WO2022168665A1 - 新規化合物、及び該化合物を含有する硬化性樹脂組成物 - Google Patents

新規化合物、及び該化合物を含有する硬化性樹脂組成物 Download PDF

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WO2022168665A1
WO2022168665A1 PCT/JP2022/002585 JP2022002585W WO2022168665A1 WO 2022168665 A1 WO2022168665 A1 WO 2022168665A1 JP 2022002585 W JP2022002585 W JP 2022002585W WO 2022168665 A1 WO2022168665 A1 WO 2022168665A1
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acid
curable resin
group
resin composition
compound
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French (fr)
Japanese (ja)
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健一 玉祖
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Adeka Corp
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Adeka Corp
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Priority to US18/260,554 priority Critical patent/US20240084065A1/en
Priority to CN202280010118.5A priority patent/CN116848105A/zh
Priority to EP22749540.5A priority patent/EP4289837A4/en
Priority to JP2022579457A priority patent/JP7731382B2/ja
Priority to KR1020237022619A priority patent/KR20230142703A/ko
Publication of WO2022168665A1 publication Critical patent/WO2022168665A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/223—Di-epoxy compounds together with monoepoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/145—Compounds containing one epoxy group
    • 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
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings

Definitions

  • the present invention relates to novel compounds and curable resin compositions. Specifically, it relates to a novel imide compound having an epoxy group, and to a curable resin composition containing an epoxy resin, a curing agent, and the compound.
  • Epoxy resins are widely used industrially as components of paints, adhesives, various molding materials, and the like.
  • the epoxy resin is usually used in combination with a curing agent, and as the curing agent, various curing agents such as acid anhydride curing agents, amine curing agents, and phenolic curing agents are known. It is
  • imidazole curing agents are anionic polymerization curing agents, so they can be cured by adding a small amount. Since it is also useful in that it is volatile and has low toxicity, it can be suitably used for electrical and electronic parts.
  • Patent Document 1 proposes to use a reaction product of an imidazole compound and an epoxy resin in an epoxy curing system
  • Patent Document 2 discloses modified imidazole, modified Curing agent compositions for epoxy resins comprising amines and phenolic compounds have been proposed.
  • the problem to be solved by the present invention is to provide a material from which a curable resin composition having an excellent balance between curability and storage stability can be obtained.
  • the present invention is a compound represented by the following formula (1).
  • R 1 to R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, a nitro group or a nitrile group; 5 to R 7 each independently represent a hydrogen atom or a methyl group, ring A represents (a1) or (a2), and * forms a condensed ring with an imide ring.
  • the present invention also provides a curable resin composition containing an epoxy resin as component (A), a curing agent as component (B), and the above compound as component (C).
  • the curable resin composition of the present invention can be suitably used as a one-pack curing type curable resin composition.
  • FIG. 1 is a diagram showing the results of GPC measurement of the compound produced in Example 1.
  • FIG. 2 is a diagram showing the results of 1 H-NMR measurement of the compound produced in Example 1.
  • the compounds of the present invention are described below.
  • the compound of the present invention is a compound represented by the following formula (1).
  • R 1 to R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, a nitro group or a nitrile group; 5 to R 7 each independently represent a hydrogen atom or a methyl group, ring A represents (a1) or (a2), and * forms a condensed ring with an imide ring.
  • alkyl groups having 1 to 10 carbon atoms represented by R 1 to R 4 in formula (1) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tertiary amyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group and isodecyl group, and alkoxy groups having 1 to 10 carbon atoms.
  • groups include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, pentyloxy, hexyloxy, heptyloxy, octoxy, nonyloxy and decyloxy groups.
  • Halogen atoms include, for example, fluorine, chlorine, bromine and iodine.
  • the ring A is (a1), and R 1 to R 4 are The following compound (1A), which is a hydrogen atom or a methyl group, is preferred.
  • R 5 to R 7 and R 11 to R 14 each independently represent a hydrogen atom or a methyl group.
  • the compound of the present invention is not particularly limited, it can be produced, for example, according to the scheme below.
  • the phenol compound represented by the formula (1a) can be produced by carrying out a normal imidization reaction using an acid anhydride having ring A and an aminophenol compound.
  • Examples of the method for carrying out the imidization reaction include the following methods. (1) An acid anhydride having a ring A and an aminophenol compound are reacted at a low temperature of 150° C. or less, specifically at 0 to 120° C., preferably at 40 to 100° C. to obtain an amic acid compound ( 1m), followed by imidization reaction by raising the temperature to 100 to 200° C.
  • thermo imidization (2) A method of synthesizing an amic acid compound (1m) in the same manner as in (1) above, and then chemically imidizing it with an imidizing agent such as acetic anhydride (chemical imidization). (3) A method of synthesizing an amic acid compound in the same manner as in (1) above, and then subjecting it to an imidization reaction by heating under reflux in an azeotropic dehydration solvent in the presence or absence of a catalyst (azeotropic dehydration ring closure law) Among these methods, method (1) is preferred.
  • the imidization reaction is preferably carried out in an organic solvent.
  • the organic solvent used is not particularly limited, but examples include saturated hydrocarbons such as pentane, hexane, heptane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; dichloromethane and chloroform.
  • the amount of the organic solvent used is not particularly limited, but is 1 to 10,000 parts by mass, preferably 10 to 500 parts by mass, relative to 1 part by mass of the acid anhydride having ring A and the aminophenol compound.
  • the imidization reaction is preferably carried out in a solution by dissolving the raw materials in an organic solvent, but may be carried out in a slurry state.
  • the imidization reaction may be carried out in the presence of an organic base catalyst or an acid catalyst.
  • organic base catalyst include triethylamine, tributylamine, tripentylamine, N,N-dimethylaniline, N,N-diethylaniline, pyridine, ⁇ -picoline, ⁇ -picoline, ⁇ -picoline, 2,4- Examples include lutidine, 2,6-lutidine, quinoline and isoquinoline, with pyridine and ⁇ -picoline being preferred.
  • These organic base catalysts may be used alone or in combination of two or more.
  • the acid catalyst examples include inorganic acids such as hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfuric anhydride, nitric acid, phosphoric acid, phosphorous acid, phosphotungstic acid, and phosphomolybdic acid; methanesulfonic acid, ethanesulfone; acid, trifluoromethanesulfonic acid, benzenesulfonic acid, sulfonic acids such as p-toluenesulfonic acid; carboxylic acids such as acetic acid and oxalic acid; chloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid Halogenated carboxylic acids; solid acids such as silica, alumina and activated clay; cationic ion exchange resins and the like. Sulfuric acid, phosphoric acid and p-toluenesul
  • the amount of the catalyst used is not particularly limited as long as the reaction rate is substantially improved, but it is 0.001 to 10 mol, preferably 0.001 to 10 mol, per 1 mol of the acid anhydride having ring A and the aminophenol compound. 0.005 to 5 mol, more preferably 0.01 to 1 mol.
  • the total reaction time for the reaction to obtain the amic acid compound and the imidization reaction varies depending on the type of raw materials used, the type of organic solvent, the type of catalyst, the type and amount of the solvent for azeotropic dehydration, and the reaction temperature. As a guideline, it is 1 to 24 hours, usually several hours. When carrying out direct thermal imidization, as a guideline, the reaction is carried out until the amount of distilled water reaches approximately the theoretical amount.
  • the reaction pressure in the reaction for obtaining an amic acid compound and in the imidization reaction is not particularly limited, but it is usually atmospheric pressure.
  • the reaction atmosphere is not particularly limited, it is usually air, nitrogen, helium, neon or argon atmosphere, preferably inert gas nitrogen and argon atmospheres.
  • the method for isolating the phenol compound represented by the formula (1a) from the reaction mixture of the acid anhydride having ring A and the aminophenol compound is not particularly limited. Isolation may be by filtration or centrifugation. On the other hand, when the target compound is dissolved in the reaction solvent, the solvent may be distilled off under reduced pressure, an appropriate poor solvent may be added to the reaction mixture, or the reaction mixture may be drained into the poor solvent. It may be precipitated and isolated by filtration or centrifugation.
  • the isolated phenol compound represented by formula (1a) When it is necessary to further purify the isolated phenol compound represented by formula (1a), it may be purified by adopting a method known as a conventional method. Recrystallization method, column chromatography method, sludge treatment, activated carbon treatment and the like can be mentioned.
  • the glycidyl etherification reaction is carried out by reacting the phenol compound represented by the formula (1a) with an excess amount of epichlorohydrin in the presence of a base and, if necessary, in the presence of a catalyst.
  • the reaction is usually carried out at a reaction temperature of 50-80° C. under reduced pressure conditions of 30-250 Torr. Further, the reaction time is usually 2 to 30 hours.
  • bases used in the glycidyl etherification reaction include sodium hydroxide, potassium hydroxide and calcium hydroxide.
  • the catalyst used in the glycidyl etherification reaction includes Lewis acids, interlayer transfer catalysts, and the like.
  • the Lewis acid include boron trifluoride, tin chloride and zinc chloride.
  • the interlayer transfer catalyst include tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, methyltridecylammonium chloride, N,N-dimethylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium chloride, nium iodide, N-butyl-N-methylpyrrolidinium bromide, N-benzyl-N-methylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium bromide, N-butyl-N-methylmorpholinium Bromide, N-butyl-N-methylmorpholinium iodide, N-allyl-N-methylmorpholinium
  • the amount of epichlorohydrin used in the glycidyl etherification reaction is preferably 1 mol or more, particularly preferably in the range of 2 to 10 mol, per 1 mol of the hydroxyl group of the phenol compound represented by the above formula (1a). It is preferably 0.1 to 2.0 mol, particularly preferably 0.3 to 1.5 mol, per 1 mol of the hydroxyl group of the phenol compound represented by formula (1a).
  • an interlayer transfer catalyst it is preferably used in an amount of 0.01 to 10% by mass, particularly 0.2 to 2% by mass, relative to the phenol compound represented by formula (1a).
  • the glycidyl etherification reaction can be performed using organic solvents such as hydrocarbons, ethers and ketones, but can also be performed using excess epichlorohydrin as a solvent.
  • the target compound represented by the formula (1) is obtained by the above.
  • the curable resin composition of the present invention contains an epoxy resin as component (A), a curing agent as component (B), and a compound represented by formula (1) as component (C).
  • the epoxy resin which is the component (A) should have at least two epoxy groups in the molecule, and can be used without any particular restrictions on the molecular structure, molecular weight, and the like.
  • epoxy resin examples include polyglycidyl etherified mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol and phloroglucinol; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis(orthocresol), ethylidene.
  • Bisphenol isopropylidenebisphenol (bisphenol A), isopropylidenebis(orthocresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene) , 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolak, ortho-cresol novolak, ethyl Polyglycidyl etherified products of polynuclear polyhydric phenol compounds such as phenol novolak, butylphenol novolak, octylphenol novolak, resorcinol novolak and terpene phenol; ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyethylene glycol, polypropylene glycol,
  • epoxy resins are in the form of internal cross-linking with isocyanate-terminated prepolymers, and have high molecular weights with polyvalent active hydrogen compounds (polyhydric phenols, polyamines, carbonyl group-containing compounds, polyphosphate esters, etc.). It can also be used in the form An epoxy resin may be used independently and may use 2 or more types together.
  • Examples of the (B) component curing agent include acid anhydride curing agents, phenol curing agents, amine curing agents, polythiol curing agents, and imidazole curing agents.
  • Examples of the acid anhydride curing agent include hymic anhydride, phthalic anhydride, maleic anhydride, methyl hymic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, benzophenonetetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, hydrogenated methylnadic anhydride and the like.
  • phenol-based curing agent examples include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyloc resin), naphthol aralkyl resin, trisphenyl roll methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensation novolac resin, naphthol-cresol co-condensation novolac resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nuclei are linked by bismethylene groups), Biphenyl-modified naphthol resins (polyhydric naphthol compounds in which phenol nuclei are linked by bismethylene groups), aminotriazine-modified phenol resins (compounds having a phenol skeleton, a triazine ring and
  • amine curing agent examples include alkylene diamine such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, hexamethylenediamine and metaxylenediamine.
  • alkylene diamine such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, hexamethylenediamine and metaxylenediamine.
  • Diamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,3-diaminomethylcyclohexane, 1,2-diaminocyclohexane, 1 ,4-diamino-3,6-diethylcyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexyl Alicyclic polyamines such as propane, bis(4-aminocyclohexyl) sulfone, 4,4'-diaminodicyclohexyl ether, 2,2'-dimethyl-4,4'-diaminodic
  • a modified amine-based curing agent obtained by modifying the amines can also be used. Modification methods include dehydration condensation with carboxylic acid, addition reaction with epoxy resin, addition reaction with isocyanate, Michael addition reaction, Mannich reaction, condensation reaction with urea, and condensation reaction with ketone.
  • carboxylic acids that can be used to modify the amines include maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, and trimer acid.
  • phthalic acid isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, and other aliphatic, aromatic or alicyclic polybasic acids, etc. are mentioned.
  • Isocyanate compounds that can be used to modify the amines include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, phenylene diisocyanate, xylylene diisocyanate, Aromatics such as tetramethylxylylene diisocyanate, 1,5-naphthylene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate, dianisidine diisocyanate and tetramethylxylylene diisocyanate Diisocyanates; alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, trans-1,4-cyclohexyl diisocyanate and norbornene di
  • isocyanate compounds can be used in the form of modified products such as carbodiimide-modified, isocyanurate-modified and biuret-modified, and can also be used in the form of blocked isocyanates blocked with various blocking agents.
  • polythiol-based curing agent examples include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), dipentaerythritol hexakis (3-mercaptopropionate), and dipentaerythritol hexakis.
  • imidazole curing agent examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl- 4-methylimidazole, 2-aminopropylimidazole, 1-phenylmethyl-2-imidazole, 1-phenylmethyl-2-ethyl-4-methylimidazole, 1-phenylmethyl-2-phenylimidazole, 1-butoxycarbonylethyl- 2-methylimidazole, 1-butoxycarbonylethyl-2-ethyl-4-methylimidazole, 1-butoxycarbonylethyl-2-phenylimidazole, 1-(2-ethylhexyl)carbonylethyl-2-methylimidazole, 1-(2 -ethylhexyl)carbonylethyl-2-ethyl
  • ADEKA HARDNER EH-3636AS examples include ADEKA HARDNER EH-3636AS, ADEKA HARDNER EH-4351S (manufactured by ADEKA; dicyandiamide latent curing agent), ADEKA HARDNER EH-5011S, and ADEKA HARDNER EH-.
  • imidazole-based curing agents are preferred, and in particular unmodified compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be cured using a relatively small amount, and other curing agents It is preferable because the effect as a curing accelerator can also be exhibited when combined with.
  • the amount of the curing agent is not particularly limited, but it is preferably 1 to 70 parts by mass, more preferably 1 to 50 parts by mass, based on 100 parts by mass of the epoxy resin as component (A). More preferably, 3 to 30 parts by mass is particularly preferable.
  • curing agent and a known epoxy resin curing accelerator can be used together as needed.
  • curing accelerators include phosphines such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; amines such as benzyldimethylamine and 2,4,6-tris(dimethylaminomethyl)phenol; trimethylammonium chloride.
  • quaternary ammonium salts such as; 3-(p-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, ureas such as isophorone diisocyanate-dimethylurea and tolylene diisocyanate-dimethylurea; complexes of boron trifluoride and amines; and complexes of boron trifluoride and ether compounds.
  • These curing accelerators may be used alone or in combination of two or more.
  • the content of the epoxy resin curing accelerator is not particularly limited and can be appropriately set according to the application of the curable resin composition.
  • the curable resin composition of the present invention contains the compound represented by the formula (1) as component (C).
  • component (C) contains the compound represented by the formula (1) as component (C).
  • containing at least one of the compounds represented by the formulas (1-1) to (1-4) as the component (C) provides a curable resin composition excellent in curability and storage stability. It is preferable because it can be obtained.
  • the content of component (C) is preferably 1 to 2000 parts by mass, more preferably 10 to 1000 parts by mass, and 30 to 500 parts by mass based on 100 parts by mass of component (B). is more preferred. If the content of component (C) is less than 1 part by mass, the effect of imparting stability to the curable resin composition may not be obtained, and if it exceeds 2000 parts by mass, the curability may be adversely affected. be.
  • the curable resin composition of the present invention can contain antioxidants such as phosphorus antioxidants, phenolic antioxidants and sulfur antioxidants.
  • Examples of the phosphorus-based antioxidant include triphenylphosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tris(dinonylphenyl)phosphite, tris( mono- and di-mixed nonylphenyl) phosphites, bis(2-tert-butyl-4,6-dimethylphenyl) ethyl phosphite, diphenyl acid phosphite, 2,2'-methylenebis(4,6-di-tert-butyl phenyl)octylphosphite, diphenyldecylphosphite, phenyldiisodecylphosphite, tributylphosphite, tris(2-ethylhexyl)phosphite, tridecylphosphit
  • phenol antioxidant examples include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4- hydroxyphenyl)propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, tridecyl 3,5-di-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis[(3,5 -di-tert-butyl-4-hydroxyphenyl)propionate], 4,4′-thiobis(6-tert-butyl-m-cresol), 2-octylthio-4,6-di(3,5-di-tert-butyl -4-hydroxyphenoxy)-s-triazine, 2,2′-methylenebis(4-methyl-6-tert-butylphenol), bis[3,3-bis(4-
  • sulfur-based antioxidants examples include dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid such as dialkylthiodipropionates, and pentaerythritol tetra( ⁇ -dodecylmercaptopropionate).
  • the curable resin composition of the present invention can contain light stabilizers such as UV absorbers and hindered amine light stabilizers.
  • Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4′-(2 -methacryloyloxyethoxyethoxy)benzophenone and 2-hydroxybenzophenones such as 5,5′-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-( 2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl -5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-dodecyl-5-methylphenyl)benzotriazole, 2-(2-hydroxy-3-tert-butyl-5-C7-9 mixed
  • hindered amine light stabilizer examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate , tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) bis(tridecyl)-1,2,3,4-butane tetracarboxylate, Bis(1,2,2,6,6-p
  • the curable resin composition of the present invention can contain a silane coupling agent.
  • the silane coupling agent include ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)-N'- ⁇ -( aminoethyl)- ⁇ -aminopropyltriethoxysilane, ⁇ -anilinopropyltriethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltriethoxysilane, vinyltriethoxysilane , N- ⁇ -(N-vinylbenzylaminoethyl)- ⁇ -aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -chloro
  • the curable resin composition of the present invention may contain a filler.
  • the filler include silica such as fused silica and crystalline silica; magnesium hydroxide, aluminum hydroxide, zinc molybdate, calcium carbonate, silicon carbonate, calcium silicate, potassium titanate, beryllia, zirconia, zircon, Powders such as foresterite, steatite, spinel, mullite and titania, and beads obtained by spheroidizing these powders; fibers such as glass fibers, pulp fibers, synthetic fibers and ceramic fibers;
  • the curable resin composition of the present invention can contain various solvents, preferably organic solvents.
  • organic solvent include ethers such as tetrahydrofuran, 1,2-dimethoxyethane and 1,2-diethoxyethane; isobutanol, n-butanol, isopropanol, n-propanol, amyl alcohol, benzyl alcohol, furfuryl alcohols such as alcohol and tetrahydrofurfuryl alcohol; ketones such as methyl ethyl ketone, methyl isopropyl ketone and methyl butyl ketone; aromatic hydrocarbons such as benzene, toluene and xylene; triethylamine, pyridine, dioxane and acetonitrile.
  • the curable resin composition of the present invention may contain other various additives as necessary.
  • the additives include phenol compounds such as biphenol; reactive diluents such as monoalkyl glycidyl ether; non-reactive diluents (plasticizers) such as dioctyl phthalate, dibutyl phthalate, benzyl alcohol and coal tar; Aramid cloth, reinforcing materials such as carbon fiber; pigments; candelilla wax, carnauba wax, Japan wax, wart wax, beeswax, lanolin, spermaceti, montan wax, petroleum wax, aliphatic wax, aliphatic ester, aliphatic ether, Lubricants such as aromatic esters and ethers; thickeners; thixotropic agents; antifoam agents; rust inhibitors;
  • adhesive resins such as cyanate ester resins, xylene resins and petroleum resins can also be used in combination.
  • the curable resin composition of the present invention can be used as a one-component curing type curable resin composition because it is possible to adjust the balance between curability and storage stability.
  • Applications of the curable resin composition of the present invention are not particularly limited, but include, for example, adhesives for electronic parts, sealing materials for electronic parts, casting materials, paints and structural adhesives.
  • Example 1 A flask equipped with a rotor, thermometer, and Dean-Stark apparatus was charged with 65.7 g (0.4 mol) of norbornene dicarboxylic anhydride, 43.7 g (0.4 mol) of p-aminophenol, and 350 g of xylene, and heated at 100°C. Stirred for 2 hours. 3.4 g (0.02 mol) of p-toluenesulfonic acid and 50 g of N-methylpyrrolidone were added thereto, the temperature was raised, and reflux dehydration was carried out over 4 hours. After cooling to room temperature, 500 mL of water was added and stirred. The solid was separated by filtration and recrystallized with methanol/toluene, and the crystals were separated by filtration to obtain purple crystals (melting point: 251°C).
  • the resulting viscous liquid turned into light brown crystals with a melting point of 100°C after being left for one day.
  • GPC measurement and 1 H-NMR measurement were performed. The results are shown in FIGS. 1 and 2, respectively.
  • the epoxy equivalent of the light brown crystals obtained was 413 g/eq. (Theoretical value: 311 g/eq.). These results confirmed that the pale brown crystals obtained were the compound represented by the formula (1-1).
  • Examples 2 to 7 As shown in Table 1, ADEKA RESIN EP-4100E (manufactured by ADEKA; bisphenol A type epoxy resin) as the epoxy resin of component (A), and 2-ethyl-4-methylimidazole (2E4MZ) as the curing agent of component (B). Or ADEKA HARDNER EH-2021 (made by ADEKA; adduct type imidazole), a curable resin composition was produced using the compound obtained in Example 1 as the component (C), and storage stability and curability were evaluated. gone.
  • Example 1 A curable resin composition was produced in the same manner as in Example 2 except that the compound obtained in Example 1 was not used, and storage stability and curability were evaluated.
  • Storage stability The storage stability was evaluated by placing the curable resin composition in a beaker, allowing it to stand at room temperature, and confirming the number of days until it gelled. If gelation does not occur within 3 days, there is no practical problem, and it is judged that the storage stability is excellent.
  • Curability was evaluated by coating a glass plate with a curable resin composition using a bar coater, heating at 150° C. for 2 hours, and checking the state of curing. Those with no tack were rated as ⁇ , those with tack were rated as ⁇ , and those that were liquid were rated as x. In the case of ⁇ and ⁇ , it is judged that the curability is excellent.
  • Example 1 a compound represented by the formula (1-1), which is a novel compound, was obtained.
  • Table 1 the curable resin composition in which this compound is combined with an epoxy resin and a curing agent has excellent curability and storage stability compared to a curable resin composition that does not use this compound. It is clear that
  • a one-component curable resin composition that is excellent in curability and storage stability. It can be suitably used for paints, structural adhesives and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Epoxy Resins (AREA)
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PCT/JP2022/002585 2021-02-03 2022-01-25 新規化合物、及び該化合物を含有する硬化性樹脂組成物 Ceased WO2022168665A1 (ja)

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US18/260,554 US20240084065A1 (en) 2021-02-03 2022-01-25 Novel compound, and curable resin composition containing said compound
CN202280010118.5A CN116848105A (zh) 2021-02-03 2022-01-25 新型化合物及含有该化合物的固化性树脂组合物
EP22749540.5A EP4289837A4 (en) 2021-02-03 2022-01-25 Novel compound, and curable resin composition containing said compound
JP2022579457A JP7731382B2 (ja) 2021-02-03 2022-01-25 新規化合物、及び該化合物を含有する硬化性樹脂組成物
KR1020237022619A KR20230142703A (ko) 2021-02-03 2022-01-25 신규 화합물 및 상기 화합물을 함유하는 경화성 수지조성물

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See also references of EP4289837A4

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US20240084065A1 (en) 2024-03-14
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CN116848105A (zh) 2023-10-03
KR20230142703A (ko) 2023-10-11

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