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
  • C08G59/20—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
• • 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
  • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

• the present invention relates to an epoxy resin mixture that gives a composition excellent in fluidity and a cured product excellent in flame retardancy and heat resistance.
• the present invention relates to electrical and electronic material applications that require high functionality, particularly to an epoxy resin mixture, an epoxy resin composition, and a cured product thereof suitable as a semiconductor sealant and a thin film substrate material.
• Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been.
• the thickness of the layer is thin, and in order to reduce the linear expansion coefficient, filling with fine filler Necessary. Therefore, in this application as well, it is necessary to reduce the viscosity of the resin composition as before.
• the present invention is an epoxy resin mixture capable of providing an epoxy resin composition capable of providing a cured product excellent in heat resistance and flame retardancy while having excellent fluidity, an epoxy resin composition containing the same, And it aims at providing the hardened
• the present invention is (1) 1,1′-bis (2-glycidyloxynaphthyl) and substituted (or unsubstituted) 4,4′-bisglycidyloxybiphenyl (provided that the substituent has an aromatic ring, the number of substituents is 4 or less.
• the epoxy resin mixture according to item (1) obtained by reacting with (4) The epoxy resin composition according to any one of the preceding items (1) to (3), and an epoxy resin composition essential to contain a curing agent; (5) The epoxy resin mixture according to any one of the above items (1) to (3), and an epoxy resin composition essential to contain a polymerization catalyst; (6) The present invention provides a cured product obtained by curing the epoxy resin composition according to (4) or (5).
• the epoxy resin mixture of the present invention has an extremely low viscosity and is an epoxy resin that contributes to the fluidity of the composition, and its cured product is excellent in heat resistance and flame retardancy. Therefore, it is useful for insulating materials for electrical and electronic parts, laminates (printed wiring boards, build-up boards, etc.), various composite materials including CFRP, adhesives, paints, and the like. In particular, it is extremely useful for a semiconductor sealing material for protecting a semiconductor element.
• the epoxy resin mixture of the present invention comprises 1,1′-bis (2-glycidyloxynaphthyl) and substituted or unsubstituted 4,4′-bisglycidyloxybiphenyl (provided that the aromatic ring has a substituent, Is 4 or less and the carbon number is 4 or less).
• 1,1′-bis (2-glycidyloxynaphthyl) is a reaction product of binol and epihalohydrin
• 4,4′-bisglycidyloxybiphenyl is 4,4′-biphenol (provided that the aromatic ring has a substituent, the number of substituents is 4 or less, and the number of carbon atoms is 4 or less).
• the substituent is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a methoxy group, an ethoxy group, or a propoxy group.
• R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and an alkoxy group
• G represents a glycidyl group
• t represents an integer of 1 to 4
• substituted or unsubstituted 4,4′-biphenol include the following structures.
• the purity is preferably 90 area% or more, more preferably 93 area% or more, further preferably 95 area% or more, and particularly preferably 98 area% or more in terms of GPC.
• Impurities include those having a quinone structure and raw material naphthol compounds, each of which is 2 area% or less, preferably 1 area% or less. Purity can be controlled by crystallization or washing. If the purity is low, the properties of the resulting epoxy resin mixture of the present invention may deteriorate. Further, the loss on drying is preferably 0.2% or less, more preferably 0.1% or less. If the loss on drying is large, the production line may be soiled in the production process.
• the melting point is preferably 200 to 220 ° C, more preferably 212 to 219 ° C.
• 4,4′-biphenol (provided that the aromatic ring has a substituent, the number of substituents is 4 or less and the number of carbon atoms is 4 or less). Specific examples thereof include 4,4′-biphenol, 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diol, and 3,3′-dimethylbiphenyl-4,4′-. Diol etc. are mentioned. In the present invention, 4,4′-biphenol and 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diol are preferable from the viewpoint of availability, and 4,4′-diol is preferable from the handling property of the epoxy resin mixture. 4'-biphenol is preferred.
• the number of substituents is 4 or less and the number of carbon atoms is 4 or less.
• the temperature is preferably 70 to 140 ° C, more preferably 80 to 130 ° C.
• the epoxy resin mixture of the present invention has 1,1′-bis (2-glycidyloxynaphthyl) and substituted (or unsubstituted) 4,4′-bisglycidyloxybiphenyl (provided that the aromatic ring has a substituent)
• the number of substituents is 4 or less and the number of carbon atoms is 4 or less. Even if they are mixed evenly, binol and substituted (or unsubstituted) 4,4′-biphenol (however, the substituent is an aromatic ring) In this case, the number of substituents may be 4 or less, and the number of carbon atoms may be 4 or less.) May be mixed and reacted with epihalohydrin. In the present invention, the latter is particularly preferred from the viewpoint of ease of production and molecular connections.
• binol (AA) and 4,4′-biphenol provided that the aromatic ring has a substituent, the number of substituents is 4 or less, and the number of carbons is 4 or less. .
• (BB) is simultaneously reacted with epihalohydrin to form an epoxy resin mixture.
• the mixture of (AA) and (BB) is referred to as the phenol mixture of the present invention.
• the epihalohydrin is preferably epichlorohydrin which is industrially easily available.
• the amount of epihalohydrin used is usually 3.0 to 15 moles, preferably 3.0 to 10 moles, more preferably 3.5 to 8.5 moles, particularly preferably 1 mole per hydroxyl group of the phenol mixture of the present invention. 4.5 to 8.5 moles.
• the amount is less than 3.0 mol, the epoxy equivalent may be increased, and the workability of the resulting epoxy resin may be deteriorated.
• the amount exceeds 15 mol the amount of the solvent may be increased.
• an alkali metal hydroxide for the reaction with epihalohydrin.
• the alkali metal hydroxide that can be used include sodium hydroxide, potassium hydroxide, and the like, and a solid substance may be used, or an aqueous solution thereof may be used. From the viewpoint of property and handling, it is preferable to use a solid material molded into a flake shape.
• the amount of alkali metal hydroxide used is usually 0.90 to 1.5 mol, preferably 0.95 to 1.25 mol, more preferably 0.99 to 1. mol, per mol of hydroxyl group in the phenol mixture. 15 moles.
• quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride may be added as a catalyst.
• the amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol mixture of the present invention.
• a nonpolar protic solvent dimethylsulfoxide, dioxane, dimethylimidazolidinone, etc., dimethylsulfoxide and dioxane are preferred in the present invention
• an alcohol having 1 to 5 carbon atoms are used in combination. Is preferred. Examples of the alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol (methanol is preferred in the present invention).
• the amount of the nonpolar protic solvent or alcohol having 1 to 5 carbon atoms is usually 2 to 50% by weight, preferably 4 to 25% by weight, based on the amount of epihalohydrin used.
• epoxidation may be performed while controlling the moisture in the system by a technique such as azeotropic dehydration.
• a technique such as azeotropic dehydration.
• the electrical reliability of the obtained epoxy resin mixture may be lowered, and it is preferable to synthesize with the water content controlled to 5% or less.
• an epoxy resin mixture is obtained using a nonpolar proton solvent, an epoxy resin mixture having excellent electrical reliability can be obtained, and therefore a nonpolar proton solvent can be suitably used.
• the reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. In particular, in the present invention, 60 ° C. or higher is preferable for higher-purity epoxidation, and reaction under conditions close to reflux conditions is particularly preferable.
• the reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 3 hours. If the reaction time is short, the reaction cannot proceed, and if the reaction time is long, a by-product may be formed. After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure.
• the recovered epoxy resin mixture is a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.).
• a ketone compound having 4 to 7 carbon atoms for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.
• the amount of the alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, relative to 1 mol of the hydroxyl group of the phenol mixture of the present invention used for epoxidation.
• the reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
• the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin mixture of the present invention.
• a plate-like body plate shape, sheet shape, belt shape or the like having a temperature of 100 ° C. or less, more preferably 80 ° C. or less.
• a stepwise cooling method of cooling at 60 ° C. or lower after cooling at 80 ° C. or lower may be used.
• the appearance of the most preferable epoxy resin mixture obtained has a turbid color with a crystallinity (specifically, it is not cloudy or amorphous).
• 1,1′-bis (2-glycidyloxynaphthyl) and substituted (or unsubstituted) 4,4′-bisglycidyloxybiphenyl provided that the aromatic ring has a substituent
• the number of substituents is 4 or less and the number of carbon atoms is 4 or less.
• the binol structure and the biphenol structure are —CH 2.
• Preferred resin properties of the epoxy resin mixture of the present invention include epoxy equivalents (1,1′-bis (2-glycidyloxynaphthyl) and 4,4′-bisglycidyloxybiphenyl which are mixtures of the obtained epoxy resin of the present invention) (And an average value of epoxy equivalents of the structure (C) when the structure (C) is contained) is 190 to 350 g / eq. And more preferably 200 to 300 g / eq. It is. When the epoxy equivalent is within the above range, an epoxy resin excellent in heat resistance and electrical reliability of the cured product can be obtained. Epoxy equivalent is 350 g / eq.
• the ring of the epoxy is not completely closed, and many compounds having no functional group may be contained, and the epoxy equivalent may not be lowered. Many of these compounds that could not be ring-closed often contain chlorine, and as an electronic material application, the release of chlorine ions under high-temperature and high-humidity conditions and the resulting corrosion of wiring may occur.
• the total chlorine remaining in the epoxy resin is preferably 5000 ppm or less, more preferably 3000 ppm or less, and particularly preferably 2000 ppm or less.
• about chlorine ion and sodium ion, 5 ppm or less is preferable respectively, More preferably, it is 3 ppm or less.
• Chlorine ions are described above. Needless to say, cations such as sodium ions are also very important factors particularly in power device applications, and contribute to a defective mode when a high voltage is applied.
• the epoxy resin mixture of the present invention has a form on the resin having a softening point.
• the softening point is preferably 55 to 130 ° C, more preferably 60 to 120 ° C. If the softening point is too low, blocking during storage may be a problem. On the other hand, if the softening point is too high, handling may be reduced during kneading with other resins.
• the melt viscosity is preferably 2 Pa ⁇ s (ICI melt viscosity 150 ° C. cone plate method) or less. When an inorganic material (filler or the like) is mixed and used, the fluidity is lowered, and the glass cloth or the like has a finer mesh and the impregnation property may be lowered.
• the epoxy resin composition of the present invention containing the epoxy resin mixture of the present invention (hereinafter also referred to as curable resin composition) will be described.
• a curing agent or a polymerization catalyst is used as an essential component.
• the curable resin composition of this invention can classify
• the curable resin composition A is a composition containing the epoxy resin mixture of the present invention and a curing agent as essential components.
• the curable resin composition B is a composition containing the epoxy resin mixture of the present invention and a polymerization catalyst as essential components.
• the polymerization catalyst that can be contained in the curable resin composition B of the present invention can be used without limitation as long as it is a catalyst that is polymerized by heat or light. Specifically, a curing accelerator or an acidic curing catalyst can be used.
• curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza.
• -Tertiary amines such as bicyclo (5,4,0) undecene-7
• phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, etc.
• Quaternary phosphonium salts such as quaternary ammonium salts, triphenylbenzyl phosphonium salts, triphenylethyl phosphonium salts, tetrabutyl phosphonium salts (counter ions of quaternary salts are halogen, organic acid ions, Special designations such as hydroxide ions Bur, in particular an organic acid ion, a hydroxide ion.) Include metal compounds such as tin octylate. When a curing accelerator is used, 0.01 to 5.0 parts by weight is used as necessary with respect to 100 parts by weight of the epoxy resin.
• a cationic polymerization initiator is preferable, and a light or thermal cationic polymerization initiator is particularly preferable.
• a cationic polymerization initiator that is activated by active energy rays and / or a cationic polymerization initiator that is activated by heat it can be used as the curable resin composition B described later.
• Cationic polymerization initiators that initiate cationic polymerization of the curable resin composition B of the present invention by irradiation with active energy rays include diazonium salts, iodonium salts, sulfonium salts, selenium salts, pyridinium salts, ferrocenium salts, phosphonium salts. And iodonium salts and sulfonium salts, more preferably diaryl iodonium salts and dialkylphenacyl sulfonium salts, and diaryl iodonium salts can be preferably used.
• the anions include BF 4 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , PF 6 ⁇ , and B (C 6 F 5) 4 - and the like, preferably SbF 6 -, PF 6 -, or B (C 6 F 5) 4 - , and particularly preferably SbF 6 - or B (C 6 F 5) 4 - It is.
• a compound that is activated by heat to initiate cationic polymerization that is, a thermal cationic polymerization initiator
• a thermal cationic polymerization initiator can also be used in the curable resin composition B of the present invention.
• the thermal cationic polymerization initiator include various onium salts such as quaternary ammonium salts, phosphonium salts and sulfonium salts, and combinations of alkoxysilanes and aluminum complexes.
• Adeka Opton CP-66 and Adeka Opton CP-77 both trade names, manufactured by ADEKA
• Sun-Aid SI-60L Sun-Aid SI-80L
• Sun-Aid SI-100L both trade names, three Shin Chemical Industry Co., Ltd.
• CI series Nihon Soda Co., Ltd.
• the proportion of the epoxy resin mixture of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more.
• the epoxy resin mixture of the present invention is used as a modifier of the curable resin composition, it is added in a proportion of 1 to 30% by weight.
• epoxy resins include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins, and the like.
• bisphenol A bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc
• curable resin composition A Thermal curing with a curing agent
• the curing agent contained in the curable resin composition A of the present invention include a phenol resin, a phenol compound, an amine compound, an acid anhydride compound, an amide compound, and a carboxylic acid compound.
• Specific examples of the curing agent that can be used are as follows.
• Phenolic resins phenolic compounds; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hy Loxyace
• Preferable phenol resins include phenol aralkyl resins (resins having an aromatic alkylene structure), particularly preferably a structure having at least one selected from phenol, naphthol, and cresol, and the alkylene portion serving as the linker is benzene.
• a resin characterized by at least one selected from a structure, a biphenyl structure, and a naphthalene structure specifically examples include zylock, naphthol zylock, phenol biphenylene novolak resin, cresol-biphenylene novolak resin, phenol-naphthalene novolak resin, etc.
• Acid anhydride compounds carboxylic acid compounds; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydro Phthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2, Acid anhydrides such as 3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, etc .; by addition reaction of various alcohols, carbinol-modified silicone, and the above-mentioned acid anhydrides Although the obtained carboxylic acid resin is mentioned, it
• curing agents that can be used in combination include, but are not limited to, imidazole, trifluoroborane-amine complexes, guanidine derivative compounds, and the like. These may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a phenol resin from the viewpoint of reliability.
• the amount of the curing agent used is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy groups of all epoxy resins.
• curing may be incomplete and good cured properties may not be obtained.
• a curing accelerator may be used in combination with the curing agent.
• Specific examples of the curing accelerator that can be used include those described above.
• 0.01 to 5.0 parts by weight is used as necessary with respect to 100 parts by weight of the epoxy resin.
• the curable resin composition A of the present invention may contain a phosphorus-containing compound as a flame retardant imparting component.
• the phosphorus-containing compound may be a reactive type or an additive type.
• Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa
• Phosphate esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred.
• antioxidant to the curable resin composition A of this invention as needed.
• Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more.
• the amount of the antioxidant used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the resin component in the curable resin composition of the present invention. It is.
• phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl- ⁇ - (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-thiobis (3 Methyl-6-tert-butyl
• sulfur antioxidant examples include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like.
• phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4 -Phosphites such as -di-t-butyl-4-methylphenyl) phosphite, bis [2-tert-butyl-6-methyl
• antioxidants can be used alone, but two or more kinds may be used in combination.
• a phosphorus-based antioxidant is particularly preferable.
• HALS hindered amine-based light stabilizers
• HALS is not particularly limited, but typical examples include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4- Polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate -2,2,6,6-tetramethylpiperidine polycondensate, poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ (2,2,6,6-tetra
• the curable resin composition A of the present invention can be blended with a binder resin as necessary.
• the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins.
• the blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin component. 20 parts by weight are used as needed.
• An inorganic filler can be added to the curable resin composition A of the present invention as necessary.
• inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like.
• the present invention is not limited to these. These may be used alone or in combination of two or more.
• the content of these inorganic fillers is used in an amount of 0 to 95% by weight in the curable resin composition of the present invention.
• the curable resin composition of the present invention includes various agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers.
• agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers.
• a compounding agent and various thermosetting resins can be added.
• the curable resin composition A of the present invention can be obtained by uniformly mixing each component.
• the curable resin composition A of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, until the epoxy resin mixture of the present invention and a curing agent and, if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are uniform using an extruder, a kneader, a roll, or the like as necessary Mix well to obtain a curable resin composition. After potting and melting the curable resin composition (without melting in the case of liquid), it is molded using a casting or transfer molding machine, and further 80-200 The cured product of the present invention can be obtained by heating at a temperature of 2 to 10 hours.
• the curable resin composition A of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone as necessary, and the curable resin composition varnish.
• the curable resin composition of the present invention is obtained by hot press-molding a prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating. It can be set as the hardened
• the solvent is used in an amount usually accounting for 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent.
• cured material containing a carbon fiber can also be obtained as it is, for example with a RTM system.
• the curable resin composition A of the present invention can be used as a modifier for a film-type composition. Specifically, it can be used to improve the flexibility of the B-stage.
• the curable resin composition A of the present invention is applied onto a release film as the curable resin composition varnish, the solvent is removed under heating, and then B-stage is performed. Thus, it is obtained as a sheet-like adhesive.
• This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.
• Curable resin composition B (cationic curing with acidic curing catalyst)
• the curable resin composition B of the present invention that is cured using an acidic curing catalyst contains a photopolymerization initiator or a thermal polymerization initiator as an acidic curing catalyst.
• a photopolymerization initiator or a thermal polymerization initiator as an acidic curing catalyst.
• a cationic polymerization initiator is preferable, and a light or thermal cationic polymerization initiator is particularly preferable. It can be used as the curable resin composition B by blending a cationic polymerization initiator activated by active energy rays and / or a cationic polymerization initiator activated by heat.
• Examples of the cationic polymerization initiator for initiating cationic polymerization of the curable resin composition B of the present invention by irradiation with active energy rays include those described above.
• the active energy rays for curing the curable resin composition B of the present invention X-rays, electron beams, ultraviolet rays, visible light, and the like can be used, preferably ultraviolet rays or visible rays, particularly preferably. Is ultraviolet light.
• the wavelength range is not particularly limited, but is preferably 150 to 400 nm, more preferably 200 to 380 nm.
• ultraviolet rays are used, cationic polymerization can be efficiently started.
• the curable resin composition B of the present invention can be used in combination with a sensitizer in order to further increase the activity of the photocationic polymerization initiator, if necessary.
• a sensitizer that can be used in the present invention, for example, a compound disclosed by Crivello in Advanced in Polymer Polymer (Adv. Polymer Polymer Sci., 62, 1 (1984)) can be used. Specific examples include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and benzoflavine.
• thioxanthones such as benzophenone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2,4-dichlorothioxanthone.
• Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1 ⁇ -hydroxyalkylphenones such as phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, ⁇ such as camphorquinone -Dicarbo Nil compounds and the like.
• thioxanthones and ⁇ -hydroxyalkylphenones can be particularly preferably used.
• the blending amount of the cationic photopolymerization initiator in the curable resin composition B of the present invention can be appropriately adjusted according to the type of active energy ray and the irradiation amount.
• the amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts, and still more preferably 1 to 3 parts with respect to 100 parts by mass in total of the cationic curable resin composition. Part.
• the amount of the cationic polymerization initiator is less than 0.1 part, the curability may be lowered.
• the amount is more than 10 parts by weight, the amount of the component that is really necessary for the cured product is reduced. In some cases, physical properties may be deteriorated, and coloring of the cured product may become intense.
• the blending amount when a sensitizer is added to the curable resin composition B of the present invention can be appropriately adjusted according to the type of active energy ray and the irradiation amount.
• the amount is preferably 5 parts by mass or less, more preferably 0.2 to 2 parts with respect to 100 parts by mass in total of the curable resin composition B.
• the blending amount of the sensitizer is more than 5 parts by mass, the components that are truly necessary for the cured product may be reduced to deteriorate the physical properties of the cured product, or the cured product may be intensely colored.
• the active energy ray is ultraviolet light or visible light
• the cation curable resin composition is exposed to air.
• the humidity of the atmosphere is preferably low, preferably 80% humidity. H. 70% R.V. H. More preferably, it is as follows.
• a method of sending dry air in front of the light irradiation device or a method of reducing the humidity by attaching a heating device can be employed.
• Examples of the compound that is activated by heat to initiate cationic polymerization include those described above.
• the blending ratio of the thermal cationic polymerization initiator to the curable resin composition B of the present invention is preferably in the range of 0.01 to 10 parts by mass, more preferably 100 parts by mass with respect to the cationic curable resin composition. Is 0.1 to 5 parts, more preferably 0.5 to 3 parts.
• the blending ratio is less than 0.01 parts by mass, the ring-opening reaction of the ring-opening polymerizable group may not be allowed to proceed sufficiently even if it is activated by the action of heat.
• the curable resin composition B of the present invention is added with various compounding agents such as the above inorganic fillers, silane coupling materials, mold release agents, pigments, and various thermosetting resins as necessary. can do.
• the curable resin composition B of the present invention can be obtained by uniformly mixing each component. It is also possible to dissolve in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or ⁇ -butyrolactone and make it uniform, and then use it after removing the solvent by drying. In this case, the solvent is used in an amount of 10 to 70% by weight, preferably 15 to 70% by weight, in the mixture of the curable resin composition B of the present invention and the solvent.
• the curable resin composition B of the present invention can be cured by irradiating with ultraviolet rays, but the amount of ultraviolet irradiation varies depending on the curable resin composition, and therefore is determined by the respective curing conditions.
• the heating after the light irradiation may be performed in the normal curing temperature range of the curable resin composition B.
• the temperature is preferably from room temperature to 150 ° C. for 30 minutes to 7 days.
• the shape of the cured product obtained by curing these curable resin compositions B can be variously selected depending on the application, it is not particularly limited. For example, it may be a film shape, a sheet shape, a bulk shape, or the like.
• the molding method varies depending on the applicable part and member, for example, molding methods such as casting method, casting method, screen printing method, spin coating method, spray method, transfer method, dispenser method, etc. can be applied, It is not limited to these.
• polishing glass, hard stainless steel polishing plate, polycarbonate plate, polyethylene terephthalate plate, polymethyl methacrylate plate, or the like can be applied.
• a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyimide film, or the like can be applied in order to improve releasability from the mold.
• the photo cation curable resin composition B of the present invention dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or ⁇ -butyrolactone is used as a copper-clad laminate,
• the composition of the present invention is applied to a film thickness of 5 to 160 ⁇ m on a substrate such as a ceramic substrate or a glass substrate by a method such as screen printing or spin coating to form a coating film.
• the coating film is preliminarily dried at 60 to 110 ° C., and then irradiated with ultraviolet rays (for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a laser beam, etc.) through a negative film having a desired pattern.
• ultraviolet rays for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a laser beam, etc.
• post-exposure baking is performed at 70 to 120 ° C.
• the unexposed part is dissolved and removed (developed) with a solvent such as polyethylene glycol monoethyl ether, and if necessary, sufficient by irradiation with ultraviolet rays and / or heating (eg, at 100 to 200 ° C. for 0.5 to 3 hours). Curing is performed to obtain a cured product. In this way, it is also possible to obtain a printed wiring board.
• the cured product obtained by curing the curable resin composition A and the curable resin composition B of the present invention can be used for various applications.
• Examples include general uses in which the curable resin composition A or the curable resin composition B is used.
• adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials ( In addition to the sealing agent, the additive to other resins, etc. are mentioned.
• the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives.
• adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).
• sealing agent and substrate potting sealing for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold sealing, ICs, LSIs for COB, COF, TAB, etc.
• substrate use as which a functionality, such as a network board
• Epoxy equivalent Conforms to JIS K 7236 (ISO 3001) ICI melt viscosity: JIS K 7117-2 (ISO 3219) compliant Softening point: JIS K 7234 compliant
• GPC Column (Shodex KF-603, KF-602.5, KF-602, KF-601x2) The coupled eluent is tetrahydrofuran. The flow rate is 0.5 ml / min. Column temperature is 40 ° C Detection: RI (differential refraction detector)
• Example 1 To a flask equipped with a stirrer, reflux condenser, and stirrer, add 214.7 parts of binol, 46.6 parts of 4,4′-biphenol, 740 parts of epichlorohydrin, and 296 parts of dimethyl sulfoxide while purging with nitrogen. And dissolved under stirring, and the temperature was raised to 45 ° C. Next, 84 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 45 ° C. for 2 hours and at 70 ° C. for 75 minutes. After completion of the reaction, excess solvents such as epichlorohydrin were distilled off from the oil layer under reduced pressure using a rotary evaporator.
• the residue was dissolved by adding 800 parts of methyl isobutyl ketone, washed with water, and heated to 75 ° C. Under stirring, 30 parts by weight of 30% by weight sodium hydroxide aqueous solution was added and the reaction was carried out for 1 hour. Then, the oil layer was washed with water until the water became neutral, and the resulting solution was reduced in pressure using a rotary evaporator. Methyl isobutyl ketone and the like were distilled off below to obtain 360 parts of the epoxy resin mixture (EP1) of the present invention. The epoxy equivalent of the obtained epoxy resin was 207 g / eq. The ICI melt viscosity at a softening point of 87.5 ° C. and 150 ° C. was 0.03 Pa ⁇ s or less.
• Example 2 and Comparative Examples 1 and 2 ⁇ Heat resistance test>
• the epoxy resin obtained above was blended in the proportions (parts by weight) shown in Table 1, and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition for sealing.
• This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine.
• the tableted epoxy resin composition was transfer-molded (175 ° C. ⁇ 60 seconds), and after demolding, cured under the conditions of 160 ° C. ⁇ 2 hours + 180 ° C. ⁇ 6 hours to obtain a test piece for evaluation.
• cured material was measured in the following ways.
• TMA Heat resistance
• HDT Heat resistance
• the epoxy resin of the present invention which is a mixture of a binol structure and a biphenol structure is compared with a cured product using a binol structure epoxy resin (Comparative Example 1) and a cured product using a biphenol structure epoxy resin (Comparative Example 2). It can be seen that it has a structure that exhibits both high heat resistance and a low coefficient of linear expansion, and is compatible with both high heat resistance and dimensional stability.
• Example 3 and Comparative Examples 3, 4 Heat resistance test and flame retardancy test>
• the epoxy resin obtained above was blended in the proportions (parts by weight) shown in Table 2, and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition for sealing.
• This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine.
• the tableted epoxy resin composition was transfer-molded (175 ° C. ⁇ 60 seconds), and after demolding, cured under the conditions of 160 ° C. ⁇ 2 hours + 180 ° C. ⁇ 6 hours to obtain a test piece for evaluation.
• the flame retardant test results are also shown in Table 2.
• the curing accelerator C1 is the same as described above.
• cured material was measured in the following ways.
• the epoxy resin mixture of the present invention which is a mixture of a binol structure and a biphenol structure is a cured product using an epoxy resin having a binol structure (Comparative Example 3), and a cured product using an epoxy resin having a biphenol structure (Comparative Example). It can be seen that it has a structure that can achieve both high heat resistance and high flame retardancy compared to 4).
• Example 4 and Comparative Example 5 ⁇ Fluidity test>
• the epoxy resin obtained above was blended in the proportions (parts by weight) shown in Table 3, and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition for sealing.
• This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The spiral flow was measured for the tableted epoxy resin composition with a transfer molding machine at 175 ° C. and a molding pressure of 70 kg / cm 2 .
• the curing agent P2, the curing accelerator C1, the inorganic filler, the coupling agent, and the release agent are the same as described above.
• the epoxy resin of the present invention which is a mixture of a binol structure and a biphenol structure, generally has a higher fluidity than a cured product using a biphenol structure epoxy resin having a high fluidity (Comparative Example 5). I understand. (Despite the gel time of the same second, the spiral flow is long.)
• Example 5 and Comparative Examples 6, 7, 8, 9 ⁇ Comparison with other structures in heat resistance and water absorption tests>
• the epoxy resin shown below was mix
• This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine.
• the tableted epoxy resin composition was transfer-molded (175 ° C. ⁇ 60 seconds), and after demolding, cured under the conditions of 160 ° C. ⁇ 2 hours + 180 ° C. ⁇ 6 hours to obtain a test piece for evaluation.
• cured material was measured in the following ways.
• TMA Heat resistance
• EP4 Mixture of orthocresol novolac type epoxy resin and biphenol type epoxy resin (epoxy equivalent 205g / eq. Softening point 91 ° C ICI melt viscosity 0.03Pa ⁇ s or less)
• EP5 Mixture of phenol aralkyl type epoxy resin and biphenol type epoxy resin (epoxy equivalent 214g / eq. Softening point 102 °C ICI melt viscosity 0.09Pa ⁇ s)
• EP6 Mixture of biphenyl type phenol aralkyl type epoxy resin and biphenol type epoxy resin (epoxy equivalent 240g / eq. Softening point 93 ° C ICI melt viscosity 0.03Pa ⁇ s)
• the structural formula of the phenol aralkyl type epoxy resin is as shown in the following formula (A), and the structural formula of the biphenyl type phenol aralkyl type epoxy resin is as shown in the following formula (B).
• the epoxy resin of the present invention is superior in heat resistance compared to similar modified resins of other structures, and generally the water absorption rate is worse when the heat resistance is increased, but the water absorption characteristics are not as large as others. Thus, it can be seen that the heat resistance and water resistance are excellent.
• Example 6 ⁇ Mechanical strength, coefficient of linear expansion, moisture absorption, crack resistance, impact resistance, molding shrinkage, gel time> 207 parts of epoxy resin EP1, 103 parts of P1, and 2 parts of C1 were blended and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition for sealing.
• This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine.
• the tableted epoxy resin composition was transfer-molded (175 ° C. ⁇ 60 seconds), and after demolding, cured under the conditions of 160 ° C. ⁇ 2 hours + 180 ° C. ⁇ 6 hours to obtain a test piece for evaluation.
• cured material was measured in the following ways.
• Example 7 and Comparative Examples 10 and 11 ⁇ Fluidity test>
• the epoxy resin obtained above was blended in the proportions (parts by weight) shown in Table 5, and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition for sealing.
• This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The spiral flow was measured for the tableted epoxy resin composition with a transfer molding machine at 175 ° C. and a molding pressure of 70 kg / cm 2 .
• the curing agent P2, the curing accelerator C1, the inorganic filler, the coupling agent, and the release agent are the same as described above.
• the epoxy resin of the present invention which is a mixture of a binol structure and a biphenol structure has higher fluidity than a cured product using an epoxy resin having another structure. (Despite the gel time of about the same second, the spiral flow is long.)
• composition using the epoxy resin mixture of the present invention is excellent in fluidity, and that the cured product is particularly excellent in flame retardancy and heat resistance, and a semiconductor that requires high functionality is required. It can be seen that it is useful for a sealing material and a thin film substrate material (including an interlayer insulating film) that requires high filler filling.
• the epoxy resin composition containing the epoxy resin mixture of the present invention is useful for insulating materials for electrical and electronic parts and various composite materials including laminated boards (printed wiring boards, build-up boards, etc.) and CFRP, adhesives, paints, etc. It is.

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