Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
  • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
  • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
  • C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
• • 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
  • C08G59/26—Di-epoxy compounds heterocyclic
• • 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

Definitions

• the present invention relates to a novel diolefin compound and an epoxy resin suitable for electrical and electronic material applications.
• Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., adhesives, paints, laminates, moldings It is used in a wide range of fields such as materials, casting materials and resists.
• electronic devices such as mobile phones with cameras, ultra-thin liquid crystals, plasma TVs, and light-weight notebook computers have become key to light, thin, short, and small.
• Very high characteristics have been demanded for packaging materials represented by resins.
• the structure of the tip package is complicated, and there are an increasing number of things that are difficult to seal without liquid sealing.
• a cavity down type structure such as Enhanced BGA needs to be partially sealed and cannot be handled by transfer molding.
• highly functional liquid epoxy resins has been demanded.
• RTM has been used as a composite material, a car body or a ship structural material because of its simplicity of manufacturing method.
• a low-viscosity epoxy resin is desired because it is easily impregnated into carbon fiber or the like.
• alicyclic epoxy compounds are superior in terms of electrical insulation and transparency, and are used in a variety of transparent sealing materials.
• cured material is hard and toughness is inferior remains on the other hand, and examination is advanced in order to improve this fault (patent document 1).
• alicyclic epoxy resins having a structure as generally known conventionally have an ester bond in the structure. Since it has an ester group in the molecule, it has hydrolyzability, and when used under conditions such as high temperature and high humidity or generation of strong acid, the physical properties of the cured product may be lowered. Therefore, an epoxy compound having an alicyclic skeleton in the molecule but not having an ester group is desired. Examples of such an epoxy compound include those disclosed in Patent Documents 2 and 3. There are not many types of existing alicyclic epoxy compounds, and there are many compounds whose raw materials before epoxidation are relatively expensive.
• epoxidized dicyclopentadiene Even if it is inexpensive, epoxidized dicyclopentadiene has sublimation properties due to its low polarity and low molecular weight, which is not preferable in terms of work, but also has a high density of functional groups between molecules and toughness. The cured product is inferior to.
• An object of the present invention is to provide a novel alicyclic epoxy resin having no ester bond in the molecule.
• the present invention provides (1) the following formula (1)
• the epoxy resin of the present invention does not have an ester bond in the molecular structure, and further gives a cured product having excellent mechanical properties.
• the curable resin composition of the present invention containing the epoxy resin of the present invention has a wide range of applications such as electric / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resists, etc., and particularly low colorability. Therefore, it is extremely useful for optical materials.
• the diolefin compound of the present invention can be obtained by reacting a cyclohexene aldehyde derivative with a trimethylolalkane derivative.
• a cyclohexene aldehyde derivative examples include cyclohexene carbaldehyde, methylcyclohexene carbaldehyde, and ethylcyclohexene carbaldehyde.
• the trimethylolalkane derivative include ditrimethylolpropane, ditrimethylolmethane, ditrimethylolethane, and ditrimethylolbutane.
• the trimethylolalkane derivative is usually used in an amount of 0.4 to 0.6 mol, preferably 0.45 to 0.55 mol, per mol of the cyclohexene aldehyde derivative.
• the diolefin compound of the present invention can be produced by applying a normal cyclic acetalization reaction.
• the reaction is carried out by azeotropic dehydration using a solvent such as toluene or xylene as a reaction medium (US Pat. No. 2,945,008), while polyhydric alcohol is dissolved in concentrated hydrochloric acid and aldehydes are gradually added.
• a method for carrying out the reaction JP-A-48-96590
• a method using water as a reaction medium US Pat. No. 3,092,640
• a method using an organic solvent as a reaction medium JP-A-7-215979
• a solid A method using an acid catalyst Japanese Patent Application Laid-Open No. 2007-230992 is known.
• any of the above-described methods may be used.
• a method of acetalizing a cyclohexene aldehyde derivative and a trimethylol alkane derivative by a dehydration reaction under acidic conditions can be mentioned.
• an acidic catalyst mineral acids such as sulfuric acid and phosphoric acid: organic acids such as toluenesulfonic acid, methanesulfonic acid and ion exchange resin: heteropolyester such as tungstic acid and molybdic acid Acid, activated clay, inorganic acid, stannic chloride, zinc chloride, ferric chloride, and other organic and inorganic acid salts that show acidity
• an acidic catalyst mineral acids such as sulfuric acid and phosphoric acid: organic acids such as toluenesulfonic acid, methanesulfonic acid and ion exchange resin: heteropolyester such as tungstic acid and molybdic acid Acid, activated clay, inorganic acid, stannic chloride, zinc chloride, ferric chloride, and other organic and inorganic acid salts that show acidity
• the diolefin compound of the present invention thus synthesized has a structure as shown in the above formula (1).
• the resulting diolefin compound generally exhibits a liquid state due to its structure.
• the diolefin body of the present invention represented by the formula (1) can be oxidized to form the epoxy resin of the present invention.
• the oxidation method include, but are not limited to, a method of oxidizing with a peracid such as peracetic acid, a method of oxidizing with a hydrogen peroxide solution, and a method of oxidizing with air (oxygen).
• a peracid such as peracetic acid
• a method of oxidizing with a hydrogen peroxide solution a method of oxidizing with air (oxygen).
• Specific examples of the epoxidation method using peracid include the method described in JP-A-2006-52187.
• Various methods can be applied to the method of epoxidation with hydrogen peroxide solution.
• JP-A-59-108793, JP-A-62-234550, JP-A-5-213919, Techniques such as those disclosed in JP-A-11-349579, JP-B-1-33471, JP-A-2001-17864, JP-B-3-57102 and the like can be applied.
• the diolefin compound, polyacids and quaternary ammonium salt of the present invention are reacted in an organic solvent, buffer solution and hydrogen peroxide emulsion.
• the polyacid used in the present invention is not particularly limited as long as it is a compound having a polyacid structure, but a polyacid containing tungsten or molybdenum and a salt thereof are preferred, a polyacid containing tungsten and a salt thereof are more preferred, and tungsten Acid salts are particularly preferred
• Specific polyacids and salts thereof include tungsten acids such as tungstic acid, 12-tungstophosphoric acid, 12-tungstoboric acid, 18-tungstophosphoric acid, 12-tungstophosphoric acid and their salts, molybdenum And acids, molybdenum acids such as phosphomolybdic acid, and salts thereof.
• Examples of the counter cation of these salts include quaternary ammonium ions, alkaline earth metal ions, and alkali metal ions. Specific examples include alkaline earth metal ions such as calcium ions and magnesium ions, and alkali metal ions such as sodium, potassium and cesium, but are not limited thereto. Particularly preferred counter cations are sodium ion, potassium ion, calcium ion and ammonium ion.
• the amount to be used is 1.0 to 20 mmol, preferably 2.0 to 20 mmol, more preferably 2 in terms of metal elements (moles of tungsten atoms for tungthenic acid, and molybdenum atoms for molybdic acid) per mol of raw material. .5-10 mmol.
• quaternary ammonium salt having a total carbon number of 10 or more, preferably 25 to 100, can be preferably used, and in particular, those whose alkyl chains are all aliphatic chains are preferred.
• tridecanylmethylammonium salt dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (a mixed type of a compound in which the alkyl group is an octyl group and a compound in which the decanyl group is a compound) ammonium salt
• trihexa examples include decylmethylammonium salt, trimethylstearylammonium salt, tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, and di-cured tallow alkyldimethylammonium salt.
• nitrate ion, sulfate ion, hydrogen sulfate ion, acetate ion, carbonate ion, etc. are particularly preferred from the point of not containing halogen, and carboxylate such as acetate ion is particularly preferred due to the small number of side reactions during epoxidation. Particularly preferred.
• the amount of the quaternary ammonium salt used is preferably 0.01 to 10 times the valence of the polyacids (preferably tungstic acids) used. More preferably, it is 0.05 to 6.0 times equivalent, still more preferably 0.05 to 4.5 times equivalent (however, the particularly preferred range varies depending on the type and combination of polyacids).
• the quaternary ammonium salt is preferably in the range of 0.02 to 20 mol with respect to 1 mol of tungstic acid.
• it is trivalent in the case of tungstophosphoric acid, it is similarly 0.03 to 20 mol, and in the case of silicotungstic acid, it is tetravalent, so 0.04 to 40 mol is preferable.
• the amount of the quaternary ammonium salt is lower than 0.01 times the valence of the polyacid, the epoxidation reaction is difficult to proceed (in some cases, the reaction proceeds faster), and a by-product is formed. The problem of being easy arises.
• the amount is more than 10 times equivalent, not only is the post-treatment difficult, but there is a function of suppressing the reaction, which is not preferable.
• any buffer can be used, but it is preferable to use an aqueous phosphate solution in this reaction.
• the pH is preferably adjusted between pH 2 and 6, more preferably pH 3-5. When the pH is less than 2, the epoxy group hydrolysis reaction and polymerization reaction easily proceed. On the other hand, when the pH exceeds 6, the reaction becomes extremely slow and the reaction time is too long.
• a phosphoric acid-phosphate aqueous solution which is a preferable buffer, 0.1 to 10 molar equivalents of phosphoric acid (or a phosphate such as sodium dihydrogen phosphate) is used with respect to hydrogen peroxide.
• a method of adjusting pH with a basic compound for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, etc.
• a basic compound for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, etc.
• the pH is added so that the above-mentioned pH is obtained when hydrogen peroxide is added.
• sodium dihydrogen phosphate, disodium hydrogen phosphate, or the like The preferred phosphate concentration is 0.1 to 60% by weight, preferably 5 to 45% by weight.
• a buffer solution is not used, and a phosphate such as disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, sodium tripolyphosphate (or a hydrate thereof) is directly added without adjusting the pH.
• the amount of phosphate used in this case is usually 0.1 to 5 mol% equivalent, preferably 0.2 to 4 mol% equivalent, more preferably 0.3 to 3 mol% equivalent to hydrogen peroxide. is there. In this case, if the amount exceeds 5 mol% equivalent to hydrogen peroxide, pH adjustment is required. If the amount is less than 0.1 mol% equivalent, the resulting hydrolyzate of the epoxy compound tends to proceed or the reaction is slow. The harmful effect of becoming.
• This reaction is epoxidized using hydrogen peroxide.
• hydrogen peroxide used in this reaction, an aqueous solution having a hydrogen peroxide concentration of 10 to 40% by weight is preferable because of easy handling. When the concentration exceeds 40% by weight, handling becomes difficult and the decomposition reaction of the produced epoxy resin also tends to proceed.
• This reaction uses an organic solvent.
• the amount of the organic solvent to be used is 0.3 to 10, preferably 0.3 to 5, more preferably 0.5 to 2.5 by weight with respect to the diolefin compound 1 as a reaction substrate. is there. When the weight ratio exceeds 10, the progress of the reaction is extremely slow, which is not preferable.
• organic solvents that can be used include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, and alcohols such as methanol, ethanol, isopropanol, butanol, hexanol and cyclohexanol. It is done.
• ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone
• ethers such as diethyl ether, tetrahydrofuran and dioxane
• ester compounds such as ethyl acetate, butyl acetate and methyl formate
• nitriles such as acetonitrile Compounds and the like
• Particularly preferred solvents are alkanes such as hexane, cyclohexane and heptane, and aromatic hydrocarbon compounds such as toluene and xylene.
• reaction operation method for example, when the reaction is performed in a batch-type reaction kettle, a diolefin compound, hydrogen peroxide (aqueous solution), polyacids (catalyst), a buffer solution, a quaternary ammonium salt, and an organic solvent are added. In addition, stir in two layers. There is no specific designation for the stirring speed. Since heat is often generated when hydrogen peroxide is added, a method of gradually adding hydrogen peroxide after each component may be added.
• the reaction temperature is not particularly limited, but is preferably 0 to 90 ° C, more preferably 0 to 75 ° C, particularly preferably 15 ° C to 60 ° C.
• the reaction temperature is too high, the hydrolysis reaction tends to proceed, and when the reaction temperature is low, the reaction rate becomes extremely slow.
• reaction time depends on the reaction temperature, the amount of catalyst, etc., from the viewpoint of industrial production, a long reaction time is not preferable because it consumes a great deal of energy.
• a preferred range is 1 to 48 hours, preferably 3 to 36 hours, and more preferably 4 to 24 hours.
• the quenching treatment is preferably performed using a basic compound. It is also preferable to use a reducing agent and a basic compound in combination.
• a preferable treatment method there is a method of quenching the remaining hydrogen peroxide using a reducing agent after neutralization adjustment to pH 6 to 10 with a basic compound. If the pH is less than 6, the heat generated during the reduction of excess hydrogen peroxide is large, which may cause decomposition products.
• reducing agents include sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, and vitamin C.
• the reducing agent is used usually in an amount of 0.01 to 20 times mol, more preferably 0.05 to 10 times mol, and still more preferably 0.05 to 3 times mol with respect to the number of moles of excess hydrogen peroxide. is there.
• Basic compounds include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, phosphorus such as sodium phosphate and sodium hydrogen phosphate. Examples thereof include basic solids such as acid salts, ion exchange resins, and alumina.
• the amount used is water or organic solvents (for example, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl isobutyl ketone and methyl ethyl ketone, hydrocarbons such as cyclohexane, heptane and octane, methanol, ethanol, isopropyl alcohol, etc.
• the amount used is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times the number of moles of excess hydrogen peroxide. Mole, more preferably 0.05 to 3 times mole. These may be added as water or a solution of the above-mentioned organic solvent, or may be added alone.
• a solid base that does not dissolve in water or an organic solvent it is preferable to use an amount of 1 to 1000 times by weight with respect to the amount of hydrogen peroxide remaining in the system. More preferably, it is 10 to 500 times, and further preferably 10 to 300 times.
• the treatment may be carried out after separation of an aqueous layer and an organic layer described later.
• the organic layer and the aqueous layer do not separate, or if the organic solvent is not used, perform the operation by adding the above-mentioned organic solvent and react from the aqueous layer. Extract the product.
• the organic solvent used at this time is 0.5 to 10 times, preferably 0.5 to 5 times in weight ratio to the raw material diolefin compound. This operation is repeated several times as necessary, and the separated organic layer is purified by washing with water as necessary.
• the obtained organic layer is subjected to ion exchange resin, metal oxide, activated carbon, composite metal salt, clay mineral, etc., if necessary, to remove impurities, further washed with water, filtered, etc., and then the solvent is distilled off.
• the desired epoxy resin can be obtained. In some cases, it may be further purified by column chromatography or distillation.
• the epoxy resin of the present invention thus obtained has the formula (2)
• any combination of A to D may be used.
• the compounds of various structures as shown in FIG. Further, polymerized high molecular weight polymer of epoxy groups and other side reaction products are generated depending on the reaction conditions.
• the obtained epoxy resin can be used as various resin raw materials such as epoxy acrylate and derivatives thereof, oxazolidone compounds, and cyclic carbonate compounds.
• the curable resin composition of the present invention contains the epoxy resin of the present invention as an essential component.
• two methods of heat curing with a curing agent (curable resin composition A) and cationic curing with an acid as a curing catalyst (curable resin composition B) can be applied.
• the epoxy resin of the present invention can be used alone or in combination with other epoxy resins.
• the proportion of the epoxy resin 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 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.
• 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.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetofu Non, o-hydroxy
• an alicyclic epoxy resin or an epoxy resin of a silsesquioxane structure is preferable.
• an alicyclic epoxy resin a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.
• epoxy resins include esterification reaction of cyclohexene carboxylic acid and alcohols or esterification reaction of cyclohexene methanol and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.) Described), or Tyschenko reaction of cyclohexene aldehyde (method described in JP 2003-170059 A, JP 2004-262871 A, etc.), and further transesterification reaction of cyclohexene carboxylic acid ester (JP 2006-052187 A). And the like, which are obtained by oxidizing a compound that can be produced by the method described in Japanese Patent Publication No.
• the alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane.
• Diols Diols, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol, ditrimethylolpropane, etc.
• carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.
• epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celoxide 2021P, Epolide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel) (Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited thereto (Reference: Review Epoxy Resin Basic Edition I p76-85). These may be used alone or in combination of two or more.
• curable resin composition A Thermal curing with a curing agent
• curing agent contained in the curable resin composition A of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds.
• the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, Bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclo
• 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.
• curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza- And tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate.
• a curing accelerator 0.1 to 5.0 parts by weight is used as necessary with respect to 100 parts by weight of the total 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.
• antioxidants examples include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant.
• 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-t-butylphenol), 2,2'-methylenebis (4-ethyl
• sulfur antioxidant examples include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyll-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 within 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 20 parts per 100 parts by weight of the resin component. Part by weight is used as needed.
• An inorganic filler can be added to the curable resin composition A of the present invention as necessary.
• inorganic fillers powders of silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, etc., or these spheroidized Examples include, but are not limited to, beads.
• a nano-sized material 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.
• a fluorescent substance can be added as needed.
• the phosphor has, for example, a function of forming white light by absorbing a part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed.
• fluorescent substance A conventionally well-known fluorescent substance can be used, For example, the rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated.
• phosphors such as YAG phosphors, TAG phosphors, orthosilicate phosphors, thiogallate phosphors, sulfide phosphors, and the like can be mentioned.
• YAlO 3 Ce, Y 3 Al 5 O 12 : Ce, Y 4 Al 2 O 9 : Ce, Y 2 O 2 S: Eu, Sr 5 (PO 4 ) 3 Cl: Eu, (SrEu) O.Al 2 O 3 and the like are exemplified.
• the particle diameter of the phosphor those known in this field are used, and the average particle diameter is preferably 1 to 250 ⁇ m, particularly preferably 2 to 50 ⁇ m.
• the addition amount is 1 to 80 parts by weight, preferably 5 to 60 parts by weight, based on 100 parts by weight of the resin component.
• 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.
• the epoxy resin of the present invention, a curing agent and, if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are sufficient until uniform using an extruder, kneader, roll, etc. as necessary.
• potting the curable resin composition melting it (without melting in the case of a liquid), molding using a casting or transfer molding machine, and further 80 to 200 ° C.
• the cured product of the present invention can be obtained by heating for 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, and the curable resin composition varnish is obtained.
• Curing of the curable resin composition A of the present invention by hot press molding a prepreg obtained by impregnating a substrate such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating. It can be a thing.
• 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 which contains a carbon fiber by a RTM system with a liquid composition can also be obtained.
• the curable resin composition A of the present invention can also be used as a film type composition modifier. 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 A of the present invention is used as an optical semiconductor sealing material or die bond material.
• the curing agent (curing agent composition) containing the epoxy resin of the present invention prepare an epoxy resin composition by thoroughly mixing additives such as curing accelerators, coupling materials, antioxidants, light stabilizers, etc., and use it as a sealing material or for both die-bonding materials and sealing materials Is done.
• a mixing method a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill or the like is used to mix at room temperature or warm.
• Optical semiconductor elements such as high-intensity white LEDs are generally GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN laminated on a substrate of sapphire, spinel, SiC, Si, ZnO or the like.
• Such a semiconductor chip is bonded to a lead frame, a heat sink, or a package using an adhesive (die bond material).
• a wire such as a gold wire is connected to pass an electric current.
• the semiconductor chip is sealed with a sealing material such as an epoxy resin in order to protect it from heat and moisture and play a role of a lens.
• the curable resin composition A of the present invention can be used as this sealing material or die bond material. From the viewpoint of the process, it is advantageous to use the curable resin composition A of the present invention for both the die bond material and the sealing material.
• the curable resin composition A of the present invention is applied by dispenser, potting, or screen printing, and then the semiconductor chip is placed thereon. Then, the semiconductor chip can be bonded by heat curing.
• the heating methods such as hot air circulation, infrared rays and high frequency can be used.
• the heating conditions are preferably 80 to 230 ° C. for about 1 minute to 24 hours.
• post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.
• a compression molding method or the like in which a semiconductor chip fixed on a substrate is immersed therein and heat-cured and then released from a mold is used.
• the injection method include dispenser, transfer molding, injection molding and the like.
• methods such as hot air circulation, infrared rays and high frequency can be used.
• the heating conditions are preferably 80 to 230 ° C. for about 1 minute to 24 hours.
• post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.
• the cured product of the present invention obtained by curing the curable resin composition A of the present invention can be used for various applications including optical component materials.
• the optical material refers to general materials used for applications that allow light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned. It is a peripheral material for liquid crystal display devices such as a substrate material, a light guide plate, a prism sheet, a polarizing plate, a retardation plate, a viewing angle correction film, an adhesive, and a film for a liquid crystal such as a polarizer protective film in the liquid crystal display field.
• color PDP plasma display
• LED sealing materials used in the device
• LED sealing material front glass protective film, front glass substitute material, adhesive, and substrate material for plasma addressed liquid crystal (PALC) display
• light guide plate prism sheet
• polarizing plate Phase difference plate
• viewing angle correction film adhesive
• polarizer protective film front glass protective film in organic EL (electroluminescence) display
• front glass substitute material front glass substitute material
• adhesive various in field emission display (FED) Film substrate
• FED field emission display
• VD video disc
• CD / CD-ROM CD-R / RW
• DVD-R / DVD-RAM MO / MD
• PD phase change disc
• disc substrate materials for optical cards Pickup lenses, protective films, sealing materials, adhesives and the like.
• optical equipment In the field of optical equipment, they are steel camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor parts. It is also a photographic lens and viewfinder for video cameras. Projection lenses for projection televisions, protective films, sealing materials, adhesives, and the like. These include lens materials, sealing materials, adhesives, and films for optical sensing devices.
• optical components In the field of optical components, they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. For optical passive components and optical circuit components, there are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like.
• OEIC optoelectronic integrated circuit
• automotive lamp reflectors In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Rusted steel plate, interior panel, interior material, wire harness for protection / bundling, fuel hose, automobile lamp, glass substitute.
• it is a multilayer glass for railway vehicles.
• they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wire harnesses, and corrosion resistant coatings.
• it In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film.
• Next generation optical / electronic functional organic materials include peripheral materials for organic EL elements, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical computing elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.
• sealing agents potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip
• underfill for sealing, and sealing (reinforcing underfill) when mounting IC packages such as BGA and CSP.
• the curable resin composition A of the present invention can be used for general applications in which thermosetting resins such as epoxy resins are used. Specifically, adhesives, paints, coating agents, molding materials ( Sheet, film, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealing materials, sealing materials, cyanate resin compositions for substrates, and acrylic esters as resist curing agents And additives to other resins and the like.
• thermosetting resins such as epoxy resins are used.
• adhesives examples include civil engineering, architectural, automotive, general office, and medical adhesives, as well as 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 agents potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip
• underfill for QFP, BGA, CSP, etc., and sealing can be used.
• 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 photocationic polymerization initiator is particularly preferable.
• the cationic polymerization initiator include those having an onium salt such as an iodonium salt, a sulfonium salt, and a diazonium salt, and these can be used alone or in combination of two or more.
• active energy ray cationic polymerization initiators include metal fluoroboron complex salts and boron trifluoride complex compounds (US Pat. No. 3,379,653), bis (perfluoroalkylsulfonyl) methane metal salts (US Pat. No.
• Aromatic iodonium complexes and aromatic sulfonium complexes (US Pat. No. 4,256,828), and bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluorometal salts (Journal of Polymer Science, Polymer Chemistry, 2 Volume, 1789 (1984)).
• mixed ligand metal salts of iron compounds and silanol-aluminum complexes can also be used.
• the amount of the cationic polymerization initiator used is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total epoxy resin component.
• polymerization initiators include, for example, benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinolpropan-1-one, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1- Chloroanthraquinone, 2-amylanthraquinone, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,
• the photosensitizer include anthracene, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acridine orange, acridine yellow, phosphine R, benzo
• examples include flavin, cetoflavin T, perylene, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, and triethylamine.
• the photosensitizer is used in an amount of 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total epoxy resin component.
• various compounding agents such as inorganic fillers, silane coupling materials, mold release agents, pigments, and various thermosetting resins can be added to the curable resin composition B of the present invention as necessary. . Specific examples are as described above.
• 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, the ultraviolet irradiation amount varies depending on the curable resin composition, and thus 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, and examples include molding methods such as casting method, casting method, screen printing method, spin coating method, spray method, transfer method, dispenser method, etc. It is not limited. As the mold, 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 B of the present invention can be used for various applications including optical component materials.
• the optical material refers to general materials used for applications that allow light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned. It is a peripheral material for liquid crystal display devices such as a substrate material, a light guide plate, a prism sheet, a polarizing plate, a retardation plate, a viewing angle correction film, an adhesive, and a film for a liquid crystal such as a polarizer protective film in the liquid crystal display field.
• color PDP plasma display
• LED sealing materials used in the device
• LED sealing material front glass protective film, front glass substitute material, adhesive, and substrate material for plasma addressed liquid crystal (PALC) display
• light guide plate prism sheet
• polarizing plate Phase difference plate
• viewing angle correction film adhesive
• polarizer protective film front glass protective film in organic EL (electroluminescence) display
• front glass substitute material front glass substitute material
• adhesive various in field emission display (FED) Film substrate
• FED field emission display
• VD video disc
• CD / CD-ROM CD-R / RW
• DVD-R / DVD-RAM MO / MD
• PD phase change disc
• disc substrate materials for optical cards Pickup lenses, protective films, sealing materials, adhesives and the like.
• optical equipment In the field of optical equipment, they are steel camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor parts. It is also a photographic lens and viewfinder for video cameras. Projection lenses for projection televisions, protective films, sealing materials, adhesives, and the like. These include lens materials, sealing materials, adhesives, and films for optical sensing devices.
• optical components In the field of optical components, they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. For optical passive components and optical circuit components, there are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like.
• OEIC optoelectronic integrated circuit
• automotive lamp reflectors In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Rusted steel plate, interior panel, interior material, wire harness for protection / bundling, fuel hose, automobile lamp, glass substitute.
• it is a multilayer glass for railway vehicles.
• they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wire harnesses, and corrosion resistant coatings.
• it In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film.
• Next generation optical / electronic functional organic materials include peripheral materials for organic EL elements, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical computing elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.
• sealing agents potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip
• underfill for sealing, and sealing (reinforcing underfill) when mounting IC packages such as BGA and CSP.
• optical material examples include general uses in which the curable resin composition B is used.
• adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), In addition to insulating materials (including printed circuit boards and wire coatings), sealants, additives to other resins and the like can be 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).
• the epoxy equivalent was measured using an E-type viscometer at JIS K-7236 and the viscosity at 25 ° C.
• the analysis conditions in gas chromatography were as follows: HP5-MS (0.25 mm IDx 15 m, thickness 0.25 ⁇ m) was used for the separation column, and the column oven temperature was set to the initial temperature of 100. The temperature was set at 0 ° C., the temperature was raised at a rate of 15 ° C. per minute and held at 300 ° C. for 25 minutes. Helium was used as a carrier gas.
• the measurement in gel permeation chromatography is as follows.
• the column is a Shodex® SYSTEM-21 column (KF-803L, KF-802.5 ( ⁇ 2), KF-802), the coupled eluent is tetrahydrofuran, and the flow rate is 1 ml / min.
• the column temperature was 40 ° C., detection was performed at UV (254 nm), and a standard polystyrene manufactured by Shodex was used for the calibration curve.
• Example 1 To a flask equipped with a stirrer, reflux condenser, and stirrer, add 150 parts of water, 55.1 parts of 3-cyclohexenecarbaldehyde, 62.6 parts of ditrimethylolpropane, and 7.3 parts of concentrated hydrochloric acid while purging with nitrogen. The reaction was carried out at 60 ° C. for 10 hours. After completion of the reaction, 100 parts of water and 30 parts of a 3% aqueous sodium hydroxide solution were added, and further neutralized with disodium hydrogen phosphate. To this, 200 parts of methyl isobutyl ketone was added, washed with 100 parts of water three times, and then the solvent and the like were removed, thereby removing the following formula (4).
• Example 2 To a flask equipped with a stirrer, reflux condenser, stirrer, and Dean-Stark bottle, while purging with nitrogen, 150 parts of toluene, 55.1 parts of 3-cyclohexenecarbaldehyde, 62.6 parts of ditrimethylolpropane, p-toluenesulfone The reaction was carried out for 10 hours while adding 1.5 parts of acid and removing water under reflux conditions. After completion of the reaction, 3 parts of sodium tripolyphosphate was added, stirred at 100 ° C.
• Example 3 A flask equipped with a stirrer, reflux condenser, and stirrer was charged with 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, 0.78 disodium hydrogen phosphate, and di-cured tallow alkyldimethylammonium acetate 2 while purging with nitrogen. .7 parts (50% by weight hexane solution from Lion Akzo) was added to form a tungstic acid catalyst, and then 120 parts of toluene, 108 parts of the compound of formula (4) (D-2) obtained in Example 2 was added and stirred again to obtain a liquid in an emulsion state.
• Example 3 (Heat resistance test: DMA) The curable resin composition obtained in Example 3 was vacuum degassed for 20 minutes, and then gently poured into a test piece mold having a width of 7 mm, a length of 5 cm, and a thickness of about 800 ⁇ m. Did. The cast was cured under the following conditions to obtain a dynamic viscoelastic test piece. Using these test pieces, a dynamic viscoelasticity test was performed under the conditions shown below. Curing conditions 120 ° C. ⁇ 1 hour + 150 ° C.
• Dynamic viscoelasticity measuring instrument DMA-2980, manufactured by TA-instruments Measurement temperature range: -30 ° C to 280 ° C Temperature rate: 2 ° C./min Test piece size: A material cut into 5 mm ⁇ 50 mm was used (thickness was about 800 ⁇ m). Analysis conditions Tg: The peak point of Tan- ⁇ in DMA measurement was defined as Tg.
• Thermomechanical property test: TMA The curable resin composition obtained in Example 3 was subjected to vacuum defoaming for 20 minutes, then cast in a Teflon (registered trademark) ⁇ 5 mm tube, and the cast was cured under the above conditions to obtain a test piece. It was. Using this test piece, a heat resistance test was performed under the conditions shown below. Measurement conditions Dynamic viscoelasticity measuring instrument: TM-7000 manufactured by Vacuum Riko Co., Ltd. Measurement temperature range: 40 ° C-250 ° C Temperature rate: 2 ° C./min Test piece size: ⁇ 5 mm A material cut into 10 mm was used.
• LED lighting test In the lighting test, a lighting test was performed at a current twice as high as 30 mA, which is a specified current, for the test LED mounted on the substrate. Detailed conditions are shown below. As a measurement item, the illuminance after lighting for 200 hours was measured using an integrating sphere, and the illuminance retention rate of the test LED was calculated. Detailed lighting conditions Light emission wavelength: 465nm Drive system: constant current system, 60 mA (light emitting element regulation current is 30 mA) Driving environment: 85 ° C, 85% Evaluation: Illuminance after 200 hours and its illuminance retention rate
• the epoxy resin of the present invention does not have an ester bond in the resin skeleton, and as a result of the lighting test with the LED, the optical characteristics that can withstand the light, humidity, and heat of the LED, and the electrical property It was revealed that a cured product having excellent characteristics can be provided.

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• 2009
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