WO2010041670A1 - Diolefin compound, epoxy resin, curable resin composition and cured product - Google Patents
Diolefin compound, epoxy resin, curable resin composition and cured product Download PDFInfo
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- WO2010041670A1 WO2010041670A1 PCT/JP2009/067432 JP2009067432W WO2010041670A1 WO 2010041670 A1 WO2010041670 A1 WO 2010041670A1 JP 2009067432 W JP2009067432 W JP 2009067432W WO 2010041670 A1 WO2010041670 A1 WO 2010041670A1
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- 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
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- 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
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- 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
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- 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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Abstract
Description
またコンポジット材、車の車体や船舶の構造材として、近年、その製造法の簡便さからRTMが使用されている。このような組成物においてはカーボンファイバー等への含浸のされやすさから低粘度のエポキシ樹脂が望まれている。 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. In recent years, especially in the field of semiconductor-related materials, 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. In particular, the structure of the tip package is complicated, and there are an increasing number of things that are difficult to seal without liquid sealing. For example, a cavity down type structure such as Enhanced BGA needs to be partially sealed and cannot be handled by transfer molding. For these reasons, the development of highly functional liquid epoxy resins has been demanded.
In recent years, RTM has been used as a composite material, a car body or a ship structural material because of its simplicity of manufacturing method. In such a composition, a low-viscosity epoxy resin is desired because it is easily impregnated into carbon fiber or the like.
すなわち本発明は
(1)下記式(1) As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention provides (1) the following formula (1)
で表されるジオレフィン化合物、
(2)上記(1)に記載のジオレフィン化合物を酸化することにより得られるエポキシ樹脂、
(3)過酸化水素または過酸を用いて酸化して得られた上記(2)に記載のエポキシ樹脂、
(4)上記(2)または(3)に記載のエポキシ樹脂と硬化剤および/または硬化触媒を含有する硬化性樹脂組成物、
(5)上記(4)に記載の硬化性樹脂組成物を硬化してなる硬化物、
に関する。 (In the formula, plural Rs each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
A diolefin compound represented by:
(2) an epoxy resin obtained by oxidizing the diolefin compound according to (1) above,
(3) The epoxy resin according to the above (2) obtained by oxidation using hydrogen peroxide or peracid,
(4) A curable resin composition containing the epoxy resin according to the above (2) or (3) and a curing agent and / or a curing catalyst,
(5) Hardened | cured material formed by hardening | curing curable resin composition as described in said (4),
About.
使用できるシクロヘキセンアルデヒド誘導体としては、シクロヘキセンカルボアルデヒド、メチルシクロヘキセンカルボアルデヒド、エチルシクロヘキセンカルボアルデヒド等が挙げられる。またトリメチロールアルカン誘導体としては、ジトリメチロールプロパン、ジトリメチロールメタン、ジトリメチロールエタン、ジトリメエチロールブタン等が挙げられる。トリメチロールアルカン誘導体は、シクロヘキセンアルデヒド誘導体1モルに対し、通常0.4~0.6モル、好ましくは0.45~0.55モル使用する。
本発明のジオレフィン化合物は、通常の環状アセタール化反応を応用すれば製造できる。例えば、反応媒体にトルエン、キシレンなどの溶媒を用いて共沸脱水しながら反応を行う方法(米国特許第2945008号公報)、濃塩酸に多価アルコールを溶解した後アルデヒド類を徐々に添加しながら反応を行う方法(特開昭48-96590号公報)、反応媒体に水を用いる方法(米国特許第3092640号公報)、反応媒体に有機溶媒を用いる方法(特開平7-215979号公報)、固体酸触媒を用いる方法(特開2007-230992号公報)等が知れている。 The diolefin compound of the present invention can be obtained by reacting a cyclohexene aldehyde derivative with a trimethylolalkane derivative.
Examples of the cyclohexene aldehyde derivative that can be used include cyclohexene carbaldehyde, methylcyclohexene carbaldehyde, and ethylcyclohexene carbaldehyde. Examples of 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. For example, 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.
過酸によるエポキシ化の手法としては具体的には特開2006-52187号公報に記載の手法などが挙げられる。
過酸化水素水によるエポキシ化の手法においては種々の手法が適応できるが、具体的には、特開昭59-108793号公報、特開昭62-234550号公報、特開平5-213919号公報、特開平11-349579号公報、特公平1―33471号公報、特開2001-17864号公報、特公平3-57102号公報等に挙げられるような手法が適応できる。 The diolefin body of the present invention represented by the formula (1) can be oxidized to form the epoxy resin of the present invention. Examples of 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).
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. Specifically, 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.
本発明のジオレフィン化合物、ポリ酸類及び4級アンモニウム塩を有機溶剤、緩衝液及び過酸化水素水のエマルジョン状態で反応を行う。 Hereinafter, a particularly preferable method for obtaining the epoxy resin of the present invention will be exemplified.
The diolefin compound, polyacids and quaternary ammonium salt of the present invention are reacted in an organic solvent, buffer solution and hydrogen peroxide emulsion.
具体的なポリ酸およびその塩としては、タングステン酸、12-タングスト燐酸、12-タングストホウ酸、18-タングスト燐酸、12-タングストケイ酸等のタングステン系の酸およびそれらの塩、モリブデン酸、リンモリブデン酸等のモリブデン系の酸およびそれらの塩等、が挙げられる。
これらの塩のカウンターカチオンとしては4級アンモニウムイオン、アルカリ土類金属イオン、アルカリ金属イオンなどが挙げられる。
具体的にはカルシウムイオン、マグネシウムイオン等のアルカリ土類金属イオン、ナトリウム、カリウム、セシウム等のアルカリ金属イオンなどが挙げられるがこれらに限定されない。
特に好ましいカウンターカチオンとしてはナトリウムイオン、カリウムイオン、カルシウムイオン、アンモニウムイオンである。
使用量としては原料1モルに対し、金属元素換算(タングテン酸ならタングステン原子、モリブデン酸ならモリブデン原子のモル数)で1.0~20ミリモル、好ましくは2.0~20ミリモル、さらに好ましくは2.5~10ミリモルである。 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.
具体的にはトリデカニルメチルアンモニウム塩、ジラウリルジメチルアンモニウム塩、トリオクチルメチルアンモニウム塩、トリアルキルメチル(アルキル基がオクチル基である化合物とデカニル基である化合物の混合タイプ)アンモニウム塩、トリヘキサデシルメチルアンモニウム塩、トリメチルステアリルアンモニウム塩、テトラペンチルアンモニウム塩、セチルトリメチルアンモニウム塩、ベンジルトリブチルアンモニウム塩、ジセチルジメチルアンモニウム塩、トリセチルメチルアンモニウム塩、ジ硬化牛脂アルキルジメチルアンモニウム塩などが挙げられるがこれらに限定されない。特に炭素数が25~100の物が好ましい。
またこれら塩のアニオン種に特に限定はなく、具体的にはハロゲン化物イオン、硝酸イオン、硫酸イオン、硫酸水素イオン、アセテートイオン、炭酸イオン、等が挙げられるが、これらに限定されない。
本発明においては特にハロゲンを含まない点から硝酸イオン、硫酸イオン、硫酸水素イオン、アセテートイオン、炭酸イオン、等が好ましく、特にエポキシ化時の副反応の少なさからアセテートイオン等のカルボン酸塩が特に好ましい。
炭素数が100を上回ると疎水性が強くなりすぎて、4級アンモニウム塩の水層への溶解性が悪くなる場合がある。炭素数が10未満であると親水性が強くなり、同様に4級アンモニウム塩の有機層への相溶性が悪くなり、好ましくない。
4級アンモニウム塩の使用量は使用するポリ酸類(好ましくはタングステン酸類)の価数倍の0.01~10倍当量が好ましい。より好ましくは0.05~6.0倍当量であり、さらに好ましくは0.05~4.5倍当量である(ただし、特に好ましい範囲はポリ酸類の種類と組み合わせによって異なる)。
例えば、タングステン酸であればH2WO4で2価であるので、タングステン酸1モルに対し、4級アンモニウム塩は0.02~20モルの範囲が好ましい。またタングストリン酸であれば3価であるので、同様に0.03~20モル、ケイタングステン酸であれば4価であるので0.04~40モルが好ましい。
4級アンモニウム塩の量が、ポリ酸類の価数倍の0.01倍当量よりも低い場合、エポキシ化反応が進行しづらい(場合によっては反応の進行が早くなる)、また副生成物ができやすいという問題が生じる。10倍当量よりも多い場合、後処理が大変であるばかりか、反応を抑制する働きがあり、好ましくない。 As the quaternary ammonium salt, a 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.
Specifically, 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. It is not limited to. Particularly preferred are those having 25 to 100 carbon atoms.
There are no particular limitations on the anionic species of these salts, and specific examples include halide ions, nitrate ions, sulfate ions, hydrogen sulfate ions, acetate ions, carbonate ions, and the like, but are not limited thereto.
In the present invention, 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.
When the number of carbon atoms exceeds 100, the hydrophobicity becomes too strong, and the solubility of the quaternary ammonium salt in the aqueous layer may deteriorate. When the number of carbon atoms is less than 10, the hydrophilicity is increased, and the compatibility of the quaternary ammonium salt with the organic layer is similarly deteriorated.
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).
For example, since tungstic acid is divalent with H 2 WO 4 , the quaternary ammonium salt is preferably in the range of 0.02 to 20 mol with respect to 1 mol of tungstic acid. In addition, since 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.
When 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. When 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.
緩衝液の使用方法は、例えば好ましい緩衝液である燐酸-燐酸塩水溶液の場合は過酸化水素に対し、0.1~10モル当量の燐酸(あるいは燐酸二水素ナトリウム等の燐酸塩)を使用し、塩基性化合物(たとえば水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム等)でpH調整を行うという方法が挙げられる。ここでpHは過酸化水素を添加した際に前述のpHになるように添加することが好ましい。また、燐酸二水素ナトリウム、燐酸水素二ナトリウムなどを用いて調整することも可能である。好ましい燐酸塩の濃度は0.1~60重量%、好ましくは5~45重量%である。
また、本反応においては緩衝液を使用せず、pH調整無しに、燐酸水素二ナトリウム、燐酸二水素ナトリウム、燐酸ナトリウム、トリポリ燐酸ナトリウムなど(またはその水和物)の燐酸塩を直接添加しても構わない。工程の簡略化、という意味合いではpH調整のわずらわしさが無く、直接の添加が特に好ましい。この場合の燐酸塩の使用量は、過酸化水素に対し、通常0.1~5モル%当量、好ましくは0.2~4モル%当量、より好ましくは、0.3~3モル%当量である。この際、過酸化水素に対し、5モル%当量を超えるとpH調整が必要となり、0.1モル%当量未満の場合、できたエポキシ化合物の加水分解物が進行しやすくなる、あるいは反応が遅くなるなどの弊害が生じる。 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.
For example, in the case of 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. And a method of adjusting pH with a basic compound (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, etc.). Here, it is preferable that the pH is added so that the above-mentioned pH is obtained when hydrogen peroxide is added. It is also possible to adjust using 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.
In this reaction, 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. It doesn't matter. In the sense of simplifying the process, there is no troublesome pH adjustment, and direct addition is particularly preferred. 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.
その使用量としては水、あるいは有機溶剤(例えば、トルエン、キシレン等の芳香族炭化水素、メチルイソブチルケトン、メチルエチルケトン等のケトン類、シクロヘキサン、ヘプタン、オクタン等の炭化水素、メタノール、エタノール、イソプロピルアルコール等のアルコール類など、各種溶剤)に溶解するものであれば、その使用量は過剰分の過酸化水素のモル数に対し、通常0.01~20倍モル、より好ましくは0.05~10倍モル、さらに好ましくは0.05~3倍モルである。これらは水、あるいは前述の有機溶剤の溶液として添加しても単体で添加しても構わない。
水や有機溶剤に溶解しない固体塩基を使用する場合、系中に残存する過酸化水素の量に対し、重量比で1~1000倍の量を使用することが好ましい。より好ましくは10~500倍、さらに好ましくは10~300倍である。水や有機溶剤に溶解しない固体塩基を使用する場合は、後に記載する水層と有機層の分離の後、処理を行っても構わない。 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.
When a solid base that does not dissolve in water or an organic solvent is used, 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. In the case of using a solid base that does not dissolve in water or an organic solvent, the treatment may be carried out after separation of an aqueous layer and an organic layer described later.
得られた有機層は必要に応じてイオン交換樹脂や金属酸化物、活性炭、複合金属塩、粘土鉱物等により、不純物を除去し、さらに水洗、ろ過等を行った後、溶剤を留去することで、目的とするエポキシ樹脂を得ることができる。場合によってはさらにカラムクロマトグラフィーや蒸留により精製しても構わない。 After the hydrogen peroxide quench (or before quenching), 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. Thus, the desired epoxy resin can be obtained. In some cases, it may be further purified by column chromatography or distillation.
で表される化合物を主成分とするが、式(3) (In the formula, plural Rs independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
The main component is a compound represented by formula (3)
に示すような各種の構造の化合物が混在する。またエポキシ基同士の重合した高分子量体や、その他副反応物が反応条件によっては生成する。 (In the formula, 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.
本発明の硬化性樹脂組成物は本発明のエポキシ樹脂を必須成分として含有する。本発明の硬化性樹脂組成物においては、硬化剤による熱硬化(硬化性樹脂組成物A)と酸を硬化触媒とするカチオン硬化(硬化性樹脂組成物B)の二種の方法が適応できる。 Hereinafter, it describes about the curable resin composition of this invention containing the epoxy resin of this invention.
The curable resin composition of the present invention contains the epoxy resin of the present invention as an essential component. In the curable resin composition of the present invention, 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.
これらエポキシ樹脂としては、シクロヘキセンカルボン酸とアルコール類とのエステル化反応あるいはシクロヘキセンメタノールとカルボン酸類とのエステル化反応(Tetrahedron vol.36 p.2409 (1980)、Tetrahedron Letter p.4475 (1980)等に記載の手法)、あるいはシクロヘキセンアルデヒドのティシェンコ反応(特開2003-170059号公報、特開2004-262871号公報等に記載の手法)、さらにはシクロヘキセンカルボン酸エステルのエステル交換反応(特開2006-052187号公報等に記載の手法)によって製造できる化合物を酸化した物などが挙げられる。
アルコール類としては、アルコール性水酸基を有する化合物であれば特に限定されないがエチレングリコール、プロピレングリコール、1,3-プロパンジオール、1,2-ブタンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、シクロヘキサンジメタノール、2,4-ジエチルペンタンジオール、2-エチル-2-ブチル-1.3-プロパンジオール、ネオペンチルグリコール、トリシクロデカンジメタノール、ノルボルネンジオールなどのジオール類、グリセリン、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、2-ヒドロキシメチル-1,4-ブタンジオールなどのトリオール類、ペンタエリスリトール、ジトリメチロールプロパンなどのテトラオール類などが挙げられる。またカルボン酸類としてはシュウ酸、マレイン酸、フマル酸、フタル酸、イソフタル酸、アジピン酸、シクロヘキサンジカルボン酸などが挙げられるがこれに限らない。 When using especially the curable resin composition of this invention for an optical use, combined use with an alicyclic epoxy resin or an epoxy resin of a silsesquioxane structure is preferable. Particularly in the case of 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.
These 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. Diol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1.3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, etc. Diols, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol, ditrimethylolpropane, etc. And the like. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.
これらエポキシ樹脂の具体例としては、ERL-4221、UVR-6105、ERL-4299(全て商品名、いずれもダウ・ケミカル製)、セロキサイド2021P、エポリードGT401、EHPE3150、EHPE3150CE(全て商品名、いずれもダイセル化学工業製)及びジシクロペンタジエンジエポキシドなどが挙げられるがこれらに限定されるものではない(参考文献:総説エポキシ樹脂 基礎編I p76-85)。
これらは単独で用いてもよく、2種以上併用してもよい。 Furthermore, the acetal compound by the acetal reaction of a cyclohexene aldehyde derivative and an alcohol form is mentioned.
Specific examples of these 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.
硬化剤による熱硬化(硬化性樹脂組成物A)
本発明の硬化性樹脂組成物Aが含有する硬化剤としては、例えばアミン系化合物、酸無水物系化合物、アミド系化合物、フェノール系化合物、カルボン酸系化合物などが挙げられる。用いうる硬化剤の具体例としては、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、ジシアンジアミド、リノレン酸の2量体とエチレンジアミンより合成されるポリアミド樹脂、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、無水ナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ブタンテトラカルボン酸無水物、ビシクロ[2,2,1]ヘプタン-2,3-ジカルボン酸無水物、メチルビシクロ[2,2,1]ヘプタン-2,3-ジカルボン酸無水物、シクロヘキサン-1,3,4-トリカルボン酸-3,4-無水物、などの酸無水物;各種アルコール、カルビノール変性シリコーン、と前述の酸無水物との付加反応により得られるカルボン酸樹脂、ビスフェノールA、ビスフェノールF、ビスフェノールS、フルオレンビスフェノール、テルペンジフェノール、4,4’-ビフェノール、2,2’-ビフェノール、3,3’,5,5’-テトラメチル-[1,1’-ビフェニル]-4,4’-ジオール、ハイドロキノン、レゾルシン、ナフタレンジオール、トリス-(4-ヒドロキシフェニル)メタン、1,1,2,2-テトラキス(4-ヒドロキシフェニル)エタン、フェノール類(フェノール、アルキル置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、ジヒドロキシナフタレン等)とホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、p-ヒドロキシベンズアルデヒド、o-ヒドロキシベンズアルデヒド、p-ヒドロキシアセトフェノン、o-ヒドロキシアセトフェノン、ジシクロペンタジエン、フルフラール、4,4’-ビス(クロロメチル)-1,1’-ビフェニル、4,4’-ビス(メトキシメチル)-1,1’-ビフェニル、1,4’-ビス(クロロメチル)ベンゼン、1,4’-ビス(メトキシメチル)ベンゼン等との重縮合物及びこれらの変性物、テトラブロモビスフェノールA等のハロゲン化ビスフェノール類、イミダゾール、トリフルオロボラン-アミン錯体、グアニジン誘導体、テルペンとフェノール類の縮合物などが挙げられるが、これらに限定されるものではない。これらは単独で用いてもよく、2種以上を用いてもよい。
本発明においては特に前述の酸無水物、カルボン酸樹脂に代表される、酸無水物構造、及びまたはカルボン酸構造を有する化合物が好ましい。 Hereinafter, each curable resin composition will be referred to.
Thermal curing with a curing agent (curable resin composition A)
Examples of the 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. Specific examples of 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, cyclohexane-1,3,4-tricarboxylic acid 3, 4 Acid anhydrides such as anhydrides; various alcohols, carbinol-modified silicones, and carboxylic acid resins obtained by addition reaction of the above acid anhydrides, 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, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) Formaldehyde, acetaldehyde Benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4, Polycondensates with 4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4′-bis (chloromethyl) benzene, 1,4′-bis (methoxymethyl) benzene and the like and their modified products Halogenated bisphenols such as tetrabromobisphenol A, imidazole, trifluoroborane-amine complexes, guanidine derivatives, and condensates of terpenes and phenols, but are not limited thereto. These may be used alone or in combination of two or more.
In the present invention, compounds having an acid anhydride structure and / or a carboxylic acid structure represented by the aforementioned acid anhydrides and carboxylic acid resins are particularly preferable.
光安定剤としては、ヒンダートアミン系の光安定剤、特にHALS等が好適である。HALSとしては特に限定されるものではないが、代表的なものとしては、ジブチルアミン・1,3,5-トリアジン・N,N’―ビス(2,2,6,6-テトラメチル-4-ピペリジル-1,6-ヘキサメチレンジアミンとN-(2,2,6,6-テトラメチル-4-ピペリジル)ブチルアミンの重縮合物、コハク酸ジメチル-1-(2-ヒドロキシエチル)-4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン重縮合物、ポリ〔{6-(1,1,3,3-テトラメチルブチル)アミノ-1,3,5-トリアジン-2,4-ジイル}{(2,2,6,6-テトラメチル-4-ピペリジル)イミノ}ヘキサメチレン{(2,2,6,6-テトラメチル-4-ピペリジル)イミノ}〕、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)〔〔3,5-ビス(1,1-ジメチルエチル)-4-ヒドリキシフェニル〕メチル〕ブチルマロネート、ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)セバケート、ビス(1-オクチロキシ-2,2,6,6-テトラメチル-4-ピペリジル)セバケート、2-(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)-2-n-ブチルマロン酸ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)、等が挙げられる。HALSは1種のみが用いられても良いし、2種類以上が併用されても良い。 Furthermore, you may add a light stabilizer to the curable resin composition A of this invention as needed.
As the light stabilizer, hindered amine-based light stabilizers, particularly HALS and the like are suitable. 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-tetramethyl-4-piperidyl) imino}], bis (1,2,2, 6,6-Pentamethyl-4-pi Peridyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di -T-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), etc. Only one HALS is used. Two or more types may be used in combination.
加熱条件は例えば80~230℃で1分~24時間程度が好ましい。加熱硬化の際に発生する内部応力を低減する目的で、例えば80~120℃、30分~5時間予備硬化させた後に、120~180℃、30分~10時間の条件で後硬化させることができる。 As a method of adhering the semiconductor chip to the substrate using the curable resin composition A of the present invention, 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. For the heating, methods such as hot air circulation, infrared rays and high frequency can be used.
For example, the heating conditions are preferably 80 to 230 ° C. for about 1 minute to 24 hours. For the purpose of reducing internal stress generated during heat-curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.
注入方法としては、ディスペンサー、トランスファー成形、射出成形等が挙げられる。
加熱は、熱風循環式、赤外線、高周波等の方法が使用できる。
加熱条件は例えば80~230℃で1分~24時間程度が好ましい。加熱硬化の際に発生する内部応力を低減する目的で、例えば80~120℃、30分~5時間予備硬化させた後に、120~180℃、30分~10時間の条件で後硬化させることができる。 As a molding method of the sealing material, as described above, an injection method in which the sealing material is injected into the mold frame in which the substrate on which the semiconductor chip is fixed is inserted and then heat-cured and molded, and the sealing material is formed on the mold. 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.
Examples of the injection method include dispenser, transfer molding, injection molding and the like.
For the heating, methods such as hot air circulation, infrared rays and high frequency can be used.
For example, the heating conditions are preferably 80 to 230 ° C. for about 1 minute to 24 hours. For the purpose of reducing internal stress generated during heat-curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.
酸性硬化触媒を用いて硬化させる本発明の硬化性樹脂組成物Bは、酸性硬化触媒として光重合開始剤あるいは熱重合開始剤を含有する。さらに、希釈剤、重合性モノマー、重合性オリゴマー、重合開始補助剤、光増感剤等の各種公知の化合物、材料等を含有していてもよい。また、所望に応じて無機充填材、着色顔料、紫外線吸収剤、酸化防止剤、安定剤等、各種公知の添加剤を含有してもよい。 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. Furthermore, you may contain various well-known compounds, materials, such as a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization start adjuvant, a photosensitizer. Moreover, you may contain various well-known additives, such as an inorganic filler, a color pigment, a ultraviolet absorber, antioxidant, a stabilizer, as needed.
活性エネルギー線カチオン重合開始剤の例は、金属フルオロホウ素錯塩および三フッ化ホウ素錯化合物(米国特許第3379653号)、ビス(ペルフルアルキルスルホニル)メタン金属塩(米国特許第3586616号)、アリールジアゾニウム化合物(米国特許第3708296号)、VIa族元素の芳香族オニウム塩(米国特許第4058400号)、Va族元素の芳香族オニウム塩(米国特許第4069055号)、IIIa~Va族元素のジカルボニルキレート(米国特許第4068091号)、チオピリリウム塩(米国特許第4139655号)、MF6-陰イオンの形のVIb族元素(米国特許第4161478号;Mはリン、アンチモンおよび砒素から選択される。)、アリールスルホニウム錯塩(米国特許第4231951号)、芳香族ヨードニウム錯塩および芳香族スルホニウム錯塩(米国特許第4256828号)、およびビス[4-(ジフェニルスルホニオ)フェニル]スルフィド-ビス-ヘキサフルオロ金属塩(Journal of Polymer Science, Polymer Chemistry、第2巻、1789項(1984年))である。その他、鉄化合物の混合配位子金属塩およびシラノール-アルミニウム錯体も使用することが可能である。
また、具体例としては、「アデカオプトマーSP150」、「アデカオプトマーSP170」(いずれも旭電化工業社製)、「UVE-1014」(ゼネラルエレクトロニクス社製)、「CD-1012」(サートマー社製)、「RP-2074」(ローディア社製)等が挙げられる。
該カチオン重合開始剤の使用量は、全エポキシ樹脂成分100重量部に対して、好ましくは、0.01~50重量部であり、より好ましくは、0.1~10重量部である。 As the acidic curing catalyst, a cationic polymerization initiator is preferable, and a photocationic polymerization initiator is particularly preferable. Examples of 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.
Examples of 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. 3,586,616), aryldiazonium Compound (US Pat. No. 3,708,296), aromatic onium salt of group VIa element (US Pat. No. 4,058,400), aromatic onium salt of group Va element (US Pat. No. 4069055), dicarbonyl chelate of group IIIa to Va element (US Pat. No. 4068091), thiopyrylium salt (US Pat. No. 4,139,655), group VIb element in the form of MF 6- anion (US Pat. No. 4,161,478; M is selected from phosphorus, antimony and arsenic), Arylsulfonium complex salts (US Pat. No. 4,231,951) ), 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)). In addition, mixed ligand metal salts of iron compounds and silanol-aluminum complexes can also be used.
As specific examples, “Adekaoptomer SP150”, “Adekaoptomer SP170” (all manufactured by Asahi Denka Kogyo Co., Ltd.), “UVE-1014” (manufactured by General Electronics Co., Ltd.), “CD-1012” (Sartomer Company) And "RP-2074" (manufactured by Rhodia).
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.
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながら水150部、3-シクロヘキセンカルボアルデヒド55.1部、ジトリメチロールプロパン62.6部、濃塩酸7.3部を加え、60℃で10時間反応を行った。反応終了後、水100部、3%水酸化ナトリウム水溶液を30部加え、さらにリン酸水素二ナトリウムで中和した。ここに、メチルイソブチルケトン200部を加え、水100部で3回水洗を行った後、溶剤等を除去することにより下記式(4) 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).
得られた化合物の形状は液状であり、GCによる純度は94%、GPCによる分析の結果、98%の純度である事を確認した。粘度は21000mPa・s(25℃ E型粘度計)であった。 101 parts of the diolefin compound (D-1) of the present invention represented by the formula:
It was confirmed that the shape of the obtained compound was liquid, the purity by GC was 94%, and the analysis by GPC confirmed that the purity was 98%. The viscosity was 21000 mPa · s (25 ° C. E-type viscometer).
撹拌機、還流冷却管、撹拌装置、ディーンスターク菅を備えたフラスコに、窒素パージを施しながらトルエン150部、3-シクロヘキセンカルボアルデヒド55.1部、ジトリメチロールプロパン62.6部、p-トルエンスルホン酸1.5部を加え、還流条件で水を抜きながら10時間反応を行った。反応終了後、トリポリリン酸ナトリウム3部加え、100℃で30分撹拌後、ろ過、さらにトルエン200部、10重量%リン酸水素二ナトリウム水溶液100部を加え、水洗、さらに、水100部で3回水洗をおこなった。ここに、メチルイソブチルケトン200部を加え、水100部で3回水洗を行った後、溶剤等を除去することにより前記式(4)で表される本発明のジオレフィン化合物(D-2)を108部得た。
得られた化合物の形状は液状であり、GCによる純度は93%、GPCによる分析の結果、98%の純度である事を確認した。粘度は22000mPa・s(25℃ E型粘度計)であった。 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. for 30 minutes, filtered, 200 parts of toluene, 100 parts of a 10 wt% disodium hydrogen phosphate aqueous solution were added, washed with water, and further 3 times with 100 parts of water. Washed with water. To this, 200 parts of methyl isobutyl ketone was added, washed three times with 100 parts of water, and then the solvent was removed to remove the diolefin compound (D-2) of the present invention represented by the above formula (4). 108 parts were obtained.
It was confirmed that the shape of the obtained compound was liquid, the purity by GC was 93%, and the analysis by GPC confirmed that the purity was 98%. The viscosity was 22000 mPa · s (25 ° C. E-type viscometer).
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながら水15部、12-タングストリン酸0.95部、燐酸水素ニナトリウム0.78、ジ硬化牛脂アルキルジメチルアンモニウムアセテート2.7部(ライオンアクゾ製 50重量%ヘキサン溶液)を加え、タングステン酸系触媒を生成させた後、トルエン120部、実施例2で得られた式(4)の化合物(D-2)108部を加え、さらに再度攪拌することでエマルジョン状態の液とした。この溶液を50℃に昇温し、激しく攪拌しながら、35%過酸化水素水55部を加え、そのまま50℃で13時間攪拌した。GCにて反応の進行を確認したところ、反応終了後の基質のコンバ-ジョンは>99%であり、原料ピークは消失していた。
ついで1%水酸化ナトリウム水溶液で中和した後、20%チオ硫酸ナトリウム水溶液25部を加え30分攪拌を行い、静置した。2層に分離した有機層を取り出し、ここにシリカゲル(ワコーゲル C-300)20部、活性炭(NORIT製 CAP SUPER)10部、ベントナイト(ホージュン製 ベンゲルSH)20部を加え、室温で1時間攪拌後、ろ過した。得られたろ液を水100部で3回水洗を行い、得られた有機層より、有機溶剤を留去することで、下記式(5) 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. The temperature of this solution was raised to 50 ° C., and while stirring vigorously, 55 parts of 35% aqueous hydrogen peroxide was added and stirred as it was at 50 ° C. for 13 hours. When the progress of the reaction was confirmed by GC, the substrate conversion after the completion of the reaction was> 99%, and the raw material peak disappeared.
Then, after neutralizing with 1% aqueous sodium hydroxide solution, 25 parts of 20% aqueous sodium thiosulfate solution was added and stirred for 30 minutes and allowed to stand. The organic layer separated into two layers was taken out, 20 parts of silica gel (Wakogel C-300), 10 parts of activated carbon (CAP SUPER made by NORIT) and 20 parts of bentonite (Bengel SH made by Hojun) were added and stirred at room temperature for 1 hour. And filtered. The obtained filtrate was washed with 100 parts of water three times, and the organic solvent was distilled off from the obtained organic layer to obtain the following formula (5).
GPCの測定結果より、式(5)の骨格の化合物(EP-1)を85%含有していることを確認した。
また、その粘度は230Pa・s(25℃ E型粘度計)であり、エポキシ当量は264g/eq.であった。 99 parts of the epoxy resin of the present invention containing as a main component a compound represented by the formula:
From the GPC measurement results, it was confirmed that 85% of the compound (EP-1) having a skeleton of formula (5) was contained.
The viscosity is 230 Pa · s (25 ° C. E-type viscometer), and the epoxy equivalent is 264 g / eq. Met.
実施例3で得られた硬化性樹脂組成物を真空脱泡20分間実施後、横7mm、縦5cm、厚み約800μmの試験片用金型に静かに注型し、その後上からポリイミドフィルムでフタをした。その注型物を下記条件で硬化させ動的粘弾性用試験片を得た。これらの試験片を用い、下記に示した条件で、動的粘弾性試験を実施した。
硬化条件
120℃×1時間+150℃×3時間
測定条件
動的粘弾性測定器:TA-instruments製、DMA-2980
測定温度範囲:-30℃~280℃
温速度:2℃/分
試験片サイズ:5mm×50mmに切り出した物を使用した(厚みは約800μm)。
解析条件
Tg:DMA測定に於けるTan-δのピーク点をTgとした。 (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 μm. 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. × 3 hours Measuring conditions 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 μm).
Analysis conditions Tg: The peak point of Tan-δ in DMA measurement was defined as Tg.
実施例3で得られた硬化性樹脂組成物を真空脱泡20分間実施後、テフロン(登録商標)製のφ5mmチューブにて注形し、その注型物を上記条件で硬化させ試験片を得た。この試験片を用い、下記に示した条件で、耐熱性試験を実施した。
測定条件
動的粘弾性測定器:真空理工(株)製 TM-7000
測定温度範囲:40℃~250℃
温速度:2℃/分
試験片サイズ:φ5mm 10mmに切り出した物を使用した。 (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) φ5 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: φ5 mm A material cut into 10 mm was used.
実施例3で得られた本発明のエポキシ樹脂(EP-1)、比較例として(3,4-エポキシシクロヘキシルメチル-(3,4-エポキシ)シクロヘキシルカルボキシレート(ダウ・ケミカル社製 ERL-4221 エポキシ当量 140g/eq. 以下、EP-3と称す)について、硬化剤としてH1、シクロヘキサン-1,2,4-トリカルボン酸-1,2-無水物(三菱瓦斯化学株式会社製 H-TMAn 以下、H2と称す)、硬化促進剤としてC1を使用し、下記表2に示す配合比(重量部)で配合し、20分間脱泡を行い、本発明の硬化性組成物を得た。 Examples 6 and 7, Comparative Examples 1 and 2
The epoxy resin (EP-1) of the present invention obtained in Example 3 and (3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexyl carboxylate (ERL-4221 epoxy manufactured by Dow Chemical Company) as a comparative example Equivalent 140 g / eq., Hereinafter referred to as EP-3), H1, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd., H-TMAn, hereinafter H2) C1 was used as a curing accelerator, blended at a blending ratio (parts by weight) shown in Table 2 below, defoamed for 20 minutes, and the curable composition of the present invention was obtained.
(LED試験)
実施例6,7、及び比較例1,2で得られた硬化性樹脂組成物を真空脱泡20分間実施後、シリンジに充填し精密吐出装置を使用して、発光波長465nmを持つ発光素子を搭載した5mm角の表面実装型LEDに注型した。その後、所定の硬化条件で硬化させることで、試験用LEDを得た。
(LED点灯試験)
点灯試験は、試験用LEDを基板に実装したものにつき、規定電流である30mAの2倍の電流での点灯試験を行った。詳細な条件は下記に示した。測定項目としては、200時間点灯後の照度を積分球を使用して測定し、試験用LEDの照度の保持率を算出した。
点灯詳細条件
発光波長:465nm
駆動方式:定電流方式、60mA(発光素子規定電流は30mA)
駆動環境:85℃、85%
評価:200時間後の照度とその照度保持率 Using the obtained curable resin composition, an LED test was conducted in the manner described below. Curing conditions are 120 ° C. × 1 hour after pre-curing at 120 ° C. × 1 hour.
(LED test)
The curable resin compositions obtained in Examples 6 and 7 and Comparative Examples 1 and 2 were vacuum degassed for 20 minutes, and then filled into a syringe and a light emitting element having an emission wavelength of 465 nm was obtained using a precision discharge device It was cast into a 5 mm square surface-mounted LED. Thereafter, a test LED was obtained by curing under predetermined curing conditions.
(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
なお、本出願は、2008年10月6日付けで出願された日本特許出願(特願2008-259469)に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。 Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2008-259469) filed on October 6, 2008, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.
Claims (5)
- 請求項1に記載のジオレフィン化合物を酸化することにより得られるエポキシ樹脂。 An epoxy resin obtained by oxidizing the diolefin compound according to claim 1.
- 過酸化水素または過酸を用いて酸化して得られた請求項2に記載のエポキシ樹脂。 The epoxy resin according to claim 2 obtained by oxidation using hydrogen peroxide or peracid.
- 請求項2または3に記載のエポキシ樹脂と硬化剤および/または硬化触媒を含有する硬化性樹脂組成物。 A curable resin composition comprising the epoxy resin according to claim 2 or 3 and a curing agent and / or a curing catalyst.
- 請求項4に記載の硬化性樹脂組成物を硬化してなる硬化物。 Hardened | cured material formed by hardening | curing curable resin composition of Claim 4.
Priority Applications (2)
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CN200980148946.XA CN102239157B (en) | 2008-10-06 | 2009-10-06 | Diolefin compound, epoxy resin, curable resin composition and cured product |
JP2010532933A JP5469078B2 (en) | 2008-10-06 | 2009-10-06 | Diolefin compound, epoxy resin, curable resin composition, and cured product |
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Application Number | Priority Date | Filing Date | Title |
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JP2008-259469 | 2008-10-06 | ||
JP2008259469 | 2008-10-06 |
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PCT/JP2009/067432 WO2010041670A1 (en) | 2008-10-06 | 2009-10-06 | Diolefin compound, epoxy resin, curable resin composition and cured product |
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JP (1) | JP5469078B2 (en) |
CN (2) | CN103788059A (en) |
TW (1) | TWI510478B (en) |
WO (1) | WO2010041670A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103485480A (en) * | 2013-10-08 | 2014-01-01 | 江苏明福钢结构有限公司 | Net rack with steel structure |
JP5492081B2 (en) * | 2009-03-19 | 2014-05-14 | 日本化薬株式会社 | Diolefin compound, epoxy resin and composition |
CN106120508A (en) * | 2016-06-22 | 2016-11-16 | 赵传宝 | A kind of colored pressing mold concrete artistic terrace |
WO2023199845A1 (en) * | 2022-04-15 | 2023-10-19 | 株式会社レゾナック | Heat-curable adhesive composition, layered film, connected structure, and production method therefor |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111138383B (en) * | 2019-12-30 | 2022-03-01 | 昌德新材科技股份有限公司 | Alicyclic epoxy resin and preparation method thereof |
CN112341407A (en) * | 2020-10-23 | 2021-02-09 | 如皋市丹凤纺织有限公司 | Synthetic method of yarn impregnation auxiliary agent |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2005029632A (en) * | 2003-07-09 | 2005-02-03 | Konica Minolta Medical & Graphic Inc | Ink composition for ink jet, method for forming image and epoxy compound |
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KR101005948B1 (en) * | 2002-09-05 | 2011-01-05 | 다이셀 가가꾸 고교 가부시끼가이샤 | Process for preparation of alicyclic diepoxy compounds, curable epoxy resin compositions, epoxy resin compositions for the encapsulation of electronic components, stabilizers for electrical insulating oils, and casting epoxy resin compositions for electrical insulation |
JP2004099467A (en) * | 2002-09-05 | 2004-04-02 | Daicel Chem Ind Ltd | Method for producing alicyclic epoxy compound |
JP2004262874A (en) * | 2003-03-03 | 2004-09-24 | Daicel Chem Ind Ltd | Method for producing diepoxycyclooctanes |
-
2009
- 2009-10-06 CN CN201310659598.0A patent/CN103788059A/en active Pending
- 2009-10-06 CN CN200980148946.XA patent/CN102239157B/en not_active Expired - Fee Related
- 2009-10-06 JP JP2010532933A patent/JP5469078B2/en not_active Expired - Fee Related
- 2009-10-06 TW TW098133796A patent/TWI510478B/en not_active IP Right Cessation
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Patent Citations (1)
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JP2005029632A (en) * | 2003-07-09 | 2005-02-03 | Konica Minolta Medical & Graphic Inc | Ink composition for ink jet, method for forming image and epoxy compound |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5492081B2 (en) * | 2009-03-19 | 2014-05-14 | 日本化薬株式会社 | Diolefin compound, epoxy resin and composition |
CN103485480A (en) * | 2013-10-08 | 2014-01-01 | 江苏明福钢结构有限公司 | Net rack with steel structure |
CN106120508A (en) * | 2016-06-22 | 2016-11-16 | 赵传宝 | A kind of colored pressing mold concrete artistic terrace |
WO2023199845A1 (en) * | 2022-04-15 | 2023-10-19 | 株式会社レゾナック | Heat-curable adhesive composition, layered film, connected structure, and production method therefor |
Also Published As
Publication number | Publication date |
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CN103788059A (en) | 2014-05-14 |
TW201029984A (en) | 2010-08-16 |
TWI510478B (en) | 2015-12-01 |
JPWO2010041670A1 (en) | 2012-03-08 |
JP5469078B2 (en) | 2014-04-09 |
CN102239157B (en) | 2014-01-08 |
CN102239157A (en) | 2011-11-09 |
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