硫黄原子、窒素原子などが例示される。 In the formulas (4) to (7), each R 8 independently represents an aromatic or aliphatic hydrocarbon group which may have a substituent which may contain a hetero atom. In addition, as a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are illustrated.
　式（４）～（７）中のＲ8は、エポキシ樹脂組成物の硬化性を調整する観点から種々の置換基を選択することができ、特に限定されないが、Ｒ8が示すヘテロ原子を含んでいてもよい置換基を有していてもよい芳香族炭化水素基としては、例えば、フェニル基、ナフチル基、ビフェニレニル基、フルオレニル基、アンスリル基、ｐ－トルエンスルホニル基（トシル基）などの炭素数６～１８のアリール基；ベンジル基、フェニルエチル基などのアリールアルキル基；スチリル基、シンナミル基などのアリールアルケニル基；等が挙げられる。
　また、Ｒ8が示すヘテロ原子を含んでいてもよい置換基を有していてもよい脂肪族炭化水素基としては、例えば、アルキル基、アルケニル基、アルキニル基などの炭素数１～１２の飽和または不飽和の鎖式炭化水素基が挙げられ、その具体例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、ヘキシル基、イソヘキシル基、２－エチルヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、ビニル基、アリル基、イソプロペニル基、－ＣＨ＝ＣＨ－（ＣＨ2）8－基、エチニル基などが挙げられる。 R 8 in the formulas (4) to (7) can be selected from various substituents from the viewpoint of adjusting the curability of the epoxy resin composition, and is not particularly limited, but includes a hetero atom represented by R 8. Examples of the aromatic hydrocarbon group which may have a substituent may be carbon such as phenyl group, naphthyl group, biphenylenyl group, fluorenyl group, anthryl group, p-toluenesulfonyl group (tosyl group), etc. And arylaryl groups such as benzyl group and phenylethyl group; arylalkenyl groups such as styryl group and cinnamyl group; and the like.
In addition, examples of the aliphatic hydrocarbon group which may have a substituent which may include a hetero atom represented by R 8 include, for example, a saturated group having 1 to 12 carbon atoms such as an alkyl group, an alkenyl group and an alkynyl group. Or an unsaturated chain hydrocarbon group, and specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, Isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, 2-ethylhexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, vinyl, allyl, isopropenyl, A —CH═CH— (CH 2 ) 8 — group, an ethynyl group and the like can be mentioned.
　これらのうち、Ｒ8が示す基としては、エポキシ樹脂組成物の硬化性が優れるという理由から、ヘテロ原子を含んでいてもよい置換基を有していてもよい芳香族炭化水素基が好ましく、炭素数６～１８のアリール基がより好ましく、ｐ－トルエンスルホニル基がさらに好ましい。 Among these, as the group represented by R 8 , an aromatic hydrocarbon group which may have a substituent which may contain a hetero atom is preferable because the curability of the epoxy resin composition is excellent, An aryl group having 6 to 18 carbon atoms is more preferable, and a p-toluenesulfonyl group is more preferable.
　式（３）中のＲ5が示す基としては、ヒドロキシ基または式（４）～（７）のいずれかで表される基であれば特に限定されないが、エポキシ樹脂組成物の硬化性が優れるという理由から、ヒドロキシ基または式（６）で表される基が好ましい。 The group represented by R 5 in formula (3) is not particularly limited as long as it is a hydroxy group or a group represented by any one of formulas (4) to (7), but the curability of the epoxy resin composition is excellent. Therefore, a hydroxy group or a group represented by the formula (6) is preferable.
　式（３）中のＲ6が示す炭素数１～６のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基などが挙げられ、なかでも、メチル基、エチル基であるのが好ましい。 Examples of the alkyl group having 1 to 6 carbon atoms represented by R 6 in the formula (3) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Among them, a methyl group and an ethyl group are preferable.
　式（３）中のＲ7が示す置換基を有していてもよい不飽和炭化水素基としては、例えば、置換基を有していてもよい芳香族炭化水素基が挙げられ、その具体例としては、フェニル基、ナフチル基、ビフェニレニル基、フルオレニル基、アンスリル基、ｐ－トルエンスルホニル基（トシル基）などの炭素数６～１８のアリール基；ベンジル基、フェニルエチル基などのアリールアルキル基；スチリル基、シンナミル基などのアリールアルケニル基；等が挙げられる。 Examples of the unsaturated hydrocarbon group which may have a substituent represented by R 7 in formula (3) include an aromatic hydrocarbon group which may have a substituent, and specific examples thereof. As an aryl group having 6 to 18 carbon atoms such as a phenyl group, a naphthyl group, a biphenylenyl group, a fluorenyl group, an anthryl group, a p-toluenesulfonyl group (tosyl group); an arylalkyl group such as a benzyl group or a phenylethyl group; Arylalkenyl groups such as a styryl group and a cinnamyl group;
　これらのうち、Ｒ7が示す基としては、エポキシ樹脂組成物の硬化性が優れるという理由から、炭素数６～１８のアリール基、アリールアルケニル基が好ましく、ナフチル基、スチリル基がより好ましい。 Of these, the group represented by R 7 is preferably an aryl group or arylalkenyl group having 6 to 18 carbon atoms, and more preferably a naphthyl group or a styryl group, because the epoxy resin composition has excellent curability.
　式（３）中のＸが示す非求核性アニオン性基としては、例えば、下記式（８）で表されるテトラキス（ペンタフルオロフェニル）ボレート、ＳｂＦ6、ＢＦ4、ＰＦ6、ＡｓＦ6、ＳｂＣｌ4等が挙げられる。 Examples of the non-nucleophilic anionic group represented by X in the formula (3) include tetrakis (pentafluorophenyl) borate represented by the following formula (8), SbF 6 , BF 4 , PF 6 , AsF 6 , SbCl 4, and the like.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　これらのうち、エポキシ樹脂組成物の硬化性が優れるという理由から、テトラキス（ペンタフルオロフェニル）ボレート、ＳｂＦ6、ＢＦ4、ＰＦ6が好ましく、テトラキス（ペンタフルオロフェニル）ボレートがより好ましい。 Of these, tetrakis (pentafluorophenyl) borate, SbF 6 , BF 4 , and PF 6 are preferred, and tetrakis (pentafluorophenyl) borate is more preferred because of the excellent curability of the epoxy resin composition.
　以上説明したような、式（３）で表されるスルホニウム塩化合物の具体例としては、下記式（３Ａ）～（３Ｄ）で表されるスルホニウム塩化合物を好適に挙げることができる。 As specific examples of the sulfonium salt compound represented by the formula (3) as described above, the sulfonium salt compounds represented by the following formulas (3A) to (3D) can be preferably exemplified.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
（安定剤）
　本発明の硬化剤組成物に含有される安定剤は、下記式（１）で表される化合物である。このような安定剤は、上述したカチオン重合開始剤と併用されて、エポキシ樹脂組成物の貯蔵安定性に資する。 (Stabilizer)
The stabilizer contained in the curing agent composition of the present invention is a compound represented by the following formula (1). Such a stabilizer contributes to the storage stability of the epoxy resin composition in combination with the cationic polymerization initiator described above.
　式（１）中、Ｒ1は、ヒドロキシ基、カルボキシ基、または、下記式（２）で表される基を示し、Ｒ2は、炭素数１～６のアルキル基を示し、Ｒ3は、水素原子または炭素数１～６のアルキル基を示す。ただし、Ｒ3が水素原子を示すときは、Ｒ1はカルボキシ基を示す。 In the formula (1), R 1 represents a hydroxy group, a carboxy group, or a group represented by the following formula (2), R 2 represents an alkyl group having 1 to 6 carbon atoms, and R 3 represents A hydrogen atom or an alkyl group having 1 to 6 carbon atoms is shown. However, when R 3 represents a hydrogen atom, R 1 represents a carboxy group.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　式（２）中、Ｒ4は、炭素数１～６のアルキル基、または、置換基を有していてもよい芳香族炭化水素基を示す。 In the formula (2), R 4 represents an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group which may have a substituent.
　式（２）中のＲ4が示す炭素数１～６のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基などが挙げられ、なかでも、メチル基、エチル基であるのが好ましい。
　また、式（２）中のＲ4が示す置換基を有していてもよい芳香族炭化水素基としては、例えば、フェニル基、ナフチル基、ビフェニレニル基、フルオレニル基、アンスリル基、ｐ－トルエンスルホニル基（トシル基）などの炭素数６～１８のアリール基；ベンジル基、フェニルエチル基などのアリールアルキル基；スチリル基、シンナミル基などのアリールアルケニル基；等が挙げられる。 Examples of the alkyl group having 1 to 6 carbon atoms represented by R 4 in the formula (2) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Among them, a methyl group and an ethyl group are preferable.
In addition, examples of the aromatic hydrocarbon group which may have a substituent represented by R 4 in the formula (2) include a phenyl group, a naphthyl group, a biphenylenyl group, a fluorenyl group, an anthryl group, and p-toluenesulfonyl. Aryl groups having 6 to 18 carbon atoms such as a group (tosyl group); arylalkyl groups such as benzyl group and phenylethyl group; arylalkenyl groups such as styryl group and cinnamyl group;
　式（１）中のＲ1が示す基としては、エポキシ樹脂組成物の貯蔵安定性がより優れるという理由から、ヒドロキシ基、カルボキシ基が好ましい。 As group which R < 1 > in Formula (1) shows, a hydroxy group and a carboxy group are preferable from the reason that the storage stability of an epoxy resin composition is more excellent.
　式（１）中のＲ2が示す炭素数１～６のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基などが挙げられ、なかでも、メチル基、エチル基であるのが好ましい。
　式（１）中のＲ3が示す炭素数１～６のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基などが挙げられ、なかでも、メチル基、エチル基であるのが好ましい。 Examples of the alkyl group having 1 to 6 carbon atoms represented by R 2 in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Among them, a methyl group and an ethyl group are preferable.
Examples of the alkyl group having 1 to 6 carbon atoms represented by R 3 in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Among them, a methyl group and an ethyl group are preferable.
　式（１）中のＲ3が示す基としては、水素原子または炭素数１～６のアルキル基であれば特に限定されないが、エポキシ樹脂組成物の貯蔵安定性がより優れるという理由から、炭素数１～６のアルキル基が好ましい。 The group represented by R 3 in the formula (1) is not particularly limited as long as it is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, but for the reason that the storage stability of the epoxy resin composition is more excellent, 1-6 alkyl groups are preferred.
　以上説明したような、式（１）で表される化合物の具体例としては、下記式（１Ａ）または（１Ｂ）で表される化合物を好適に挙げることができる。 As specific examples of the compound represented by the formula (1) as described above, a compound represented by the following formula (1A) or (1B) can be preferably exemplified.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　このような安定剤の含有量は、上述したカチオン重合開始剤に対して、０．００１～２０質量％であるのが好ましく、０．０１～１０質量％であるのがより好ましく、０．０５～１０質量％であるのがさらに好ましい。
　安定剤の含有量がこの範囲であれば、本発明の硬化剤組成物を用いたエポキシ樹脂組成物において、貯蔵安定性がより優れる。 The content of such a stabilizer is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, based on the above-described cationic polymerization initiator, and 0.05 More preferably, it is ˜10% by mass.
If content of a stabilizer is this range, in the epoxy resin composition using the hardening | curing agent composition of this invention, storage stability will be more excellent.
　本発明の硬化剤組成物の製造方法については特に限定されず、例えば、上述したカチオン重合開始剤および安定剤を、減圧下または不活性雰囲気下で、十分に混練し、均一に分散させる方法が挙げられる。
　なお、後述する本発明のエポキシ樹脂組成物の製造方法が、本発明の硬化剤組成物の製造方法を兼ねていてもよい。 The method for producing the curing agent composition of the present invention is not particularly limited. For example, there is a method in which the above-described cationic polymerization initiator and stabilizer are sufficiently kneaded and uniformly dispersed under reduced pressure or an inert atmosphere. Can be mentioned.
In addition, the manufacturing method of the epoxy resin composition of this invention mentioned later may serve as the manufacturing method of the hardening | curing agent composition of this invention.
＜エポキシ樹脂組成物＞
　次に、本発明のエポキシ樹脂組成物について説明する。本発明のエポキシ樹脂組成物は、エポキシ樹脂と、上述した本発明の硬化剤組成物とを含有するものであれば特に限定されない。
　本発明のエポキシ樹脂組成物は、エポキシ樹脂の硬化剤として本発明の硬化剤組成物を含有するため、硬化性が損なわれることなく、貯蔵安定性に優れる。 <Epoxy resin composition>
Next, the epoxy resin composition of the present invention will be described. The epoxy resin composition of this invention will not be specifically limited if it contains an epoxy resin and the hardening | curing agent composition of this invention mentioned above.
Since the epoxy resin composition of the present invention contains the curing agent composition of the present invention as a curing agent for the epoxy resin, the curability is not impaired and the storage stability is excellent.
　このとき、本発明の硬化剤組成物の含有量は、エポキシ樹脂１００質量部に対して、０．１～２０質量部であるのが好ましく、０．５～１０質量部であるのがより好ましい。本発明の硬化剤組成物の含有量がこの範囲であれば、本発明のエポキシ樹脂組成物の貯蔵安定性がより優れ、かつ、ガラス転移点の高い硬化物が得られる。 At this time, the content of the curing agent composition of the present invention is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin. . If content of the hardening | curing agent composition of this invention is this range, the storage stability of the epoxy resin composition of this invention will be more excellent, and the hardened | cured material with a high glass transition point will be obtained.
（エポキシ樹脂）
　本発明のエポキシ樹脂組成物に含有されるエポキシ樹脂としては、エポキシ基を２個以上有するものであれば特に限定されず、従来公知のものを用いることができ、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ジアミノジフェニルメタン型エポキシ樹脂、アミノフェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＦ型エポキシ樹脂、水添ビフェノール型エポキシ樹脂、ポリアルキレングリコール型エポキシ樹脂、脂環式エポキシ樹脂などが挙げられ、これらを１種単独で用いてもよく、２種以上を併用してもよい。
　このようなエポキシ樹脂としては、市販品を用いることができる。例えば、ビスフェノールＡ型エポキシ樹脂としては、例えば、エピコート８２８（ＪＥＲ社製）、ＥＰ４１００Ｅ（ＡＤＥＫＡ社製）等が挙げられ、ポリアルキレングリコール型エポキシ樹脂としては、例えば、ＥＰ４０００Ｓ、ＥＰ４０１０Ｓ（いずれもＡＤＥＫＡ社製）等が挙げられ、脂環式エポキシ樹脂としては、例えば、セロキサイド２０２１Ｐ（ダイセル化学社製）が挙げられる。 (Epoxy resin)
The epoxy resin contained in the epoxy resin composition of the present invention is not particularly limited as long as it has two or more epoxy groups, and conventionally known ones can be used, for example, bisphenol A type epoxy resin, Bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, diaminodiphenylmethane type epoxy resin, aminophenol type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, hydrogenated bisphenol A type epoxy resin, water Bisphenol F type epoxy resin, hydrogenated biphenol type epoxy resin, polyalkylene glycol type epoxy resin, alicyclic epoxy resin, and the like may be used, and these may be used alone or in combination of two or more. Good.
A commercial item can be used as such an epoxy resin. For example, examples of the bisphenol A type epoxy resin include Epicoat 828 (manufactured by JER) and EP4100E (manufactured by ADEKA). Examples of the polyalkylene glycol type epoxy resin include EP4000S and EP4010S (both are ADEKA). Examples of the alicyclic epoxy resin include Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd.).
（添加剤）
　本発明のエポキシ樹脂組成物は、本発明の目的を損わない範囲で、必要に応じて、例えば、充填剤、反応遅延剤、老化防止剤、酸化防止剤、顔料（染料）、可塑剤、揺変性付与剤、紫外線吸収剤、難燃剤、溶剤、界面活性剤（レベリング剤を含む）、分散剤、脱水剤、接着付与剤、帯電防止剤などの各種添加剤を含有することができる。 (Additive)
The epoxy resin composition of the present invention is, as necessary, for example, a filler, a reaction retarding agent, an antioxidant, an antioxidant, a pigment (dye), a plasticizer, as long as the object of the present invention is not impaired. Various additives such as a thixotropic agent, an ultraviolet absorber, a flame retardant, a solvent, a surfactant (including a leveling agent), a dispersant, a dehydrating agent, an adhesion imparting agent, and an antistatic agent can be contained.
　本発明のエポキシ樹脂組成物の製造方法については特に限定されず、例えば、エポキシ樹脂と、本発明の硬化剤組成物と、必要に応じて使用できる添加剤とを、減圧下または不活性雰囲気下で、ボールミル等の混合装置を用いて十分に混練し、均一に分散させる方法が挙げられる。
　なお、本発明のエポキシ樹脂組成物の製造方法が、上述した本発明の硬化剤組成物の製造方法を兼ねていてもよい。 The method for producing the epoxy resin composition of the present invention is not particularly limited. For example, the epoxy resin, the curing agent composition of the present invention, and an additive that can be used as necessary are used under reduced pressure or under an inert atmosphere. And a method of sufficiently kneading and uniformly dispersing using a mixing device such as a ball mill.
In addition, the manufacturing method of the epoxy resin composition of this invention may serve as the manufacturing method of the hardening | curing agent composition of this invention mentioned above.
　本発明のエポキシ樹脂組成物は、貯蔵安定性に優れるので１液型とすることができる。本発明のエポキシ樹脂組成物を１液型とする場合、本発明のエポキシ樹脂組成物を容器に入れ、密閉して室温以下（例えば、－２０～２５℃）で保管することができる。 Since the epoxy resin composition of the present invention is excellent in storage stability, it can be a one-component type. When the epoxy resin composition of the present invention is a one-pack type, the epoxy resin composition of the present invention can be placed in a container, hermetically sealed and stored at room temperature or lower (for example, −20 to 25 ° C.).
　本発明のエポキシ樹脂組成物は、加熱条件下で短時間加熱することによって、硬化させることができる。加熱温度は、６０～２５０℃であるのが好ましく、生産上硬化時間を短縮させる観点から、６０～２００℃であるのがより好ましい。 The epoxy resin composition of the present invention can be cured by heating for a short time under heating conditions. The heating temperature is preferably 60 to 250 ° C., and more preferably 60 to 200 ° C. from the viewpoint of shortening the curing time in production.
　本発明のエポキシ樹脂組成物を使用することができる被着体としては、例えば、ガラス材料、プラスチック材料、金属、有機無機複合材料などが挙げられる。
　本発明のエポキシ樹脂組成物の用途としては、特に限定されないが、例えば、封止材、積層板、接着剤、シーリング材、塗料などが挙げられる。また、本発明のエポキシ樹脂組成物は、低温で短時間に硬化することができ、これにより、硬化時に生じる内部応力を低減できるため、例えば、異方性導電フィルムなどの電子材料分野での用途に好適に用いることができる。 Examples of adherends to which the epoxy resin composition of the present invention can be used include glass materials, plastic materials, metals, and organic-inorganic composite materials.
Although it does not specifically limit as a use of the epoxy resin composition of this invention, For example, a sealing material, a laminated board, an adhesive agent, a sealing material, a coating material etc. are mentioned. In addition, the epoxy resin composition of the present invention can be cured at a low temperature in a short time, thereby reducing the internal stress that occurs during curing. For example, it can be used in the field of electronic materials such as anisotropic conductive films. Can be suitably used.
　以下に、実施例を挙げて本発明を具体的に説明する。ただし、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
＜エポキシ樹脂組成物の調製＞
　下記第１表に示す組成（単位は質量部）になるように、各成分を配合して攪拌機（コンディショニングミキサー ＭＸ－２０、シンキー社製）を用いて均一に混合し、硬化剤組成物の調製も兼ねて、エポキシ樹脂組成物を調製した。 <Preparation of epoxy resin composition>
Preparation of a curing agent composition by blending each component so as to have the composition shown in Table 1 below (unit: parts by mass) and uniformly mixing with a stirrer (conditioning mixer MX-20, manufactured by Sinky Corporation) In addition, an epoxy resin composition was prepared.
＜評価＞
　調製した各エポキシ樹脂組成物について、それぞれ、下記の方法でゲルタイムおよび粘度上昇率を測定することで、硬化性および貯蔵安定性を評価した。結果を下記第１表に示す。 <Evaluation>
About each prepared epoxy resin composition, sclerosis | hardenability and storage stability were evaluated by measuring a gel time and a viscosity increase rate with the following method, respectively. The results are shown in Table 1 below.
（ゲルタイム）
　調製した各エポキシ樹脂組成物について、安田式ゲルタイムテスター（安田精機製作所社製、Ｎｏ．１５３ゲルタイムテスター）を用いて１５０℃でのゲルタイム（単位：秒）を測定した。
　なお、安田式ゲルタイムテスターは、オイルバス中、試料を入れた試験管の中でローターを回転させ、ゲル化が進み一定のトルクが掛かると磁気カップリング機構によりローターが落ちタイマーが止まる装置である。 (Geltime)
About each prepared epoxy resin composition, the gel time (unit: second) in 150 degreeC was measured using the Yasuda-type gel time tester (The Yasuda Seiki Seisakusho make, No.153 gel time tester).
The Yasuda-type gel time tester is a device that rotates the rotor in a test tube containing a sample in an oil bath, and when the gelation proceeds and a certain torque is applied, the rotor is dropped by the magnetic coupling mechanism and the timer is stopped. .
（粘度上昇率）
　調製した各エポキシ樹脂組成物を４０℃のオーブンに入れて、初期および２時間経過後の粘度をそれぞれ測定し、その増加率を粘度上昇率とした。Ｅ型粘度計 VISCONIC EHD型（東機産業社製）を用いて初期粘度を測定した。次いで、得られた初期粘度および２時間後の粘度の値を下記式に当てはめて、粘度上昇率を算出した。
　（粘度上昇率）＝（２時間後の粘度）／（初期粘度） (Viscosity increase rate)
Each prepared epoxy resin composition was put in an oven at 40 ° C., and the viscosity at the initial stage and after the lapse of 2 hours was measured. The initial viscosity was measured using an E-type viscometer VISCONIC EHD type (manufactured by Toki Sangyo Co., Ltd.). Subsequently, the viscosity increase rate was calculated by applying the obtained initial viscosity and the value of the viscosity after 2 hours to the following formula.
(Viscosity increase rate) = (Viscosity after 2 hours) / (Initial viscosity)
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
　上記第１表に示す各成分の詳細は、以下のとおりである。
　・エポキシ樹脂１：ビスフェノールＡ型エポキシ樹脂（ＥＰ４１００Ｅ、ＡＤＥＫＡ社製）
　・カチオン重合開始剤１：以下のようにして調製した、式（３Ａ）で表されるスルホニウム塩化合物
　まず、４－メチルチオフェノール４．５９ｇとシンナミルクロリド５ｇとをメタノールとメチルシクロヘキサンとの１：１混合溶媒中で室温で２４時間反応させ、クロライド中間体を得た。次に、得られた中間体９ｇとテトラキス（ペンタフルオロフェニル）ボレートのナトリウム塩水溶液（固形分１０％）２１５．８ｇとを混合し、室温で２４時間反応させることで化合物を得た。1Ｈ－ＮＭＲ分析の結果、この化合物は式（３Ａ）で表されるスルホニウム塩化合物であることが確認された。 The details of each component shown in Table 1 are as follows.
Epoxy resin 1: bisphenol A type epoxy resin (EP4100E, manufactured by ADEKA)
Cationic polymerization initiator 1: sulfonium salt compound represented by the formula (3A) prepared as follows First, 4.59 g of 4-methylthiophenol and 5 g of cinnamilk chloride were mixed with 1: 1 of methanol and methylcyclohexane. The reaction was carried out in a mixed solvent at room temperature for 24 hours to obtain a chloride intermediate. Next, 9 g of the obtained intermediate and 215.8 g of an aqueous sodium salt solution of tetrakis (pentafluorophenyl) borate (solid content 10%) were mixed and reacted at room temperature for 24 hours to obtain a compound. As a result of 1 H-NMR analysis, it was confirmed that this compound was a sulfonium salt compound represented by the formula (3A).
　・カチオン重合開始剤２：以下のようにして調製した、式（３Ｂ）で表されるスルホニウム塩化合物
　まず、１－（クロロメチル）ナフタレン１０ｇと４－メチルチオフェノール７．９ｇとをメタノール中で室温２４時間反応させ、クロライド中間体を得た。次に、得られたクロライド中間体１０ｇとテトラキス（ペンタフルオロフェニル）ボレートのナトリウム塩水溶液（固形分１０％）２２０．１６ｇとを混合し、中間体を得た。さらに、得られた中間体２ｇを乾燥したγ－ブチロラクトン２．４ｇに溶解させ、得られた溶液中に、ｐ－トルエンスルホニルイソシアネート０．４ｇを添加し、式（３Ｂ）で表されるスルホニウム塩化合物を得た。 Cationic polymerization initiator 2: sulfonium salt compound represented by the formula (3B) prepared as follows First, 10 g of 1- (chloromethyl) naphthalene and 7.9 g of 4-methylthiophenol were mixed in methanol at room temperature. Reaction was performed for 24 hours to obtain a chloride intermediate. Next, 10 g of the obtained chloride intermediate was mixed with 220.16 g of an aqueous sodium salt solution of tetrakis (pentafluorophenyl) borate (solid content 10%) to obtain an intermediate. Further, 2 g of the obtained intermediate was dissolved in 2.4 g of dried γ-butyrolactone, 0.4 g of p-toluenesulfonyl isocyanate was added to the obtained solution, and the sulfonium salt represented by the formula (3B) was added. A compound was obtained.
　・カチオン重合開始剤３：以下のようにして調製した、式（３Ｃ）で表されるスルホニウム塩化合物
　まず、１－（クロロメチル）ナフタレン１０ｇと４－メチルチオフェノール７．９ｇとをメタノール中で室温２４時間反応させ、クロライド中間体を得た。次に、得られたクロライド中間体１０ｇとテトラキス（ペンタフルオロフェニル）ボレートのナトリウム塩水溶液（固形分１０％）２２０．１６ｇとを混合し、式（３Ｃ）で表されるスルホニウム塩化合物を得た。
　・カチオン重合開始剤４：式（３Ｄ）で表されるスルホニウム塩化合物（ＳＩ６０Ｌ、三新化学社製） Cationic polymerization initiator 3: Sulphonium salt compound represented by the formula (3C) prepared as follows First, 10 g of 1- (chloromethyl) naphthalene and 7.9 g of 4-methylthiophenol were mixed in methanol at room temperature. Reaction was performed for 24 hours to obtain a chloride intermediate. Next, 10 g of the obtained chloride intermediate was mixed with 220.16 g of an aqueous sodium salt solution (solid content: 10%) of tetrakis (pentafluorophenyl) borate to obtain a sulfonium salt compound represented by the formula (3C). .
Cationic polymerization initiator 4: sulfonium salt compound represented by the formula (3D) (SI60L, manufactured by Sanshin Chemical Co., Ltd.)
　・安定剤１：式（１Ａ）で表される化合物（東京化成工業社製）
　・安定剤２：式（１Ｂ）で表される化合物（東京化成工業社製）
　・安定剤３：下記式（Ｚ）で表される化合物（東京化成工業社製） Stabilizer 1: Compound represented by formula (1A) (manufactured by Tokyo Chemical Industry Co., Ltd.)
Stabilizer 2: Compound represented by formula (1B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
-Stabilizer 3: Compound represented by the following formula (Z) (manufactured by Tokyo Chemical Industry Co., Ltd.)
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　上記第１表に示す結果から明らかなように、安定剤１または安定剤２を使用した実施例１～８は、これらを使用しない比較例１～３と比較して粘度上昇率が低く、貯蔵安定性に優れることが分かった。しかも、実施例１～８は、比較例１～３と比較して、ゲルタイムが同等であり、硬化性は損なわれなかった。
　また、安定剤３は、特許文献２に開示された安定剤であるが、この安定剤３を用いた比較例４は、例えば、安定剤を含まない比較例１と比べれば粘度上昇率の低下は見られたものの、他の実施例と比較して粘度上昇率が高く、貯蔵安定性が不十分であることが分かった。この理由として、式（１Ａ）で表される化合物である安定剤１は、オルト位に電子共与性基であるメチル基が導入されていることにより、スルフィドの求核性が高まり、貯蔵安定性が向上したものと考えられる。また、例えば、式（１Ｂ）で表される化合物である安定剤２は、スルフィドの求核性の他に、カルボキシ基のカルボニル酸素がスルホニウム塩に配位する構造をとることができるため、これらの効果により貯蔵安定性が向上したものと考えられる。 As is apparent from the results shown in Table 1 above, Examples 1 to 8 using Stabilizer 1 or Stabilizer 2 have a lower rate of increase in viscosity than Comparative Examples 1 to 3 which do not use them, and storage. It was found to be excellent in stability. In addition, Examples 1 to 8 had the same gel time as Comparative Examples 1 to 3, and the curability was not impaired.
Moreover, although the stabilizer 3 is a stabilizer disclosed in Patent Document 2, the comparative example 4 using the stabilizer 3 has, for example, a lower viscosity increase rate than the comparative example 1 that does not include the stabilizer. However, it was found that the rate of increase in viscosity was high compared to other examples, and the storage stability was insufficient. This is because the stabilizer 1 which is a compound represented by the formula (1A) has a sulfide nucleophilicity increased due to the introduction of a methyl group which is an electron-donating group at the ortho position, and storage stability. It is thought that the property improved. Further, for example, the stabilizer 2 which is a compound represented by the formula (1B) can take a structure in which the carbonyl oxygen of the carboxy group is coordinated to the sulfonium salt in addition to the nucleophilicity of the sulfide. It is considered that the storage stability was improved by the effect of.

Claims (5)

  1. 　スルホニウム塩化合物であるカチオン重合開始剤と、
    　下記式（１）で表される化合物である安定剤と、を含有する硬化剤組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式（１）中、Ｒ1は、ヒドロキシ基、カルボキシ基、または、下記式（２）で表される基を示し、Ｒ2は、炭素数１～６のアルキル基を示し、Ｒ3は、水素原子または炭素数１～６のアルキル基を示す。ただし、Ｒ3が水素原子を示すときは、Ｒ1はカルボキシ基を示す。）
    Figure JPOXMLDOC01-appb-C000002
     （式（２）中、Ｒ4は、炭素数１～６のアルキル基、または、置換基を有していてもよい芳香族炭化水素基を示す。）     A cationic polymerization initiator which is a sulfonium salt compound;
    The hardening | curing agent composition containing the stabilizer which is a compound represented by following formula (1).
    Figure JPOXMLDOC01-appb-C000001
     (In the formula (1), R 1 represents a hydroxy group, a carboxy group, or a group represented by the following formula (2), R 2 represents an alkyl group having 1 to 6 carbon atoms, and R 3 represents Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, provided that when R 3 represents a hydrogen atom, R 1 represents a carboxy group.)
    Figure JPOXMLDOC01-appb-C000002
     (In the formula (2), R 4 represents an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group which may have a substituent.)
  2. 　前記安定剤の含有量が、前記カチオン重合開始剤に対して、０．００１～２０質量％である、請求項１に記載の硬化剤組成物。 The curing agent composition according to claim 1, wherein a content of the stabilizer is 0.001 to 20% by mass with respect to the cationic polymerization initiator.
  3. 　前記カチオン重合開始剤が、下記式（３）で表されるスルホニウム塩化合物である、請求項１または２に記載の硬化剤組成物。
    Figure JPOXMLDOC01-appb-C000003
     （式（３）中、Ｒ5は、ヒドロキシ基または下記式（４）～（７）のいずれかで表される基を示し、Ｒ6は、炭素数１～６のアルキル基を示し、Ｒ7は、置換基を有していてもよい不飽和炭化水素基を示し、Ｘは、非求核性アニオン性基を示す。）
    Figure JPOXMLDOC01-appb-C000004
     （式（４）～（７）中、Ｒ8は、それぞれ独立に、ヘテロ原子を含んでいてもよい置換基を有していてもよい芳香族または脂肪族炭化水素基を示す。）     The hardening | curing agent composition of Claim 1 or 2 whose said cationic polymerization initiator is a sulfonium salt compound represented by following formula (3).
    Figure JPOXMLDOC01-appb-C000003
     (In the formula (3), R 5 represents a hydroxy group or a group represented by any of the following formulas (4) to (7), R 6 represents an alkyl group having 1 to 6 carbon atoms, 7 represents an unsaturated hydrocarbon group which may have a substituent, and X represents a non-nucleophilic anionic group.
    Figure JPOXMLDOC01-appb-C000004
     (In formulas (4) to (7), each R 8 independently represents an aromatic or aliphatic hydrocarbon group which may have a substituent which may contain a hetero atom.)
  4. 　エポキシ樹脂と、請求項１～３のいずれかに記載の硬化剤組成物とを含有する、エポキシ樹脂組成物。 An epoxy resin composition comprising an epoxy resin and the curing agent composition according to any one of claims 1 to 3.
  5. 　前記硬化剤組成物の含有量が、前記エポキシ樹脂１００質量部に対して、０．１～２０質量部である、請求項４に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 4, wherein the content of the curing agent composition is 0.1 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin.
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WO2015012467A1 (en) * 2013-07-23 2015-01-29 제일모직 주식회사 Compound containing phosphonium ion, epoxy resin composition containing same, and device manufactured by using same
KR20150011747A (en) * 2013-07-23 2015-02-02 제일모직주식회사 Compound comprising phosphonium ion, epoxy resin composition comprising the same and apparatus prepared from using the same
JP2019189698A (en) * 2018-04-20 2019-10-31 三新化学工業株式会社 Method of stabilizing epoxy resin

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KR20150011747A (en) * 2013-07-23 2015-02-02 제일모직주식회사 Compound comprising phosphonium ion, epoxy resin composition comprising the same and apparatus prepared from using the same
KR101702704B1 (en) 2013-07-23 2017-02-03 제일모직주식회사 Compound comprising phosphonium ion, epoxy resin composition comprising the same and apparatus prepared from using the same
US10047191B2 (en) 2013-07-23 2018-08-14 Samsung Sdi Co., Ltd. Compound containing phosphonium ion, epoxy resin composition containing same, and device manufactured by using same
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