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
  • C08G59/68—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
  • C08G59/686—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 nitrogen
• • 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
• • 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
• • 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
  • C08G59/4014—Nitrogen containing compounds
  • C08G59/4042—Imines; Imides
• • 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
  • 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
  • C08G59/56—Amines together with other curing agents

Definitions

• the present invention relates to a curable resin composition, and more particularly to a curable resin composition containing an epoxy resin, a curing agent, and an imide compound having an aromatic ring structure.
• 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 curable resin composition having an excellent balance between curability and storage stability.
• a curable resin composition containing an epoxy resin, a curing agent, and a specific imide compound has an excellent balance between curability and storage stability. reached.
• the present invention is selected from (A) an epoxy resin, (B) a curing agent, and (C) an imide compound represented by the following formulas (1-1), (1-2) and (1-3) It is a curable resin composition containing at least one.
• R 11 is an optionally substituted alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted, or having a substituent represents an arylalkyl group having 7 to 20 carbon atoms, which may be R 1 to R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or 1 to 1 carbon atoms.
• R 12 and R 13 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms.
• the substituents include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, haloalkyl groups having 1 to 10 carbon atoms, haloalkoxy groups having 1 to 10 carbon atoms, halogen atoms, nitro group, nitrile group, amino group or glycidyloxy group.
• the curable resin composition of the present invention can be suitably used as a one-pack curing type curable resin composition.
• the curable resin composition of the present invention is described below.
• the curable resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, and (C) a specific imide compound.
• 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.
• epoxy resin polyglycidyl ethers of polyhydric phenol compounds or their high molecular weights are preferable, and polyglycidyl ethers of bisphenols such as bisphenol A and bisphenol F or their high molecular weights are more preferable.
• a liquid is preferable because a one-component curing type curable resin composition can be obtained.
• 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 (B) is not particularly limited, but it is preferably 1 to 70 mol, preferably 1 to 50 mol, per 100 mol of the epoxy resin (A). more preferably 3 to 30 mol.
• the molar ratio means the molar ratio calculated based on the weight average molecular weight measured by GPC.
• 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 imide compound as component (C) is at least one selected from imide compounds represented by the following formulas (1-1), (1-2) and (1-3), and has such a structure. By using, it is possible to provide a curable resin composition excellent in curability and storage stability.
• R 11 is an optionally substituted alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted, or having a substituent represents an arylalkyl group having 7 to 20 carbon atoms, which may be R 1 to R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or 1 to 1 carbon atoms.
• R 12 and R 13 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms.
• the substituents include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, haloalkyl groups having 1 to 10 carbon atoms, haloalkoxy groups having 1 to 10 carbon atoms, halogen atoms, nitro group, nitrile group, amino group or glycidyloxy group.
• Examples of the alkyl group having 1 to 10 carbon atoms in the above formulas (1-1), (1-2) and (1-3) include methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group, secondary butyl group, tertiary butyl group, amyl group, isoamyl group, secondary amyl group, tertiary amyl group, hexyl group, heptyl group, octyl group, isooctyl group, tertiary octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group and the like, and examples of the alkoxy group having 1 to 10 carbon atoms include methoxy, ethoxy group, propoxy group, isopropoxy group, butoxy group, amyloxy group and hexyloxy group.
• aryl group having 6 to 20 carbon atoms examples include phenyl group, naphthyl group and anthracenyl group. includes, for example, fluorine, chlorine, bromine and iodine.
• the arylalkyl group having 7 to 20 carbon atoms is a structure in which one or more of the hydrogen atoms of the above groups exemplified as alkyl groups are replaced with the above groups exemplified as aryl groups.
• haloalkyl groups and haloalkoxy groups having 1 to 10 carbon atoms include alkyl groups and alkoxy groups having 1 to 10 carbon atoms.
• alkoxycarbonyl group having 2 to 10 carbon atoms include those having a structure in which a carbonyl group is bonded to the oxygen atom of the above group exemplified as the alkoxy group having 1 to 10 carbon atoms. and the like.
• R 5 to R 8 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 haloalkyl group having 1 to 10 carbon atoms, or a carbon atom.
• R 14 is a hydrogen atom or an optionally substituted alkyl of 1 to 10 carbon atoms group, an aryl group having 6 to 20 carbon atoms which may have a substituent, or an arylalkyl group having 7 to 20 carbon atoms which may have a substituent.
• the substituents include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, haloalkyl groups having 1 to 10 carbon atoms, haloalkoxy groups having 1 to 10 carbon atoms, halogen atoms, nitro group, nitrile group, amino group or glycidyloxy group.
• R 5 to R 8 are hydrogen atoms and R 14 is an alkyl group having 1 to 10 carbon atoms, a phenethyl group, or a phenyl group having a methoxy group as a substituent.
• Examples of the aryl group of 6 to 20 and the arylalkyl group of 7 to 20 carbon atoms which may have a substituent include the above formulas (1-1), (1-2) and (1-3 ) include the groups exemplified as these groups.
• R 12 is an alkyl group having 1 to 10 carbon atoms and a phenyl group having a trifluoromethyl group or a methoxy group as a substituent are preferred.
• R 1 to R 4 are a hydrogen atom, a methyl group, a halogen atom, a nitro group or a butoxycarbonyl group
• R 13 is a compound having 1 to 10 carbon atoms.
• a compound which is an alkyl group or a phenyl group having a methoxy group as a substituent is preferred.
• the method for producing the imide compound as component (C) is not particularly limited, but there is, for example, the following reaction method.
• (1) Synthesize an acid anhydride and an amino group-containing compound at a low temperature of 150 ° C. or less, specifically 0 to 120 ° C., preferably 40 to 100 ° C., and then to 100 to 200 ° C.
• a method of raising the imidization reaction thermal imidization
• (2) A method of synthesizing an amic acid compound in the same manner as in (1) above and then chemically imidizing it with an imidizing agent such as acetic anhydride (chemical imidization).
• Acid anhydrides used for producing the imide compound include succinic anhydride, phthalic anhydride, 3-bromophthalic anhydride, 3-methylphthalic anhydride, 3-nitrilophthalic anhydride, norbornene. -2,3-dicarboxylic anhydride and methylnorbornene-2,3-dicarboxylic anhydride, etc.
• amino group-containing compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, and isobutylamine.
• 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, based on 1 part by mass of the acid anhydride and the amino group-containing 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 0.005 to 1 mol, per 1 mol of the acid anhydride and the amino group-containing compound. 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 target imide compound from the reaction mixture of the acid anhydride and the amino group-containing compound is not particularly limited. Just do it.
• 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 imide compound When it is necessary to further purify the isolated imide compound, it may be purified by adopting a method known as a conventional method, such as a distillation purification method, a recrystallization method, and a column chromatography method. , sludge treatment and activated carbon treatment.
• the content of the imide compound as component (C) is preferably 1 to 2000 mol, more preferably 10 to 1000 mol, and 20 to 800 mol per 100 mol of component (B). is more preferred. If the content of the imide compound is less than 1 mol, the effect of imparting stability to the curable resin composition may not be obtained, and if it exceeds 2000 mol, the curability may be adversely affected.
• 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.
• BISAEP Bisphenol A type epoxy resin
• 2E4MZ 2-ethyl-4-methylimidazole
• (1-1) component (C) , (1-2) and (1-3) were used in molar ratios shown in Table 1 to produce a curable resin composition.
• the imide compound has a high melting point
• mix BISAEP and the corresponding imide compound in the stated blending amounts heat to a temperature at which the mixture becomes a completely uniform liquid, cool to room temperature, and then add a predetermined amount of 2E4MZ. to produce a curable resin composition. Curability and storage stability were evaluated using the resulting curable resin composition. Table 1 shows the results.
• the curable resin composition was placed in a glass bottle and cured by heating at 150° C. for 1 hour.

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• 2022
  • 2022-01-25 JP JP2022579458A patent/JPWO2022168666A1/ja active Pending
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