Classifications

• • 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
  • 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
  • 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
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—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
  • C08G59/66—Mercaptans

Definitions

• the present invention relates to an epoxy resin composition in which two types of specific epoxy compounds are combined.
• Epoxy resins exhibit excellent properties in a wide range of applications such as adhesives, paints, electrical insulating materials, and civil engineering and construction materials. In particular, it is used in sealants, castings, and adhesives in the electrical and electronic fields, taking advantage of the characteristics of epoxy resin such as adhesiveness and heat resistance. It is often required to maintain adhesiveness and heat resistance even under high humidity.
• Bisphenol-type epoxy resins which are inexpensive, readily available and commonly used, can be cured with a curing agent to obtain a cured product with adhesiveness and heat resistance, but the elastic modulus of the cured product is too large. Therefore, in an environment with a large temperature difference or in an environment of high humidity, there are problems such as cracking or peeling from the base material.
• One of the means to solve the above problem is to lower the elastic modulus of the cured product.
• the agent bleeds out after curing and reduces adhesion.
• As means for increasing the reliability of the cured product by lowering the elastic modulus to some extent while maintaining the adhesiveness there is a method of using a compound having an epoxy group and a long-chain alkyl group in combination (for example, Patent Document 1, etc.). .
• Patent Document 1, etc. a method of using a compound having an epoxy group and a long-chain alkyl group in combination.
• the problem to be solved by the present invention is to provide an epoxy-based material for obtaining a cured product with a reduced elastic modulus in order to maintain reliability even under conditions of large environmental changes.
• the present inventors have made intensive studies and found an epoxy resin composition using two types of specific epoxy compounds in combination, leading to the present invention. That is, the present invention provides an epoxy resin containing (A) an epoxy compound A represented by the following general formula (1), (B) an epoxy compound B represented by the following general formula (2), and (C) a curing agent. composition.
• R 1 and R 2 each independently represent an alkylene group having 2 to 4 carbon atoms
• R 3 represents a methylene group or -C(CH 3 ) 2 -
• a and b each independently represent a number from 1 to 10.
• R 4 represents a hydrocarbon group having 6 to 20 carbon atoms.
• the effect of the present invention is to provide an epoxy resin composition having a low elastic modulus necessary for maintaining reliability even under conditions of great environmental change.
• the epoxy resin composition can be suitably used in various applications such as sealing agents, castings, and adhesives in the electrical and electronic fields.
• the epoxy resin composition of the present invention comprises (A) an epoxy compound A represented by the following general formula (1), (B) an epoxy compound B represented by the following general formula (2), and (C) a curing agent, contains
• R 1 and R 2 each independently represent an alkylene group having 2 to 4 carbon atoms
• R 3 represents a methylene group or -C(CH 3 ) 2 -
• a and b each independently represent a number from 1 to 10.
• R 4 represents a hydrocarbon group having 6 to 20 carbon atoms.
• R 1 and R 2 are each independently an alkylene group having 2 to 4 carbon atoms, such as an ethylene group, a propylene group, an isopropylene group, butylene group, isobutylene group, and the like.
• ethylene group, propylene group and isopropylene group are preferable, and isopropylene group is particularly preferable, from the viewpoint that a cured product having a low elastic modulus can be obtained.
• R 1 and R 2 may be the same group or different groups, but from the viewpoint of easy synthesis, they are preferably the same group.
• a and b are each independently a number of 1 to 10, preferably 1 to 3 from the viewpoint of the balance between elastic modulus and curability. .
• a and b may be the same number or different numbers, but the same number is preferable from the viewpoint of easy synthesis.
• the average values of a and b are preferably 1 to 3, respectively.
• Epoxy compound A can be produced by a known method. Specifically, for example, a bisphenol compound such as bisphenol A or bisphenol F is added with an alkylene oxide using an alkali catalyst such as sodium hydroxide, and then epoxidized using epichlorohydrin. . When bisphenol A is used, epoxy compound A in which R 3 is —C(CH 3 ) 2 — is obtained, and when bisphenol F is used, epoxy compound A in which R 3 is a methylene group is obtained.
• alkylene oxide examples include ethylene oxide, propylene oxide, and butylene oxide.
• the number of a and b can be adjusted by adjusting the number of moles of alkylene oxide added to 1 mol of the bisphenol compound. For example, when 2 mol of propylene oxide is added, the number of a and b is Theoretically, each is 1.
• a method for epoxidation using epichlorohydrin for example, 1.6 to 3 mol of a basic compound such as sodium hydroxide and 2 to 2 to A method of epoxidation at 40 to 90° C. under normal pressure or reduced pressure conditions using 20 mol and, if necessary, a phase transfer catalyst can be mentioned. At this time, excess epichlorohydrin is preferably removed by distillation.
• phase transfer catalyst examples include tetramethylammonium salts and tetrabutylammonium salts.
• a phase transfer catalyst it is preferable to use 0.001 to 0.1 mol of the phase transfer catalyst per 1 mol of the alkylene oxide adduct of the bisphenol compound.
• the solvent examples include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate, and cyclohexanone; tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane.
• ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate, and cyclohexanone
• tetrahydrofuran 1,2-dimethoxyethane, 1,2-diethoxyethane.
• Ethers such as propylene glycol monomethyl ether; Esters such as ethyl acetate and n-butyl acetate; Aromatic hydrocarbons such as benzene, toluene, and xylene; Halogenated aliphatics such as carbon tetrachloride, chloroform, trichlorethylene, and methylene chloride Hydrocarbons; Halogenated aromatic hydrocarbons such as chlorobenzene can be mentioned.
• the resulting epoxy compound A can be separated and purified by oil-water separation using water or an organic solvent, filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, or a combination thereof. Separation and purification may be performed by
• a commercially available product may be used as the epoxy compound A, which is the component (A) of the present invention. 4003S, EP-4010S, EP-4000L and the like.
• R 4 is a hydrocarbon group having 6 to 20 carbon atoms, and such hydrocarbon groups include, for example, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 2-heptyl group, 1,4-dimethylpentyl group, tert-heptyl group, 2-methyl-1 -isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, 2-methylhexyl group, 2-propylhexyl group, n-nonyl group, isononyl group, n -decyl group, isodecyl group, n-undecyl group,
• Epoxy compound B which is the component (B) of the present invention, is preferably a cardanol-type epoxy compound from the viewpoint that it is easily available and a cured product with lower elasticity can be obtained.
• Cardanol is a phenolic lipid obtained by thermal decomposition of any naturally occurring anacardic acid, and specifically has a chemical structure represented by the following general formula (3).
• R is one of the groups shown on the right side of the parenthesis, and * represents a site that binds to the aromatic ring.
• cardanol is a mixture of phenolic compounds represented by the above general formula (3), and the ratio of each compound varies depending on what is collected from nature and on the purification conditions.
• About 5% by mass of a compound having an n-pentadecyl group having 15 carbon atoms, about 35% by mass of a compound having an (8Z)-8,11-pentadecenyl group having one unsaturated group, and two unsaturated groups About 20% by mass of a compound having one (8Z,11Z)-8,11-pentadienyl group, and a compound having a (8Z,11Z)-8,11,14-pentatrienyl group having three unsaturated groups
• Mixtures are mentioned that are about 40% by weight.
• a preferred form of the epoxy compound B which is the (B) component of the present invention, is a compound obtained by epoxidizing the cardanol described above.
• the method of epoxidation is not particularly limited, and a known method can be used. That is, with respect to 1 mol of cardanol, 0.8 to 1.5 mol of a basic compound such as sodium hydroxide, 2 to 20 mol of epichlorohydrin, and if necessary using a phase transfer catalyst, normal pressure or reduced pressure A method of epoxidation at 40 to 90° C. under these conditions may be mentioned. At this time, excess epichlorohydrin is preferably removed by distillation.
• the resulting epoxy compound B can be separated and purified by oil-water separation using water or an organic solvent, filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, or a combination thereof. Separation and purification may be performed by
• a commercial product may be used as the epoxy compound B, which is the component (B) of the present invention, and examples thereof include NC 513, Ultra LITE 513, and LITE 513E manufactured by Cardolite.
• the mass ratio A/B of component (A) and component (B) is 90/10 to 10/90 from the viewpoint of the balance between curability and elastic modulus of the cured product. is preferred, 80/20 to 20/80 is more preferred, 70/30 to 30/70 is even more preferred, and 60/40 to 40/60 is particularly preferred.
• the epoxy resin composition of the present invention may use a compound having an epoxy group other than the components (A) and (B) (hereinafter referred to as other epoxy compounds).
• other epoxy compounds include, for example, n-butyl glycidyl ether, C 12 -C 14 alkyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-sec- Reactive diluents having one epoxy group such as butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, glycidyl methacrylate, and tertiary carboxylic acid glycidyl ester; Polyglycidyl etherified products of hydric phenol compounds; dihydroxynaphthalene
• Polyglycidyl etherates ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, dicyclopentadiene dimethanol, 2,2-bis(4-hydroxycyclohexylpropane (hydrogenated bisphenol A), glycerin, Polyglycidyl ethers of polyhydric alcohols such as trimethylolpropane, pentaerythritol and sorbitol; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acids, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid
• a urethane-modified epoxy resin has an epoxy group and a urethane bond in its molecule, and can be obtained, for example, by reacting an epoxy compound having a hydroxyl group in its molecule with a compound having an isocyanate group. It can be obtained by a known method described in JP-A-2016-210922.
• reactive diluents having one epoxy group and polyglycidyl ethers of mononuclear polyhydric phenol compounds are preferable from the viewpoint of the balance between the workability of the resin composition and the elastic modulus of the cured product.
• A-type epoxy resin, bisphenol F-type epoxy resin and t-butylphenylglycidyl ether are more preferred.
• the amount used is preferably 0 to 90% by mass based on the total amount of compounds having an epoxy group, from the viewpoint of the balance between curability and elastic modulus of the cured product. It is more preferably 60% by mass, and even more preferably 0 to 30% by mass.
• Examples of the (C) curing agent of the present invention include amine-based curing agents, thiol-based curing agents, acid anhydrides, phenolic resins, cationic polymerization initiators, and the like.
• a cured product with excellent curability and good flexibility can be obtained.
• amine curing agent examples include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, and polyoxypropylenetriamine; isophoronediamine, menzenediamine, bis(4-amino -3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5 5) Alicyclic polyamines such as undecane; m-phenylenediamine, p-phenylenediamine, tolylene-2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine, mesitylene-2,6 -mononuclear polyamine
• the amine-based curing agent may be a modified amine obtained by reacting an amine compound, an epoxy compound, and, if necessary, an isocyanate compound or urea.
• amine compound examples include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, alkylenediamines such as hexamethylenediamine; diethylenetriamine, triethylenetriamine , tetraethylenepentamine and other polyalkylpolyamines; 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'-diaminodic
• Examples of the epoxy compound for obtaining the modified amine include the compounds exemplified for the other epoxy compounds above, and the (A) component and (B) component can also be used.
• Isocyanate compounds for obtaining the modified amine include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethylxylylene aromatic diisocyanates such as isocyanate, 1,5-naphthylene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate; isophorone diisocyanate , dicyclohexylmethane-4,4′-diisocyanate, trans-1,4-cyclohexyl diisocyanate, norbornene diisocyanate; tetramethylene diisocyan
• triphenylmethane triisocyanate 1-methylbenzol-2,4,6-triisocyanate, dimethyltriphenylmethanetetraisocyanate, and the like.
• Examples of methods for producing a modified amine obtained by reacting an amine compound, an epoxy compound, and urea include known methods described in Japanese Patent Publication No. 06-006620, Japanese Patent No. 3837134, and the like.
• the amine-based curing agent may be an amine-based latent curing agent.
• the latent curing agent include latent curing agents such as dicyandiamide-type, imidazole-type and polyamine-type compounds which, when mixed with an epoxy resin at room temperature, cause little change in viscosity and physical properties of the mixture.
• Examples of the dicyandiamide-type latent curing agent include dicyandiamide alone or, if necessary, a curing accelerator described later.
• the imidazole-type latent curing agent is obtained, for example, by reacting an epoxy compound with an imidazole compound containing active hydrogen at 50 to 150° C. for 1 to 20 hours, optionally using a solvent. be able to. When a solvent is used, the solvent is removed at 80 to 200° C. under normal pressure or reduced pressure after the reaction is completed.
• imidazole compound used in the production of the imidazole-type latent curing agent examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, and the like. is mentioned.
• Examples of the epoxy compound used in the production of the imidazole-type latent curing agent include the compounds exemplified in the other epoxy compounds above, and the (A) component and (B) component can also be used.
• Solvents used in the production of the imidazole-type latent curing agent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, propylene glycol monomethyl ether acetate, and cyclohexanone; tetrahydrofuran, 1,2-dimethoxy Ethers such as ethane, 1,2-diethoxyethane and propylene glycol monomethyl ether; Esters such as ethyl acetate and n-butyl acetate; Aromatic hydrocarbons such as benzene, toluene and xylene; Carbon tetrachloride, chloroform and trichlorethylene , halogenated aliphatic hydrocarbons such as methylene chloride; and halogenated aromatic hydrocarbons such as chlorobenzene.
• ketones such as methyl ethyl ketone,
• the polyamine-type latent curing agent can be obtained, for example, by reacting an epoxy compound with polyamine at 50 to 150° C. for 1 to 20 hours, using a solvent if necessary. When a solvent is used, the solvent is removed at 80 to 200° C. under normal pressure or reduced pressure after the reaction is completed.
• Examples of the polyamine used in the production of the polyamine-type latent curing agent include compounds having at least two amino groups among the amine compounds used in the above-mentioned modified amines.
• the epoxy compound and solvent used in the production of the polyamine-type latent curing agent include those similar to those used in the production of the imidazole-type latent curing agent.
• the above amine-based latent curing agent may be used in combination with phenol resins, which will be described later, in order to improve the storage stability of the composition.
• the amount of phenolic resins used in combination is, for example, 10 to 50% by mass based on the total mass of the amine-based latent curing agent.
• ADEKA HARDNER EH-3636AS manufactured by ADEKA Corporation; dicyandiamide type latent curing agent
• ADEKA HARDNER EH-4351S manufactured by ADEKA Corporation; dicyandiamide type latent curing agent
• ADEKA HARDNER EH-5011S manufactured by ADEKA Corporation; imidazole type latent curing agent
• ADEKA HARDNER EH-5046S manufactured by ADEKA Corporation; imidazole type latent curing agent
• ADEKA HARDNER EH -4357S manufactured by ADEKA Corporation; polyamine-type latent curing agent
• ADEKA HARDNER EH-5057P manufactured by ADEKA Corporation; polyamine-type latent curing agent
• ADEKA HARDNER EH-5057PK manufactured by ADEKA Corporation; polyamine type
• the amount used is the component (A), the component (B), and other epoxy compounds, from the viewpoint of the balance between the curability and the elastic modulus of the cured product. It is preferably 1 to 100 parts by mass, more preferably 5 to 60 parts by mass, based on 100 parts by mass of the total mass of.
• thiol-based curing agent examples include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), dipentaerythritol hexakis (3-mercaptopropionate), and dipentaerythritol hexakis.
• the amount used is, from the viewpoint of the balance between the curability and the elastic modulus of the cured product, the components (A), (B), and other epoxy compounds. It is preferably 1 to 100 parts by mass, more preferably 40 to 80 parts by mass, based on 100 parts by mass of the total mass of.
• Examples of the acid anhydride include hymic anhydride, phthalic anhydride, maleic anhydride, methyl hymic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydro
• Examples include phthalic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, benzophenonetetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and hydrogenated methyl nadic anhydride.
• the amount of the acid anhydride used is, from the viewpoint of the balance between the curability and the elastic modulus of the cured product, the amount of the component (A), the component (B), and other epoxy compounds. It is preferably from 30 to 300 parts by mass, more preferably from 50 to 100 parts by mass, relative to the total mass of 100 parts by mass.
• phenol resins 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, trisphenylol.
• Examples include polyhydric phenol compounds such as ring-modified novolac resins (polyhydric phenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).
• the amount of use of the (A) component, (B) component, and other epoxy compounds is determined from the viewpoint of the balance between the curability and the elastic modulus of the cured product. It is preferably 10 to 200 parts by mass, more preferably 50 to 100 parts by mass, based on 100 parts by mass of the total mass.
• the cationic polymerization initiator is a compound capable of releasing a substance that initiates cationic polymerization upon irradiation with heat or energy rays.
• a particularly preferred cationic initiator is an onium double salt or derivative thereof that releases a Lewis acid upon heat or light irradiation.
• Representative examples of such compounds include salts of cations and anions represented by the following general formulas. [A] m+ [B] m-
• the cation [A] m+ is preferably onium, and its structure can be represented, for example, by the general formula [(R 5 ) p Q] m+ .
• R 5 is an organic group having 1 to 60 carbon atoms and optionally containing any number of atoms other than carbon atoms, and p is an integer of 1 to 5.
• Each of the p R 5 's is independent and may be the same or different.
• at least one is preferably the above-described organic group having an aromatic ring.
• the anion [B] m- is preferably a halide complex, and its structure can be represented, for example, by the general formula [LX r ] m- .
• L is a metal or metalloid that is the central atom of the halide complex, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V , Cr, Mn, Co, etc.
• X is a halogen atom.
• anion [LX r ] m ⁇ represented by the above general formula include tetrafluoroborate (BF 4 ) ⁇ , hexafluorophosphate (PF 6 ) ⁇ , hexafluoroantimonate (SbF 6 ) ⁇ , hexafluoroantimonate (SbF 6 ) ⁇ , fluoroarsenate (AsF 6 ) ⁇ , hexachloroantimonate (SbCl 6 ) ⁇ and the like.
• anions that can be used in the present invention include perchlorate ion (ClO 4 ) ⁇ , trifluoromethylsulfite ion (CF 3 SO 3 ) ⁇ , fluorosulfonate ion (FSO 3 ) ⁇ , toluene Sulfonic acid anions, trinitrobenzenesulfonic acid anions, and the like can be mentioned.
• the onium salt for example, the following aromatic onium salts a) to c) can be used. Moreover, from these, the 1 type can be used individually or in mixture of 2 or more types.
• Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, and 4-methylphenyldiazonium hexafluorophosphate
• triphenylsulfonium hexafluoroantimonate tris(4-methoxyphenyl)sulfonium hexafluoroantimonate,
• cationic polymerization initiators other than the above include ( ⁇ 5 -2,4-cyclopentadien-1-yl)[(1,2,3,4,5,6,- ⁇ )-(1-methylethyl ) benzene]-iron-hexafluorophosphate and other iron-arene complexes, and aluminum complexes such as tris(acetylacetonato)aluminum, tris(ethylacetonatoacetato)aluminum, tris(salicylaldehyde)aluminum and triphenylsilanol. Also included are mixtures with silanols such as
• cationic polymerization initiators include, for example, Kayarad PCI-220 (manufactured by Nippon Kayaku Co., Ltd.), Kayarad PCI-620 (same), UVI-6990 (manufactured by Union Carbide), and Adeka Optomer SP.
• the amount used is, from the viewpoint of the balance between the curability and the elastic modulus of the cured product, the components (A), (B), and other epoxy compounds. It is preferably 0.1 to 20 parts by mass, more preferably 1 to 7 parts by mass, based on 100 parts by mass of the total mass of.
• amine-based curing agents or thiol-based curing agents are preferable from the viewpoint of low-temperature curing.
• the epoxy resin composition of the present invention may be used in combination with a curing accelerator.
• a curing accelerator By using a curing accelerator together, the curing speed can be improved.
• curing accelerators include phosphines such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, imidazoles such as 1-cyanoethyl-2-methylimidazole; imidazole salts which are salts of said imidazoles with trimellitic acid, isocyanuric acid, boron or the like; benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl ) amines such as phenol; quaternary ammonium salts such as trimethylammonium chloride; 3-(p-chlorophenyl)-1,1-
• the curing accelerator may be of a core-shell type. Specifically, as described in Japanese Patent Publication No. 07-005708, Japanese Patent No. 4405741, etc., solid tertiary amine as a core component, epoxy A masterbatch type curing accelerator in which a reaction product of a resin and an amine compound is dispersed in an epoxy resin can be mentioned. From the viewpoint of the storage stability of the epoxy resin composition, these curing accelerators are preferably used in combination with a thiol-based curing agent or an acid anhydride.
• the masterbatch type curing accelerator may be a commercially available product, for example, Novacure series manufactured by Asahi Kasei Corporation, HX-3742, HX-3721, HXA9322HP, HXA3922HP, HXA3932HP, HXA5945HP, HXA9382HP, etc. mentioned.
• the epoxy resin composition of the present invention may optionally contain a silane coupling agent.
• Silane coupling agents include, for example, ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropyltriethoxysilane, N- ⁇ -(aminoethyl)-N′- ⁇ -(amino ethyl)- ⁇ -aminopropyltriethoxysilane, ⁇ -anilinopropyltriethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltriethoxysilane, vinyltriethoxysilane, N- ⁇ -(N-vinylbenzylaminoethyl)- ⁇ -aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane,
• silane coupling agent a silane coupling agent having an epoxy group is preferable from the viewpoint of improving the adhesiveness when the epoxy resin composition of the present invention is used as an adhesive.
• silane coupling agents may be used, for example, KBM-403, KBE-403, KBM-402 manufactured by Shin-Etsu Chemical Co., Ltd. may be used.
• the amount used is 100 parts by mass of the total weight of the components (A), (B), and other epoxy compounds, from the viewpoint of the balance between the curability and the elastic modulus of the cured product. It is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 5 parts by mass.
• An inorganic filler may be added to the epoxy resin composition of the present invention, if necessary.
• examples of such inorganic fillers include silica such as fused silica, crystalline silica, and fumed silica, magnesium hydroxide, aluminum hydroxide, zinc borate, zinc molybdate, calcium carbonate, silicon nitride, silicon carbide, and boron nitride. , calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, titania, or the like, beads obtained by spheroidizing these powders, and glass fibers.
• Additives other than the inorganic filler may be used in combination with the epoxy resin composition of the present invention, if necessary.
• the above additives include non-reactive diluents (plasticizers) such as dioctyl phthalate, dibutyl phthalate, benzyl alcohol and coal tar; fibrous fillers such as glass fiber, pulp fiber, synthetic fiber and ceramic fiber; Reinforcing materials such as glass cloth, aramid cloth, carbon fiber; pigments; candelilla wax, carnauba wax, Japan wax, wart wax, beeswax, lanolin, spermaceti, montan wax, petroleum wax, aliphatic waxes, aliphatic esters, fats Lubricants such as group ethers, aromatic esters, aromatic ethers; thickeners; thixotropic agents; antioxidants; light stabilizers; UV absorbers; Commonly used additives such as alumina can be mentioned.
• tacky resins such as xylene resins
• the epoxy resin composition of the present invention preferably has a low total chlorine content. is more preferred. Since it is preferable that the total chlorine content is small, the ideal value of the total chlorine content is 0 ppm. In the present invention, the total chlorine content can be measured by combustion-coulometric method.
• the epoxy resin composition of the present invention preferably has a viscosity of 20 to 600 mPa ⁇ s, more preferably 50 to 400 mPa ⁇ s.
• the viscosity can be measured with a cone-plate rotational viscometer (E-type viscometer).
• the epoxy resin composition of the present invention can be produced by stirring, melting, mixing, and dispersing components (A) to (C) and optional components to be added as necessary, while heat-treating as necessary. can.
• the device used for stirring, melting, mixing and dispersing is not particularly limited. Bead mills, planetary stirrers and the like can be used. Also, these devices may be used in combination as appropriate.
• the epoxy resin composition of the present invention can be used as a paint for concrete, cement, mortar, various metals, leather, glass, rubber, plastics, wood, cloth, paper, etc.; Electronic circuits such as build-up adhesive films, die attach agents, underfill materials for flip chip mounting, glove top materials, liquid sealing materials for TCP, conductive adhesives, liquid crystal sealing materials, coverlays for flexible substrates, resist inks, etc. Resin materials for substrates; semiconductor sealing materials; optical materials such as optical waveguides and optical films; resin casting materials; adhesives; It can be applied to various uses such as optical semiconductor devices; fiber-reinforced resin moldings such as CFRP.
• the epoxy resin composition of the present invention has the inherent adhesiveness of epoxy resins, and has a low elastic modulus, so that the cured product has good reliability. , and adhesives for electronic parts, and particularly suitable for use as adhesives and sealants for parts for camera modules.
• Raw materials used in the examples are as follows.
• A-2 The epoxy compound produced in Production Example 2 (in general formula (1), R 1 and R 2 are isopropylene groups, R 3 is —C(CH 3 ) 2 —, a and b containing compounds with an average value of 1 each as a main component)
• D-1 ADEKA RESIN EP-4100E, bisphenol type epoxy resin (manufactured by ADEKA Co., Ltd.)
• D-2 ADEKA GLYCIROL ED-509S, t-butylphenyl glycidyl ether (manufactured by ADEKA Co., Ltd.)
• B-1 LITE 513E, cardanol type epoxy compound (manufactured by Cardolite)
• C-1 ADEKA HARDNER EH-5011S, imidazole type latent curing agent (manufactured by ADEKA Co., Ltd.)
• Examples 1 to 5 Comparative Examples 1 to 4
• Various materials were added to a 500 mL disposable cup at the compounding ratio shown in Table 1, stirred with a spatula for 10 minutes, and then stirred with a planetary stirrer to produce epoxy resin compositions of Examples and Comparative Examples. Curability, flexibility, workability, total chlorine content and viscosity of the obtained epoxy resin compositions were evaluated by the following evaluation methods. Table 1 shows the results.
• Total chlorine content was measured using a TOX-2100 total organic halogen measuring device manufactured by Nitto Seiko Analyticc Co., Ltd.
• the epoxy resin composition of the present invention was found to have an excellent balance between curability and flexibility.
• Comparative Examples 1 to 4 in which the epoxy resin composition of the present invention was not used, satisfactory results were not obtained in either curability or flexibility.
• Comparative Example 3 it was not cured under the curing conditions of 120° C. and 2 hours, so flexibility could not be evaluated.

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• 2022
  • 2022-06-22 CN CN202280038767.6A patent/CN117413002A/zh active Pending
  • 2022-06-22 EP EP22828452.7A patent/EP4361193A4/en active Pending
  • 2022-06-22 KR KR1020237041149A patent/KR20240023506A/ko active Pending
  • 2022-06-22 JP JP2023530087A patent/JPWO2022270536A1/ja active Pending
  • 2022-06-22 US US18/565,337 patent/US20240301128A1/en active Pending
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