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WO2010026777A1 - Composition de résine époxy durcie par la chaleur - Google Patents

Composition de résine époxy durcie par la chaleur Download PDF

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Publication number
WO2010026777A1
WO2010026777A1 PCT/JP2009/004417 JP2009004417W WO2010026777A1 WO 2010026777 A1 WO2010026777 A1 WO 2010026777A1 JP 2009004417 W JP2009004417 W JP 2009004417W WO 2010026777 A1 WO2010026777 A1 WO 2010026777A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
epoxy resin
formula
compound represented
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2009/004417
Other languages
English (en)
Japanese (ja)
Inventor
奥野つばさ
佐藤奈央
石川和憲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yokohama Rubber Co Ltd
Original Assignee
Yokohama Rubber Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yokohama Rubber Co Ltd filed Critical Yokohama Rubber Co Ltd
Priority to JP2010516707A priority Critical patent/JP4737345B2/ja
Priority to KR1020117006091A priority patent/KR101245132B1/ko
Priority to CN2009801344808A priority patent/CN102143987B/zh
Publication of WO2010026777A1 publication Critical patent/WO2010026777A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • 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
    • C08G59/50—Amines
    • 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
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • 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 thermosetting epoxy resin composition.
  • a composition using an aromatic diamine compound as a curing agent for an epoxy resin provides a cured product having a high glass transition temperature.
  • Patent Document 1 has previously proposed Patent Document 1 as a two-component curable resin composition that is excellent in storage stability of the first liquid containing an epoxy resin and has a high curing rate at room temperature or lower.
  • an epoxy resin composition containing a curable epoxy resin, a curing agent for epoxy resin, and tris (4-methylphenyl) phosphine triphenylborane has been proposed (see Patent Document 2).
  • curing agent of an epoxy resin it is known that the hardening time of a composition will become short.
  • an object of this invention is to provide the epoxy resin composition excellent in sclerosis
  • the present inventor uses a compound represented by the following formula (I) as a curing accelerator for an aromatic diamine compound as a curing agent for an epoxy resin.
  • a composition having a short curing time and excellent curability can be obtained, and the present invention has been completed.
  • R 1 and R 2 each represent a hydrogen atom and an alkyl group.
  • thermosetting epoxy resin composition containing an epoxy resin (A), an aromatic polyamine compound (B), and a compound represented by the following formula (I).
  • the thermosetting epoxy resin composition is provided within 3 minutes.
  • R 1 and R 2 each represent a hydrogen atom and an alkyl group.
  • thermosetting epoxy resin composition of the present invention is excellent in curability.
  • thermosetting epoxy resin composition containing the epoxy resin (A), the aromatic polyamine compound (B), and the compound represented by the following formula (I)
  • the gelation time is 150 ° C. or less within 3 minutes.
  • thermosetting epoxy resin composition In the formula, R 1 and R 2 each represent a hydrogen atom and an alkyl group.
  • the thermosetting epoxy resin composition of the present invention may be referred to as “the composition of the present invention”.
  • the epoxy resin (A) contained in the composition of the present invention is not particularly limited as long as it is a compound having two or more epoxy groups.
  • a conventionally well-known thing is mentioned. Specifically, for example, bisphenol A 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 A biphenol type epoxy resin is mentioned.
  • An epoxy resin (A) can be used individually or in combination of 2 types or more, respectively.
  • the aromatic polyamine compound (B) will be described below.
  • the aromatic polyamine compound (B) contained in the composition of the present invention is a compound in which two or more amino groups are bonded to an aromatic hydrocarbon group.
  • the aromatic polyamine compound (B) is used as a curing agent.
  • the aromatic polyamine compound (B) can react with the epoxy resin (A).
  • the composition of the present invention contains an aromatic thiirane compound (C)
  • the aromatic polyamine compound (B) can react with the epoxy resin (A) and the aromatic thiirane compound (C).
  • the aromatic polyamine compound (B) reacts preferentially with the aromatic thiirane compound (C) in the composition of the present invention, and the NH group is removed. Generate.
  • the produced NH group can react with the epoxy resin (A).
  • the amino group which an aromatic polyamine compound (B) has may react with an epoxy resin (A) directly.
  • the aromatic hydrocarbon group is not particularly limited.
  • the aromatic hydrocarbon group can have a substituent.
  • the substituent include an alkyl group and an alkoxy group.
  • the aromatic hydrocarbon group can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • R 2 is at least one selected from the group consisting of an alkylene group, an aromatic hydrocarbon group, a carbonyl group, a fluorene group, a sulfonyl group, an ether group, and a sulfide group.
  • the alkylene group include a methylene group and an ethylene group.
  • R 2 can be at least two selected from the group consisting of an alkylene group, an aromatic hydrocarbon group, a carbonyl group, a fluorene group, a sulfonyl group, an ether group and a sulfide group.
  • the aromatic polyamine compound (B) is preferably an aromatic diamine compound from the viewpoint of superior curability.
  • An aromatic diamine compound is a compound in which two amino groups are bonded to an aromatic hydrocarbon group.
  • Examples of the aromatic polyamine compound (B) include those represented by the formula (II).
  • the formula (II) two amino groups are bonded to the benzene ring.
  • R 3 and R 4 are each an alkyl group
  • R 5 is selected from the group consisting of an alkylene group, an aromatic hydrocarbon group, a carbonyl group, a fluorene group, a sulfonyl group, an ether group and a sulfide group. At least one selected, and m and n are each an integer of 0 to 4.
  • the aromatic polyamine compound represented by the formula (II) can have R 3 and R 4 as substituents.
  • the alkyl group include those having 1 to 6 carbon atoms. For example, a methyl group, an ethyl group, and a propyl group are mentioned.
  • the alkyl group is preferably a methyl group or an ethyl group from the viewpoint of excellent storage stability and fast curability.
  • the alkylene group include those having 1 to 6 carbon atoms. Examples include a methylene group and an ethylene group.
  • the alkylene group is preferably a methylene group from the viewpoint of excellent storage stability and fast curability.
  • m and n are each preferably an integer of 0 to 2 from the viewpoint of excellent storage stability and fast curability.
  • the amino group is preferably para-positioned to R 5 from the viewpoint of excellent storage stability and fast curability.
  • the aromatic hydrocarbon group is not particularly limited as long as it is divalent.
  • the aromatic hydrocarbon group can have a substituent such as a methyl group.
  • the combination of the aromatic hydrocarbon and the alkylene group is not particularly limited.
  • the alkylene group which has an aromatic hydrocarbon group is mentioned. Specifically, for example, when two alkylene groups are bonded via an aromatic hydrocarbon, when an aromatic hydrocarbon is bonded as a side chain of the alkylene group, the aromatic hydrocarbon group and the alkylene group are bonded.
  • aromatic hydrocarbon group and an alkylene group are respectively bonded to two benzene rings represented by the formula (II).
  • the aromatic hydrocarbon include a benzene ring and naphthalene.
  • the aromatic hydrocarbon can have a substituent such as a methyl group.
  • Examples of the aromatic polyamine compound (B) include a compound represented by the following formula (4) and methylene bis (2-ethyl 6-methylaniline).
  • R 2 is at least one selected from the group consisting of an alkylene group, an aromatic hydrocarbon group, a carbonyl group, a fluorene group, a sulfonyl group, an ether group, and a sulfide group.
  • the aromatic polyamine compound (B) is preferably a compound represented by the formula (4), methylene bis (2-ethyl 6-methylaniline), from the viewpoint of excellent curability and excellent storage stability.
  • R 2 is preferably an alkylene group, a carbonyl group, or a fluorene group, and more preferably a methylene group, a carbonyl group, or a fluorene group, from the viewpoint of superior curability.
  • R 2 is preferably an alkylene group, a carbonyl group, or a fluorene group from the viewpoint of better curability when the composition of the present invention contains an aromatic thiirane compound (C). More preferably, it is a group.
  • An aromatic polyamine compound (B) can be used individually or in combination of 2 types or more, respectively.
  • the aromatic polyamine compound (B) is not particularly limited for its production. A commercial item can be used as an aromatic polyamine compound (B).
  • the amount of the aromatic polyamine compound (B) is excellent in curability, and from the viewpoint that the glass transition temperature (glass transition point) of the cured product is high, the equivalent number of active hydrogens that the aromatic polyamine compound (B) has is epoxy.
  • the amount of the epoxy group contained in the resin (A) is preferably 0.5 to 2.5 equivalents, more preferably 0.7 to 2.0 equivalents.
  • the aromatic polyamine compound (B) has an amino group as a group containing active hydrogen. The amino group has two active hydrogens per nitrogen atom.
  • the compound represented by formula (I) is a curing accelerator or a curing accelerator (if the composition of the present invention further contains an aromatic thiirane compound (C), ) Is used.
  • the compound represented by the formula (I) contained in the composition of the present invention has the following structure.
  • R 1 and R 2 represent a hydrogen atom and an alkyl group, respectively.
  • R 1 represents a hydrogen atom or an alkyl group.
  • R 2 represents a hydrogen atom or an alkyl group.
  • R 1 and R 2 may be the same or different.
  • a plurality of R 1 may be the same or different.
  • a plurality of R 2 may be the same or different.
  • the alkyl group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms from the viewpoint of excellent curability and a high glass transition temperature.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.
  • Examples of the compound represented by the formula (I) include a compound represented by the formula (1) and a compound represented by the formula (2).
  • Ph represents a phenyl group or a phenylene group.
  • Ph in Me—Ph— is a phenylene group.
  • the composition of the present invention is superior in curability and has a high glass transition temperature. From the viewpoint of increasing the glass transition temperature, the compound represented by the formula (I) and / or the formula (2) is used. It is preferable to contain the compound.
  • the compound represented by the formula (1) and the compound represented by the formula (2) will be described below.
  • the compound represented by the formula (1) or the compound represented by the formula (2) is a curing accelerator or a curing acceleration assistant (the composition of the present invention further comprises an aromatic thiirane compound (C ) Is used as a curing acceleration aid).
  • the compound name of the compound represented by the formula (1) is triphenylphosphine triphenylborate, which is sometimes referred to as “TPP-S” in the present specification.
  • the compound name of the compound represented by the formula (2) is trisparamethylphenylphosphine triphenylborate, which is sometimes referred to as “TPTP-S” in the present specification.
  • the methyl group can be bonded to any of the ortho, meta and para positions.
  • the compound represented by the formula (I) is not particularly limited for its production.
  • the compound represented by the formula (1) is not particularly limited for its production.
  • a commercial item can be used as a compound represented by Formula (1). The same applies to the compound represented by the formula (2).
  • the compounds represented by formula (I) can be used alone or in combination of two or more.
  • the amount of the compound represented by the formula (I) is 1 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin (A) from the viewpoint of excellent curability and high glass transition temperature of the cured product. It is preferably 3 to 10 parts by mass.
  • the number of active hydrogen equivalents of the aromatic polyamine compound (B) is based on the epoxy group of the epoxy resin (A).
  • the amount of the compound represented by the formula (I) is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin (A).
  • the microcapsule will be described below.
  • either or both of the compound represented by the formula (I) and the aromatic polyamine compound are contained as microcapsules encapsulated by a thermoplastic resin.
  • a one-component composition that is superior in storage stability while maintaining rapid curability can be obtained.
  • the microcapsule has one or both of the compound represented by the formula (I) and the aromatic polyamine compound as a core, and has a thermoplastic resin as a shell.
  • the compound represented by the formula (I) or the aromatic polyamine compound is a solid (or a melting point exceeding 70 ° C.) at 25 to 70 ° C. from the viewpoint of easy microencapsulation when producing microcapsules. preferable.
  • the core of the microcapsule is preferably a compound represented by the formula (I) or an aromatic diamine from the viewpoint of easy microencapsulation.
  • the composition of the present invention contains the compound represented by the formula (I)
  • a microcapsule encapsulated with a thermoplastic resin and a microcapsule encapsulated with a thermoplastic resin of an aromatic polyamine compound can be contained.
  • the compound represented by the formula (I) and the aromatic polyamine compound may be encapsulated in one microcapsule.
  • thermoplastic resin used as the shell is not particularly limited.
  • urethane resin styrene butadiene elastomer
  • polyvinyl acetal resin phenoxy resin
  • polymethyl methacrylate resin polyvinyl alcohol
  • acrylic monomers such as acrylic acid ester, itaconic acid ester, crotonic acid ester, etc.
  • Monofunctional compounds such as 1 to 8 alkyl ethers and those in which part or all of the hydrogen atoms of the alkyl group of this alkyl ester are substituted with allyl groups, styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, etc.
  • thermoplastic resins can be used alone or in combination of two or more.
  • urethane resins styrene butadiene elastomers
  • polyvinyls are preferred from the viewpoints of excellent storage stability and fast curability, excellent film-forming properties and mechanical strength, and the ability to maintain the glass transition temperature of the obtained cured product. It is preferably at least one selected from the group consisting of an acetal resin, polyvinyl alcohol and phenoxy resin.
  • the urethane resin is not particularly limited as long as it is a compound having a urethane bond.
  • those obtained by reaction of polyisocyanates and polyamines those obtained by reaction of polyisocyanates and water, those obtained by reaction of polyisocyanates and polyhydric alcohols, Examples thereof include those obtained by reaction of isocyanates, polyvalent amines and polyhydric alcohols.
  • the polyvalent isocyanate used in producing the urethane resin may be a compound having two or more isocyanate groups in the molecule. Specifically, for example, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4′-diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate
  • Aromatic polyisocyanates such as xylylene-1,4-diisocyanate and polyisocyanates having an isocyanate group bonded to an alkylene group having
  • aromatic poly- ylene such as tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, and the like.
  • Isocyanates are preferred.
  • Polyvalent isocyanates can be used alone or in combination of two or more.
  • the polyvalent amine used when producing the urethane resin may be a compound having two or more amino groups in the molecule.
  • aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,12-dodecamethylenediamine; o-phenylene Aromatic polyamines such as diamine, m-phenylenediamine, and p-phenylenediamine; amino groups on alkylene groups having an aromatic hydrocarbon group such as o-xylylenediamine, m-xylylenediamine, and p-xylylenediamine
  • alicyclic polyamines such as menthanediamine, bis (4-amino-3-methylcyclohexyl) methane, isophoronediamine and 1,3-diaminocyclohexane; spiroacetal diamines.
  • the polyhydric alcohol used when using the urethane resin may be aliphatic, aromatic or alicyclic.
  • catechol resorcinol, 1,2-dihydroxy-4-methylbenzene, 1,3-dihydroxy-5-methylbenzene, 3,4-dihydroxy-1-methylbenzene, 3,5-dihydroxy-1-methylbenzene, 2,4-dihydroxyethylbenzene, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,7-naphthalenediol, 2,3-naphthalenediol, o, o'-biphenol, p, p'-biphenol, bisphenol A, bis- (2-hydroxyphenyl) methane, xylylenediol, ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7 -Heptanediol
  • the styrene butadiene elastomer is not particularly limited. For example, a conventionally well-known thing is mentioned.
  • the weight average molecular weight of the styrene butadiene elastomer is preferably 12,000 to 50,000 from the viewpoint of excellent storage stability and fast curability.
  • the weight average molecular weight is a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
  • the polyvinyl acetal resin is not particularly limited. Examples thereof include polyvinyl formal resin and polyvinyl butyral resin.
  • the weight average molecular weight of the polyvinyl acetal resin is preferably 10,000 to 60,000 from the viewpoint of excellent storage stability and fast curability.
  • Polyvinyl alcohol is not particularly limited. For example, a conventionally well-known thing is mentioned.
  • the weight average molecular weight of polyvinyl alcohol is preferably 10,000 to 150,000 from the viewpoint of excellent storage stability and fast curability.
  • Phenoxy resin is not particularly limited.
  • it is a high molecular weight epoxy resin having a molecular weight of 10,000 or more selected from bisphenol A and / or bisphenol F.
  • the microcapsule is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.
  • Each of the microcapsules can be used alone or in combination of two or more.
  • a microcapsule that encapsulates the compound represented by the formula (I) is preferable from the viewpoint of excellent storage stability and fast curability.
  • the shell material is selected from the group consisting of urethane resin, styrene butadiene elastomer, polyvinyl acetal resin, polyvinyl alcohol and phenoxy resin.
  • the aromatic polyamine compound when the microcapsule having the compound represented by the formula (I) is contained as a core, the aromatic polyamine compound may be microencapsulated or may not be microencapsulated. Moreover, when the microcapsule which has an aromatic polyamine compound as a core is contained, the compound represented by Formula (I) may be microencapsulated or may not be microencapsulated.
  • the thermoplastic resin in the microcapsule is an epoxy resin, which can maintain the glass transition temperature of the resulting cured product, is superior in storage stability and fast curability, and is excellent in film forming properties and mechanical strength.
  • the total content is preferably 1 to 20% by mass.
  • the average particle diameter (diameter) of the microcapsules is preferably 0.1 to 50 (unit: micron) from the viewpoint of excellent storage stability and fast curability.
  • the average particle size is measured using a particle size distribution analyzer SALD-7100 (manufactured by Shimadzu Corporation).
  • the thickness of the shell in the microcapsule is preferably 0.01 to 10 (unit: micron) from the viewpoints of excellent storage stability and fast curability, and excellent film forming properties and mechanical strength.
  • the thickness of the shell is measured using a particle size distribution analyzer SALD-7100 (manufactured by Shimadzu Corporation).
  • the composition of the present invention can further contain an aromatic thiirane compound (C).
  • the aromatic thiirane compound (C) that can be contained in the composition of the present invention is an aromatic hydrocarbon compound having a thiirane group and an aromatic hydrocarbon group.
  • the aromatic thiirane compound (C) is used as a curing accelerator.
  • the aromatic thiirane compound (C) can be used in place of a part of the aromatic polyamine compound (B).
  • the aromatic thiirane compound (C) reacts with the aromatic polyamine compound (B) to generate an SH group.
  • the generated SH group can react with the epoxy resin (A).
  • the aromatic hydrocarbon group that the aromatic thiirane compound (C) has is not particularly limited. For example, a phenyl group and a naphthyl group are mentioned.
  • the aromatic hydrocarbon group can have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a cycloalkyl group, and an aryl group.
  • the aromatic hydrocarbon group can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • the thiirane group and the aromatic hydrocarbon group can be bonded via an organic group.
  • the organic group is a hydrocarbon group that can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • the hydrocarbon group is not particularly limited. Examples of the organic group include —O—CH 2 —, —O—CH 2 —CH ⁇ CH—, and —O—CO—CH 2 —.
  • the equivalent number of SH groups generated from the aromatic thiirane compound (C) is based on the epoxy group of the epoxy resin (A). It is preferably 0.3 to 1.0, and more preferably 0.4 to 0.7.
  • the composition of the present invention includes an epoxy resin (A), an aromatic polyamine compound (B), a compound represented by the formula (I), and an aromatic thiirane compound (C) that can be used as necessary. If necessary, an additive can be further contained.
  • the composition of the present invention is represented by the epoxy resin (A), the aromatic polyamine compound (B), the aromatic thiirane compound (C), and the compound represented by the formula (1) and / or the formula (2). In addition to the compound, an additive can be further contained as necessary.
  • the additive examples include a curing agent other than the aromatic polyamine compound (B), a filler (filler), a reactive diluent, a plasticizer, a thixotropic agent, a pigment, a dye, an anti-aging agent, an antioxidant, Examples thereof include an antistatic agent, a flame retardant, an adhesiveness imparting agent, a dispersant, and a solvent.
  • thermosetting epoxy resin composition of the present invention examples include a one-component thermosetting epoxy resin composition and a two-component thermosetting epoxy resin composition.
  • “one-component thermosetting epoxy resin composition” may be described as “one-component type”
  • “two-component thermosetting epoxy resin composition” may be described as “two-component type”.
  • the composition of the present invention is not particularly limited for its production.
  • the epoxy resin (A), the aromatic polyamine compound (B), the compound represented by the formula (I), and the additive are sufficiently kneaded using a stirring device such as a mixing mixer under reduced pressure or in a nitrogen atmosphere. By uniformly dispersing, the composition of the present invention can be produced as a one-component composition.
  • the epoxy resin (A), the aromatic polyamine compound (B), the compound represented by the formula (1) and / or the compound represented by the formula (2) can be used as necessary.
  • the composition of the present invention can be produced as a one-component composition by sufficiently kneading and uniformly dispersing the additive under a reduced pressure or in a nitrogen atmosphere using a stirring device such as a mixing mixer.
  • the composition of the present invention is not particularly limited in its production even when the compound represented by formula (I) and / or the curing agent is encapsulated by microcapsules.
  • the microcapsule encapsulates the compound represented by the formula (I), for example, an epoxy resin, a microcapsule encapsulating the compound represented by the formula (I), a curing agent, and an addition that can be used as necessary
  • the composition of the present invention can be produced as a one-component composition by sufficiently mixing the agent under a reduced pressure or under a nitrogen atmosphere using a stirring device such as a mixing mixer.
  • the composition of the present invention can be produced as a one-component composition by sufficiently mixing using a stirring device such as a mixing mixer.
  • the condition is at 25 ° C. with respect to the initial viscosity.
  • the increase rate of the viscosity after leaving for 24 hours can be 10% or less, and is more preferable.
  • the viscosity was measured at 25 ° C. using an E-type viscometer VISCONIC EHD type (manufactured by Toki Sangyo Co., Ltd.).
  • the compound represented by formula (I) and / or the curing agent of the composition of the present invention When the compound represented by formula (I) and / or the curing agent of the composition of the present invention is encapsulated by microcapsules, it has excellent storage stability and can be stored for a long time at room temperature (20 to 30 ° C.). it can. When the composition of the present invention is a one-pack type, the workability on site is excellent.
  • the production thereof is not particularly limited.
  • a two-part type having a first liquid (main agent) containing an epoxy resin (A) and a second liquid (curing agent) containing an aromatic polyamine compound (B) and a compound represented by formula (I) It can be manufactured as a composition.
  • the additive can be added to the first liquid and / or the second liquid.
  • the first liquid and the second liquid can be produced by sufficiently kneading and uniformly dispersing using a stirring device such as a mixing mixer under reduced pressure or nitrogen atmosphere.
  • the composition of the present invention can be produced as a two-component composition having a second liquid (curing agent) to be contained.
  • the additive can be added to the first liquid and / or the second liquid.
  • the first liquid and the second liquid can be produced by sufficiently kneading and uniformly dispersing using a stirring device such as a mixing mixer under reduced pressure or nitrogen atmosphere.
  • a stirring device such as a mixing mixer under reduced pressure or nitrogen atmosphere.
  • the gelation time (gel time) of the thermosetting epoxy resin composition is 3 minutes (180 seconds) at 150 ° C.
  • the gel time is preferably within 60 seconds at 150 ° C., more preferably within 50 seconds.
  • the gel time (gel time) was measured by a method according to JIS C2161: 1997 or a method using a Yasuda gel time tester.
  • the composition of the present invention can be used, for example, for adhesives, paints, civil engineering and construction, electricity, transportation equipment, medical use, packaging use, textile use, and sports / leisure use.
  • adherend to which the composition of the present invention can be applied include metal, glass, plastic, mortar, concrete, rubber, wood, leather, cloth, and paper.
  • the method for applying the composition of the present invention to the adherend is not particularly limited. For example, a conventionally well-known thing is mentioned.
  • the temperature at which the composition of the present invention is cured is preferably from 100 to 250 ° C., more preferably from 120 to 200 ° C., from the viewpoints of excellent curability and high glass transition temperature of the cured product. .
  • the storage elastic modulus (G ′) was measured by performing forced elongation excitation in the temperature range from room temperature to 200 ° C. under the condition of a temperature rising rate of 5 ° C./min.
  • Aromatic polyamine compound (B) 4 Methylenebis (2-ethyl6-methylaniline) represented by the following formula (trade name: Kayahard MED, manufactured by Ihara Chemical Industry Co., Ltd.) -Compound represented by formula (I) 1: Compound represented by formula (1) below, manufactured by Hokuko Chemical Co., Ltd.
  • Compound 2 represented by formula (I) Compound represented by formula (2) below, manufactured by Hokuko Chemical Co., Ltd.
  • -TPP manufactured by Tokyo Chemical Industry Co., Ltd., used as a curing accelerator.
  • -Aliphatic amine a compound represented by the following formula, trade name: DMP-30, manufactured by Tokyo Chemical Industry Co., Ltd.
  • Comparative Example I-1 which does not contain the compound represented by formula (I), has a gel time at 150 ° C. of more than 3 minutes and poor curability, resulting in a glass transition. The temperature was low.
  • Comparative Example I-5 not containing the compound represented by the formula (I), the gel time at 150 ° C. exceeded 3 minutes and the curability was poor.
  • Comparative Examples I-2 to 4 which do not contain the compound represented by the formula (I) and contain another curing accelerator (TPP, aliphatic amine, amine-based latent curing agent) have a gel time at 150 ° C. Over 3 minutes, the curability was poor and the glass transition temperature was low.
  • TPP aliphatic amine, amine-based latent curing agent
  • Comparative Examples I-6 to 8 which do not contain the compound represented by the formula (I) and contain another curing accelerator (TPP, aliphatic amine, amine-based latent curing agent), the gel time at 150 ° C. is 3 minutes. And the curability was poor.
  • Comparative Example I-9 using triphenylphosphine with respect to the phenolic resin as a curing agent for the epoxy resin, the gel time at 150 ° C. exceeded 3 minutes and the curability was poor.
  • Comparative Example I-12 containing an acid anhydride curing agent the gel time at 150 ° C. exceeded 3 minutes as in Comparative Example I-9, and the curability was poor.
  • Examples I-1 to 13 had a gel time at 150 ° C. within 120 seconds, had excellent curability, and had a high glass transition temperature.
  • Examples I-1 to 13 can be cured under the conditions of 120 to 200 ° C. despite having an aromatic polyamine, and the curing time is short.
  • thermosetting epoxy resin composition of the present invention is excellent in low-temperature curability as compared with a conventional epoxy resin composition containing an epoxy resin and an aromatic polyamine. 3. Evaluation About the composition obtained as follows, gel time, a viscosity, and a viscosity increase rate were evaluated with the following method. The results are shown in Tables 3-7. (1) Gel time (fast curing) For evaluation of curability, gel time at 150 ° C. was measured on a hot plate in accordance with JIS C2161: 1997.
  • Viscosity The initial viscosity of the composition obtained as described below was measured under the condition of 25 ° C. using an E-type viscometer VISCONIC EHD type (manufactured by Toki Sangyo Co., Ltd.). In addition, the composition obtained as described below was stored in a thermostatic bath at 25 ° C. for 24 hours, and then the viscosity of the composition (viscosity after storage) was measured in the same manner as the initial viscosity. (3) Viscosity increase rate (storage stability) The viscosity increase rate was calculated by fitting the obtained initial viscosity and the viscosity value after storage to the following formula.
  • Viscosity increase rate (%) (viscosity after storage ⁇ initial viscosity) / initial viscosity ⁇ 100 As a criterion for evaluating the rate of increase in viscosity, when it was within 10%, it could be used as a one-component thermosetting epoxy resin composition.
  • Microencapsulation of the compound represented by the formula (I) (production of microcapsules having the compound represented by the formula (I) as a core) Microencapsulation was performed by a spray drying method using a spray dryer GS310 manufactured by Yamato Scientific Co., Ltd.
  • TPP-S 10 g, melting point 205 ° C., manufactured by Hokuko Chemical Co., Ltd., the same shall apply hereinafter
  • TPTP-S: 10 g, melting point 171 °C, made by Hokuko Chemical Co., Ltd. the same shall apply hereinafter
  • Microcapsules TPP-S (10 g) (or TPTP-S: 10 g) having a thickness corresponding to 20% by mass of the weight of the core are suspended in a solvent: ethyl acetate (40 g) 50 g and a thermoplastic resin solution (2 g of thermoplastic resin in a solvent) dissolved in a solvent: ethyl acetate (18 g) are mixed and spray-dried using the above spray-drying apparatus to obtain
  • TPP-S @ MC1 Shelling agent Microencapsulation was performed so that urethane resin Desmocol 500 (manufactured by Bayer Holding Co., Ltd., the same applies hereinafter) had a thickness of 10% by mass with respect to the core (TPP-S). The obtained microcapsule is designated as TPP-S @ MC1. The average particle size of TPP-S @ MC1 was 10 ⁇ m.
  • TPP-S @ MC2 Shell agent Microencapsulation was performed so that the urethane resin Desmocol 500 had a thickness of 20 mass% with respect to the core (TPP-S). The obtained microcapsule is designated as TPP-S @ MC2. The average particle size of TPP-S @ MC2 was 11 ⁇ m.
  • TPP-S @ MC3 Microencapsulation was performed so that the shell agent: styrene butadiene elastomer / tuffprene 912 (manufactured by Asahi Kasei Co., Ltd., block copolymer, hereinafter the same) had a thickness of 10% by mass with respect to the core (TPP-S).
  • the obtained microcapsule is designated as TPP-S @ MC3.
  • the average particle size of TPP-S @ MC3 was 10 ⁇ m.
  • TPP-S @ MC4 Shell agent Polyvinyl acetal resin KS10 (manufactured by Sekisui Chemical Co., Ltd., weight average molecular weight 56,000, hydroxy group 18 mol%, acetalization degree 80 mol%, the same applies hereinafter) is 10 with respect to the core (TPP-S). Microencapsulation was performed so as to obtain a thickness of mass%. The obtained microcapsule is designated as TPP-S @ MC4. The average particle size of TPP-S @ MC4 was 10 ⁇ m.
  • TPP-S @ MC5 Shell agent phenoxy resin YP-50 (manufactured by Tohto Kasei Co., Ltd., weight average molecular weight 60,000 to 80,000, the same shall apply hereinafter) is microscopic so that the thickness of the core (TPP-S) is 10 mass% Encapsulation was performed.
  • the obtained microcapsule is designated as TPP-S @ MC5.
  • the average particle size of TPP-S @ MC5 was 10 ⁇ m.
  • TPP-S @ MC6 Shell agent Microencapsulation was performed so that polyvinyl alcohol (trade name NH-18, manufactured by Nippon Synthetic Chemical Co., Ltd.) had a thickness of 10% by mass with respect to the core (TPP-S). The obtained microcapsule is designated as TPP-S @ MC6. The average particle size of TPP-S @ MC6 was 10 ⁇ m.
  • TPTP-S @ MC1 Shell agent: Microencapsulation was performed so that the phenoxy resin YP-50 had a thickness of 10 mass% with respect to the core (TPTP-S). The obtained microcapsule is designated as TPTP-S @ MC1. The average particle size of TPTP-S @ MC1 was 10 ⁇ m.
  • Curing agent (1) @ MC2 Shell agent Microencapsulation was performed so that the urethane resin Desmocol 500 had a thickness of 20 mass% with respect to the core [curing agent (1)]. Let the obtained microcapsule be hardening
  • Curing agent (1) @ MC3 Shell agent Microencapsulation was carried out so that the thickness of styrene butadiene elastomer / tuffprene 912 was 10% by mass with respect to the core [curing agent (1)]. Let the obtained microcapsule be hardening
  • Curing agent (1) @ MC4 Shell agent Microencapsulation was performed so that the polyvinyl acetal resin KS10 had a thickness of 10% by mass with respect to the core [curing agent (1)]. Let the obtained microcapsule be hardening
  • Curing agent (1) @ MC5 Shell agent Microencapsulation was performed so that the phenoxy resin YP-50 had a thickness of 10% by mass with respect to the core [curing agent (1)]. Let the obtained microcapsule be hardening
  • Curing agent (2) @ MC1 Shell agent: phenoxy resin YP-50 has a thickness of 10% by mass with respect to the core [curing agent (2): bis (aminophenyl, melting point: 237 ° C.) fluorene represented by the following formula, manufactured by JFE Chemical Co., Ltd.]. Microencapsulation was performed as described above. Let the obtained microcapsule be hardening
  • compositions were produced by using the components shown in Tables 3 to 7 in the amounts (parts by mass) shown in the same table and mixing them with a vacuum stirrer.
  • the numerical value having “eq” as a unit with respect to the amount of the curing agent is the number of equivalents of active hydrogen of the curing agent to the epoxy group (active hydrogen / epoxy group).
  • the microcapsules encapsulating the compound represented by formula (I) indicate the amount (parts by mass) as microcapsules.
  • Table 5 about the microcapsule which encloses a hardening
  • -Epoxy resin as in Table 1-Curing agent (1): similar to the aromatic polyamine compound (B) 1 in Table 1-Curing agent (2): with the aromatic polyamine compound (B) 3 in Table 1 Similarly ⁇ Curing agent (3): TMTG represented by the following formula: Trimethylolpropane tristhioglycolate, manufactured by Sakai Chemical Co., Ltd. Curing agent (4): Mercaptosilane condensate represented by the following formula (Z6362H, manufactured by Toray Dow) In the formula, n is 6 to 8.
  • Curing agent (5) Trade name PN, phenol novolak (manufactured by Nippon Kayaku Co., Ltd.)
  • Curing agent (6) trade name XYLOK-4L, xylylene glycol / phenol condensate (Mitsui Chemicals)
  • Curing agent (7) Methylenebis (2-ethyl6-methylaniline) represented by the following formula (trade name: Kayahard MED, manufactured by Ihara Chemical Industry Co., Ltd.)
  • TPTP-S @ MC1 Microcapsules containing the compound represented by the formula (I) produced as described above Curing agent (1) @ MC1 to curing agent (1) @ MC5, curing agent (2) @ MC1: microcapsules encapsulating the curing agent, prepared as described above •
  • TPP-S the same as compound 1 represented by formula (I) in Table 1 •
  • TPTP -S Same as compound 2 represented by formula (I) in
  • Comparative Example IV-9 containing a phenol resin as a curing agent and TPP as a curing accelerator, and containing a phenol resin instead of an aromatic polyamine represented by the formula (II) as a curing agent
  • Comparative Examples IV-10 to 12 containing TPP-S as inferior in rapid curability Comparative Examples II-1 to 15 and Examples III-1 to 12 had a viscosity increase rate of 10% or less, excellent storage stability, and could maintain excellent rapid curability. .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention porte sur une composition de résine époxy durcie par la chaleur présentant d'excellentes propriétés de durcissement. La composition de résine époxy durcie par la chaleur contient une résine époxy (A), un composé polyamine aromatique (B) et un composé représenté par la formule (I), et est caractérisée en ce que le temps de gélification est inférieur ou égal à 3 mn, à 150 °C. (Dans la formule, R1 et R2 représentent un atome d'hydrogène et un groupe alkyle, respectivement).
PCT/JP2009/004417 2008-09-05 2009-09-07 Composition de résine époxy durcie par la chaleur Ceased WO2010026777A1 (fr)

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JP2010516707A JP4737345B2 (ja) 2008-09-05 2009-09-07 熱硬化性エポキシ樹脂組成物
KR1020117006091A KR101245132B1 (ko) 2008-09-05 2009-09-07 열경화성 에폭시 수지 조성물
CN2009801344808A CN102143987B (zh) 2008-09-05 2009-09-07 热固化性环氧树脂组合物

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Cited By (2)

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JP2012041476A (ja) * 2010-08-20 2012-03-01 Sekisui Chem Co Ltd エポキシ樹脂硬化用マイクロカプセル
JP2018188578A (ja) * 2017-05-10 2018-11-29 信越化学工業株式会社 エポキシ樹脂組成物及び半導体装置

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* Cited by examiner, † Cited by third party
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CN102423673A (zh) * 2011-07-28 2012-04-25 西北工业大学 一种在中温下引发热固性环氧树脂固化的潜伏性微胶囊固化剂及其胶黏剂的制备方法
KR102423947B1 (ko) * 2016-02-25 2022-07-21 쇼와덴코머티리얼즈가부시끼가이샤 에폭시 수지 성형 재료, 성형물, 성형 경화물, 및 성형 경화물의 제조 방법

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JPH093164A (ja) * 1995-06-15 1997-01-07 Nitto Denko Corp マイクロカプセル型硬化剤または硬化促進剤、およびそれを含有してなるエポキシ樹脂組成物
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WO2007063580A1 (fr) * 2005-11-30 2007-06-07 Matsushita Electric Works, Ltd. Composition de resine epoxy ne contenant pas d’halogene, feuille de revetement, feuille de liaison, preimpregne, feuille stratifiee pour carte de circuit imprime
WO2008136096A1 (fr) * 2007-04-24 2008-11-13 Panasonic Electric Works Co., Ltd. Composition de résine époxyde sans halogène, pellicule de couche de fermeture, feuille de collage, préimprégné et stratifié de carte de câblage imprimé

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JPH093164A (ja) * 1995-06-15 1997-01-07 Nitto Denko Corp マイクロカプセル型硬化剤または硬化促進剤、およびそれを含有してなるエポキシ樹脂組成物
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WO2007063580A1 (fr) * 2005-11-30 2007-06-07 Matsushita Electric Works, Ltd. Composition de resine epoxy ne contenant pas d’halogene, feuille de revetement, feuille de liaison, preimpregne, feuille stratifiee pour carte de circuit imprime
WO2008136096A1 (fr) * 2007-04-24 2008-11-13 Panasonic Electric Works Co., Ltd. Composition de résine époxyde sans halogène, pellicule de couche de fermeture, feuille de collage, préimprégné et stratifié de carte de câblage imprimé

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012041476A (ja) * 2010-08-20 2012-03-01 Sekisui Chem Co Ltd エポキシ樹脂硬化用マイクロカプセル
JP2018188578A (ja) * 2017-05-10 2018-11-29 信越化学工業株式会社 エポキシ樹脂組成物及び半導体装置

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KR101245132B1 (ko) 2013-03-25
CN102143987B (zh) 2013-08-21

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