WO2011025040A1 - Agent de durcissement pour des résines époxy - Google Patents

Agent de durcissement pour des résines époxy Download PDF

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Publication number
WO2011025040A1
WO2011025040A1 PCT/JP2010/064828 JP2010064828W WO2011025040A1 WO 2011025040 A1 WO2011025040 A1 WO 2011025040A1 JP 2010064828 W JP2010064828 W JP 2010064828W WO 2011025040 A1 WO2011025040 A1 WO 2011025040A1
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group
epoxy resin
curing agent
compound
methyl
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PCT/JP2010/064828
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English (en)
Japanese (ja)
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健二 工藤
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日本合成化学工業株式会社
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Priority claimed from JP2009199379A external-priority patent/JP2011052036A/ja
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Publication of WO2011025040A1 publication Critical patent/WO2011025040A1/fr

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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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/688—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 phosphorus

Definitions

  • the present invention relates to a curing agent for epoxy resins using a compound having a phosphonate anion or an imidazole compound.
  • epoxy resin cured products have excellent performance in mechanical properties, electrical properties, thermal properties, chemical resistance, etc.
  • Various curing agents such as imidazoles, amines, dicyandiamide, acid anhydrides, phenols, hydrazines and guanidines are widely used as compounds for curing such epoxy resins. It was. And in applications such as insulation coatings for metal parts and metal exterior coatings using epoxy resin, it is necessary to cure the epoxy resin in a high temperature range of about 150 to 200 ° C, so it exhibits curing performance at high temperatures.
  • Epoxy resin curing agents have been developed.
  • the imidazoline salt described in Patent Document 1 and the curing agent composed of the imidazole compound are excellent in reactivity with an epoxy resin in a high temperature region of 150 ° C. or higher. There was little difference in the curing performance near and near 200 ° C., and this was unsuitable particularly when it was necessary to selectively cure the epoxy resin near 200 ° C. Examples of in-line coating applications such as deformed steel bars for concrete reinforcement, water pipes, steel pipes for oil transportation pipelines, etc. In some cases, epoxy resins are used for powder coatings used in the field, and in particular, selective curability is required.
  • a curing agent for epoxy resins comprising a compound (X) having a phosphonate anion or an imidazole compound (Y) containing at least one substituent selected from a carboxyl group, a carboxyalkyl group and a carboxyphenylalkyl group.
  • a curing agent for epoxy resins comprising a compound (X) having a phosphonate anion or an imidazole compound (Y) containing at least one substituent selected from a carboxyl group, a carboxyalkyl group and a carboxyphenylalkyl group.
  • R 1 represents an alkyl group having 1 to 10 carbon atoms.
  • [3] The epoxy resin curing agent according to [1] or [2], wherein the cation portion of the compound (X) having a phosphonate anion is an onium cation of a 5- to 6-membered ring compound having 1 to 3 nitrogen atoms.
  • [5] The epoxy resin curing agent according to [4], wherein the imidazolium cation has a structure represented by the following general formula (2).
  • R 1 and R 2 are each independently an alkyl group or alkenyl group having 1 to 16 carbon atoms, and R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group. Or it is an aryl group.
  • R 6 The epoxy resin curing agent according to any one of [1] to [5], which is liquid at 25 ° C.
  • the epoxy resin curing agent according to [1], wherein the imidazole compound (Y) is a compound represented by the following general formula (3) or (4).
  • R1 to R6 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the compound (X) having a phosphonate anion when the compound (X) having a phosphonate anion is liquid at normal temperature (25 ° C.), a series of epoxy resin curing steps of “addition of curing agent ⁇ uniform dispersion ⁇ temperature increase ⁇ curing”.
  • addition of curing agent ⁇ uniform dispersion ⁇ temperature increase ⁇ curing.
  • it can be mixed uniformly and efficiently when added to the epoxy resin, resulting in poor curing such as uneven curing during curing and uncured details. It was also found that it is possible to prevent.
  • the epoxy resin can be selectively cured at around 200 ° C. Further, when the compound (X) having a phosphonate anion is used, the resulting cured product is a phosphorus-containing epoxy. Since it becomes a resin hardened
  • the epoxy resin curing agent includes not only a curing agent but also a curing accelerator (curing aid).
  • the compound (X) having a phosphonate anion only needs to have a phosphonate anion as an anion portion, and the structure of the phosphonate anion is not particularly limited, but is particularly a phosphonate anion having a structure represented by the following general formula (1). Preferably there is.
  • R 1 represents an alkyl group having 1 to 10 carbon atoms.
  • R1 in the general formula (1) is an alkyl group having 1 to 10 carbon atoms, and the carbon number of the alkyl group is preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms.
  • the alkyl group may have a substituent.
  • substituents examples include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a sulfanyl group, an aryl group, a heteroaryl group, and the like. Is an aryl group.
  • Examples of the cation moiety of the compound (X) having a phosphonate anion include, for example, an onium cation, a quaternary ammonium cation, a quaternary phosphonium cation, and a tertiary sulfonium cation of a 5- to 6-membered ring compound having 1 to 3 nitrogen atoms.
  • an onium cation of a 5- to 6-membered ring compound having 1 to 3 nitrogen atoms in terms of good compatibility with the resin.
  • Examples of the onium cation of a 5- to 6-membered ring compound having 1 to 3 nitrogen atoms include an onium cation of a 5-membered ring compound such as imidazolium cation and pyrrolidinium, and an onium cation of a 6-membered ring compound such as pyridinium cation and piperidinium. Can be mentioned. Among these, an imidazolium cation is preferable in that various derivatives can be easily synthesized.
  • Examples of the imidazolium cation include those having the structure of the following general formula (2).
  • R 1 and R 2 are each independently an alkyl group or alkenyl group having 1 to 16 carbon atoms, and R 3 to R 5 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group. Or it is an aryl group.
  • R1 and R2 are each independently an alkyl group
  • the alkyl group preferably has 1 to 16 carbon atoms, more preferably 1 to 15 carbon atoms.
  • Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group, a decyl group, an undecyl group, and a hexadecyl group, preferably a methyl group and an ethyl group.
  • the alkyl group may have a substituent, and the substituent is usually a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a mercapto group, a sulfanyl group, a vinyl group, an acryloyl group, a methacryloyl group, An aryl group, a heteroaryl group, etc. are mentioned.
  • the alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms. It may have an atom, a hydroxyl group, an alkoxy group, an amino group, a sulfanyl group, an aryl group, a heteroaryl group or the like, preferably a hydroxyl group or an aryl group.
  • alkenyl groups include vinyl group, 1-propenyl group, 1-butenyl group, styryl group, 2-pyridyl group, 2-hydroxyvinyl group and the like, preferably vinyl group, 1-propenyl group, A steryl group and a 2-hydroxyvinyl group.
  • R3 to R5 are each independently an alkyl group
  • the alkyl group preferably has 1 to 12 carbon atoms, and more preferably 1 to 11 carbon atoms.
  • Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group, a decyl group, an undecyl group, and a dodecyl group, preferably a methyl group and an ethyl group.
  • the alkyl group may have a substituent, and the substituent is usually a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a mercapto group, a sulfanyl group, a vinyl group, an acryloyl group, a methacryloyl group, An aryl group, a heteroaryl group, etc. are mentioned.
  • the alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms. It may have an atom, a hydroxyl group, an alkoxy group, an amino group, a sulfanyl group, an aryl group, a heteroaryl group or the like, preferably a hydroxyl group or an aryl group.
  • alkenyl groups include vinyl group, 1-propenyl group, 1-butenyl group, styryl group, 2-pyridyl group, 2-hydroxyvinyl group and the like, preferably vinyl group, 1-propenyl group, A steryl group and a 2-hydroxyvinyl group.
  • R3 to R5 are each independently an aryl group
  • the aryl group preferably has 4 to 15 carbon atoms
  • substituents include a halogen atom, a hydroxyl group, an alkoxy group, a sulfanyl group, an amino group A group, an aryl group, a heteroaryl group and the like, preferably a hydroxyl group.
  • Such an alkenyl group is preferably a monocyclic, bicyclic or tricyclic aryl group, and specifically includes a phenyl group, a naphthyl group, an anthresenyl group, a 4-bromophenyl group, a hydroxyphenyl group, p-tolyl. Group, 4-hydroxynaphthyl group and the like, preferably phenyl group and hydroxyphenyl group.
  • 1,3-disubstituted imidazolium cation and 1,2,3-trisubstituted imidazolium cation are preferably used from the viewpoint of easy synthesis.
  • 1,3-disubstituted imidazolium cation is preferably used.
  • the substituents in these derivatives may be the same or different and may have multiple bonds or branches.
  • 1,3-disubstituted imidazolium cation represented by the general formula (2) include 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, and 1-isopropyl-3-methylimidazole.
  • 1,2,3-trisubstituted imidazolium cation represented by the general formula (2) include 1,2,3-trimethylimidazolium, 1,2-dimethyl-3-ethylimidazolium, 1, 2-dimethyl-3-isopropylimidazolium, 1-butyl-2,3-dimethylimidazolium, 1,2-dimethyl-3-isobutylimidazolium, 1-benzyl-2,3-dimethylimidazolium, 1,2- Dimethyl-3- (2-hydroxyethyl) imidazolium, 1-ethyl-3- (2-hydroxyethyl) -2-methylimidazolium, 1-isopropyl-3- (2-hydroxyethyl) -2-methylimidazolium 1-butyl-3- (2-hydroxyethyl) -2-methylimidazolium, 1- (2-hydroxyethyl) -3-isobutyl-2 Methylimidazolium, 1-benzyl-3
  • pyridinium cation examples include a pyridinium cation substituted with an alkyl group having 1 to 16 carbon atoms such as N-methylpyridinium, N-ethylpyridinium, N-isopropylpyridinium, and N-butylpyridinium.
  • a quaternary ammonium cation in addition to the onium cation of the 5- to 6-membered ring compound having 1 to 3 nitrogen atoms, a quaternary ammonium cation, a quaternary phosphonium cation, a tertiary sulfonium cation, or the like is used.
  • Examples of the quaternary ammonium cation include an ammonium cation substituted with an alkyl group having 1 to 16 carbon atoms which may have a functional group such as tetramethylammonium, tetraethylammonium, methyltributylammonium, benzyltrimethylammonium, etc. Can be given.
  • Examples of the quaternary phosphonium cation include a quaternary phosphonium cation substituted with an alkyl group having 1 to 16 carbon atoms which may have a functional group such as tetraethylphosphonium and tetrabutylphosphonium, tetraphenylphosphonium, Examples thereof include an aryl group which may have a functional group such as triphenyl (p-tolyl) phosphonium and benzyltriphenylphosphonium, and a quaternary phosphonium substituted with a benzyl group.
  • a tertiary sulfonium cation for example, a tertiary sulfonium cation substituted with an alkyl group having 1 to 16 carbon atoms which may have a functional group such as trimethylsulfonium, triethylsulfonium, tributylsulfonium, or the like, or triphenyl Examples thereof include an aryl group which may have a functional group such as phosphonium, dibenzylmethylsulfonium, benzyldimethylsulfonium, and tertiary sulfonium substituted with a benzyl group.
  • the compound (X) having a phosphonate anion obtained by combining the cation moiety and the anion moiety include 1-ethyl-3-methylimidazolium methyl phosphite, 1-ethyl-3-methylimidazole Lithium ethyl phosphite, 1-isopropyl-3-methyl imidazolium methyl phosphite, 1-butyl-3-methyl imidazolium methyl phosphite, 1-isobutyl-3-methyl imidazolium methyl phosphite Salt, 1-benzyl-3-methylimidazolium methyl phosphite, 1-ethyl-3-isopropylimidazolium ethyl phosphite, 1-butyl-3-ethylimidazolium ethyl phosphite, 1-benzyl -3-Ethylimidazolium ethyl phosphite
  • 1-ethyl-3-methylimidazolium methyl phosphite, 1-isopropyl-3-methyl imidazolium methyl phosphite can be synthesized at low cost.
  • the melting point of the compound (X) having a phosphonate anion is usually ⁇ 150 to 100 ° C., preferably ⁇ 140 to 90 ° C., more preferably ⁇ 130 to 80 ° C. If it is too high, the compatibility with the resin decreases. For this reason, the curing performance tends to be lowered.
  • the glass transition temperature (Tg) of the compound (X) having a phosphonate anion is usually ⁇ 150 to 100 ° C., preferably ⁇ 140 to 90 ° C., more preferably ⁇ 130 to 80 ° C. Since the compatibility is lowered, the curing performance tends to be lowered.
  • DSC2920 (TA Instruments) is used to measure the melting point and glass transition temperature, and 10 mg of a sample is weighed and sealed in an aluminum cell, and the sample and reference sample (aluminum empty cell) are set in the DSC. While purging with nitrogen at 50 ml / min, cool from room temperature to ⁇ 150 ° C. using liquid nitrogen, hold at that temperature for 3 minutes, and then increase the temperature when the temperature is raised to 100 ° C. at a temperature increase rate of 10 ° C./min. It can be performed by a method of measuring from a temperature data chart.
  • the compound (X) having a phosphonate anion is preferably liquid at normal temperature (25 ° C.). This is because in the series of epoxy resin curing processes of “addition of curing agent ⁇ uniform dispersion ⁇ temperature increase ⁇ curing”, compared to known epoxy curing agent that is solid at ordinary temperature, it is added to the epoxy resin and then mixed. This is because they can be uniformly mixed efficiently, and curing defects such as uneven curing during curing and uncured details can be prevented.
  • the compound (X) having a phosphonate anion when the cation moiety is an imidazolium salt, a 1-substituted imidazole and a dialkyl phosphite compound according to, for example, the method described in International Publication No. 2008/114584 Can be made to react.
  • the cation moiety is a quaternary phosphonium cation, for example, by subjecting a quaternary phosphonium halide and a dialkyl phosphite compound to a salt exchange reaction according to the method described in German Patent Application Publication No. 3332716. Can be manufactured.
  • the cation moiety is a tertiary sulfonium cation, for example, by reacting a trialkylsulfonium halide with a dialkyl phosphite compound and propylene oxide according to the method described in Japanese Patent Application Laid-Open No. 59-141557. Can be manufactured.
  • imidazole compound (Y) containing at least one substituent selected from a carboxyl group, a carboxyalkyl group, and a carboxyphenylalkyl group (hereinafter sometimes abbreviated as “imidazole compound (Y)”). explain.
  • the imidazole compound (Y) may be any imidazole compound containing at least one substituent selected from a carboxyl group, a carboxyalkyl group, and a carboxyphenylalkyl group as a substituent, and contains a plurality of such substituents. In some cases, a plurality of the same substituents may be contained, or a plurality of different substituents may be contained.
  • the number of substituents is usually 1 to 4, preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.
  • the carbon number of the alkyl group of the carboxyalkyl group is preferably 1 to 5 carbon atoms, particularly preferably 1 to 4 carbon atoms.
  • Examples of such a carboxyalkyl group include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, and a carboxybutyl group. Among these, a carboxymethyl group and a carboxyethyl group are preferably used.
  • the carbon number of the alkyl group of the carboxyphenylalkyl group is preferably 1 to 5 carbon atoms, particularly preferably 1 to 4 carbon atoms.
  • Examples of such carboxyphenylalkyl group include p-carboxyphenylmethyl group, o-carboxyphenyl group methyl, m-carboxyphenylmethyl group and the like. Among these, p-carboxyphenylmethyl group is preferably used.
  • the imidazole compound (Y) is preferably a compound represented by the following general formula (3) or (4) from the viewpoint that the curing performance of the present invention can be sufficiently exhibited.
  • R1 to R6 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • R1 to R3 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the carbon number of the alkyl group is preferably 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and specific examples include a methyl group, an ethyl group, an isopropyl group, a butyl group, an isobutyl group, and the like.
  • the alkyl group may have a substituent.
  • substituents include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a sulfanyl group, an aryl group, a heteroaryl group, and the like. Is a hydroxyl group or an aryl group.
  • (1H-2,4,5-trimethylimidazol-1-yl) acetic acid is used as the imidazole compound represented by the general formula (3), it is easy to synthesize and further exhibits sufficient curing performance. This is preferable.
  • R4 to R6 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the carbon number of the alkyl group is preferably 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and specific examples include a methyl group, an ethyl group, an isopropyl group, a butyl group, an isobutyl group, and the like. Is easy to synthesize, and R4 and R5 are preferably hydrogen atoms and R6 is preferably a methyl group.
  • the alkyl group may have a substituent.
  • substituents include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a sulfanyl group, an aryl group, a heteroaryl group, and the like. Is a hydroxyl group or an aryl group.
  • the imidazole compound represented by the general formula (4) it is particularly preferable to use 1-methyl-5-imidazolecarboxylic acid because it is easy to synthesize and can sufficiently exhibit curing performance.
  • the molecular weight of the imidazole compound (Y) is usually 100 to 750, preferably 110 to 500.
  • the melting point of the imidazole compound (Y) is usually ⁇ 150 to 250 ° C., preferably ⁇ 140 to 240 ° C., more preferably ⁇ 130 to 230 ° C. If it is too high, the compatibility with the resin will decrease. Curing performance tends to decrease.
  • the glass transition temperature (Tg) of the imidazole compound (Y) is usually ⁇ 150 to 250 ° C., preferably ⁇ 140 to 240 ° C., more preferably ⁇ 130 to 230 ° C. If it is too high, the compatibility with the resin , The curing performance tends to decrease.
  • DSC2920 (TA Instruments) is used to measure the melting point and glass transition temperature, and 10 mg of a sample is weighed and sealed in an aluminum cell, and the sample and reference sample (aluminum empty cell) are set in the DSC. While purging nitrogen at 50 ml / min, use liquid nitrogen to cool from room temperature to ⁇ 150 ° C., hold at that temperature for 3 minutes, and then increase the temperature when the temperature is raised to 300 ° C. at a temperature rising rate of 10 ° C./min. It can be performed by a method of measuring from a temperature data chart.
  • Examples of the method for producing imidazole compound (Y) include N-alkylation reaction of alkylating agents such as chloroacetic acid and p-bromobenzoic acid derivatives and N-unsubstituted imidazole derivatives, and 4 (5) -hydroxymethyl. It can be produced by an oxidation reaction of an imidazole compound.
  • the epoxy resin used in the present invention is not particularly limited as long as it has two or more epoxy groups in one molecule on average.
  • Representative epoxy resins include bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, and tetrabromobisphenol A.
  • Bisphenol type epoxy resin biphenol, dihydroxynaphthalene, epoxy resin obtained by glycidylation of other dihydric phenols such as 9,9-bis (4-hydroxyphenyl) fluorene, 1,1,1-tris (4-hydroxy Glycidylation of trisphenols such as phenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol Epoxy resin, epoxy resin obtained by glycidylation of tetrakisphenols such as 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A Novolak-type epoxy resin glycidylated novolak, aliphatic ether-type epoxy resin glycidylated polyhydric alcohols such as glycerin and polyethylene glycol
  • amine type epoxy resins such as glycidylated amine compounds and triglycidyl isocyanurate, and alicyclic epoxides such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, and the like.
  • a mixture of two or more kinds may be used.
  • additives such as a diluent, a flexibility imparting agent, a silane coupling agent, an antifoaming agent, a leveling agent, a filler, a pigment, and a dye can be added to the epoxy resin as necessary.
  • the compound (X) having the phosphonate anion is used as a curing agent for the epoxy resin, and the amount of the compound (X) having the phosphonate anion is as follows: Usually 0.1 to 30 parts by weight, preferably 0.2 to 25 parts by weight, particularly preferably 0.3 to 20 parts by weight. If the amount used is too large, the physical properties of the cured product tend to decrease, and if it is too small, the curing reaction tends not to proceed.
  • the imidazole compound (Y) is used as a curing agent for the epoxy resin.
  • the amount of the imidazole compound (Y) used is usually 0.1% with respect to 100 parts by weight of the epoxy resin. -30 parts by weight, preferably 0.2-25 parts by weight, particularly preferably 0.3-20 parts by weight. If the amount used is too large, the physical properties of the cured product tend to decrease, and if it is too small, the curing reaction tends not to proceed.
  • the compound (X) or imidazole compound (Y) having a phosphonate anion in the present invention can be used alone as a curing agent, amines, polyamines, hydrazines, acid anhydrides, dicyandiamides, imidazoles, oniums. It can also be used in combination with generally used curing agents such as salts, polythiols, phenols and ketimines. Moreover, it is also possible to use a known general epoxy resin curing accelerator (curing aid) in combination.
  • epoxy resin curing agent containing the phosphonate anion-containing compound (X) or imidazole compound (Y) in the present invention is used in combination with the above-mentioned general curing agent to promote the curing performance catalytically. Can be used.
  • the method of mixing the compound (X) having the phosphonate anion or the imidazole compound (Y) with the epoxy resin is not particularly limited.
  • the epoxy resin cured product can be obtained by heating the kneaded epoxy resin mixture.
  • the heating conditions may be appropriately selected in consideration of the type of epoxy resin, the type of curing agent, the type of additive, and the blending amount of each component.
  • a cured epoxy resin can be obtained by using the compound (X) or imidazole compound (Y) having a phosphonate anion as a curing agent.
  • the measurement conditions of the following glass transition temperature are as follows. ⁇ Devices used>: DSC2920 (manufactured by TA Instruments) ⁇ Measurement method>: 10 mg of sample was weighed and sealed in an aluminum cell, the sample and reference sample (aluminum empty cell) were set in DSC, and nitrogen was purged at 50 ml / min. It was cooled to 150 ° C. and kept at the same temperature for 3 minutes. Then, it heated up to 100 degreeC with the temperature increase rate of 10 degree-C / min, and measured the glass transition temperature from the chart which took in the data of temperature rising.
  • the supernatant diethyl ether layer was separated and removed, and further washed twice with 300 ml of diethyl ether.
  • the obtained 1-ethyl-3-methylimidazolium methyl phosphite was vacuum dried at 80 ° C. for 24 hours to give 1-ethyl-3-methylimidazolium methyl phosphite (X-1) 51 .5 g was obtained.
  • the glass transition point of (X-1) is ⁇ 90 ° C., and it is liquid at room temperature (25 ° C.).
  • the resulting solution containing crude 3-ethyl-1-methylimidazolium ethyl phosphite was cooled to 25 ° C., 300 ml of diethyl ether was added, and the mixture was vigorously stirred for 1 hour. The supernatant diethyl ether layer was separated and removed, and further washed twice with 300 ml of diethyl ether.
  • the obtained 3-ethyl-1-methylimidazolium ethyl phosphite was vacuum dried at 80 ° C. for 24 hours to give 3-ethyl-1-methylimidazolium ethyl phosphite (X-2) .5 g was obtained.
  • the glass transition point of (X-2) is ⁇ 81 ° C., and it is liquid at room temperature (25 ° C.).
  • Examples 1 to 4 Comparative Examples 1 and 2> Phosphonate anion-containing compounds (X-1) and (X-2) obtained in Production Examples 1 and 2 above, imidazole compounds (Y-1) and (Y-2) obtained in Production Examples 3 and 4 ), 2-phenyl-4,5-dihydroxymethylimidazole (melting point 224 ° C.) and 2,4,5-trimethylimidazolyl succinic acid (melting point 202 ° C.) obtained in Production Example 5 were subjected to the following epoxy resin curing test. .
  • the curing agents described in Examples 1 to 4 cure the epoxy resin at 200 ° C. within a practical curing time of 20 minutes, but do not exhibit curing performance at 150 ° C.
  • the epoxy resin can be selectively cured at 200 ° C.
  • 2-phenyl-4,5-bishydroxymethylimidazole used in Comparative Example 1 exhibits curability at both 200 ° C. and 150 ° C., and selectively exhibits curing performance at 200 ° C. is not.
  • the 2,4,5-trimethylimidazolyl succinic acid used in Comparative Example 2 also exhibits curability at both 200 ° C. and 150 ° C., and does not selectively exhibit curing performance at 200 ° C. .
  • the epoxy resin can be selectively cured at around 200 ° C., and paints (particularly, deformed steel bars for concrete reinforcement, water pipes, steel pipes for oil transportation pipelines, etc.) It is useful as a curing agent for epoxy resins used in a wide range of applications such as powder coatings used in in-line coating applications), insulating materials for electrical and electronic use, adhesives and the like.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

L'invention porte sur un agent de durcissement pour des résines époxy avec une différence dans son aptitude à faire durcir les résines époxy à approximativement 150°C et à approximativement 200°C, qui est capable d'effectuer de façon sélective des réactions de durcissement sur les résines époxy à proximité de 200°C. L'agent de durcissement pour des résines époxy comprend un composé (X) qui est doté d'un anion phosphonate ou d'un composé imidazole (Y) qui comprend au moins un substituant choisi parmi un groupe carboxyle, un groupe carboxyalkyle et un groupe (carboxy-phényl) alkyle.
PCT/JP2010/064828 2009-08-31 2010-08-31 Agent de durcissement pour des résines époxy WO2011025040A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2009-199379 2009-08-31
JP2009199379A JP2011052036A (ja) 2009-08-31 2009-08-31 エポキシ樹脂用硬化剤
JP2009-250556 2009-10-30
JP2009250556 2009-10-30

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JP2011116939A (ja) * 2009-10-30 2011-06-16 Nippon Synthetic Chem Ind Co Ltd:The エポキシ樹脂用硬化剤
EP3683210A4 (fr) * 2017-09-29 2020-08-19 Tokyo Ohka Kogyo Co., Ltd. Composé, catalyseur de durcissement époxy et procédé de production d'un composé

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JP2004016631A (ja) * 2002-06-19 2004-01-22 Kawajun Co Ltd ２陳列方式商品陳列台
WO2008152002A1 (fr) * 2007-06-14 2008-12-18 Basf Se Catalyseur pour le durcissage d'époxydes
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JP2004016631A (ja) * 2002-06-19 2004-01-22 Kawajun Co Ltd ２陳列方式商品陳列台
WO2008152002A1 (fr) * 2007-06-14 2008-12-18 Basf Se Catalyseur pour le durcissage d'époxydes
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011116939A (ja) * 2009-10-30 2011-06-16 Nippon Synthetic Chem Ind Co Ltd:The エポキシ樹脂用硬化剤
EP3683210A4 (fr) * 2017-09-29 2020-08-19 Tokyo Ohka Kogyo Co., Ltd. Composé, catalyseur de durcissement époxy et procédé de production d'un composé
US11718587B2 (en) 2017-09-29 2023-08-08 Tokyo Ohka Kogyo Co., Ltd. Compound, epoxy curing catalyst and method for producing compound

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