Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
  • C07C69/75—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a six-membered ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
  • C07D303/02—Compounds containing oxirane rings
  • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
  • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
  • C08G65/24—Epihalohydrins
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/84—Passivation; Containers; Encapsulations
  • H10K50/842—Containers
  • H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

• the present invention relates to a novel olefin compound and an epoxy resin derived from the olefin compound, which are suitable for use in electrical and electronic materials.
• the present invention also relates to a curable resin composition containing the epoxy resin and a cured product obtained by curing the curable resin composition. Furthermore, it is related with the LED device sealed with the cured resin composition.
• 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.
• RTM Resin Transfer Molding
• 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 as compared with glycidyl ether type epoxy compounds, and are used in various kinds of transparent sealing materials.
• alicyclic epoxy compounds with improved heat resistance and light resistance have been demanded particularly in fields where advanced heat / light properties such as LED applications are required (see Patent Documents 1 to 3).
• An object of the present invention is to provide a novel alicyclic epoxy resin that gives a cured product having excellent heat deterioration characteristics and optical characteristics.
• R's are present independently and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
• P is a chain alkyl having a branched structure having 6 to 20 carbon atoms in total.
• An olefin compound represented by a chain linker (2) The olefin compound according to item (1), wherein the linker P has a structure having a main chain of 3 or more carbon atoms and an alkyl branched chain in at least one position; (3) The olefin compound according to (1) or (2) above, wherein the linker P has two or more alkyl groups that are branched from the main chain, (4) The olefin compound according to any one of (1) to (3), which is represented by the following formula (D-1) or (D-2):
• the olefin compound of the present invention is a raw material of an epoxy resin (epoxy resin of the present invention) that provides a cured product excellent in heat resistance, light resistance, or moisture resistance such as heat resistance and heat resistance, as well as adhesiveness.
• epoxy resin epoxy resin of the present invention
• the curable resin composition of the present invention containing the epoxy resin of the present invention is useful for a wide range of applications such as electric / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resists and the like.
• the epoxy resin of this invention does not have an aromatic ring, it is very useful for an optical material.
• the olefin compound of the present invention has the following formula (1)
• R's are present independently and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
• P is a chain alkyl having a branched structure having 6 to 20 carbon atoms in total. It is a chain linker.
• the chain alkyl chain linker represented by P has as its main chain an alkyl chain in which two alcoholic hydroxyl groups of a diol used as a raw material are bonded as described below, and the alkyl chain It is a structure which has the alkyl chain branched from.
• the branched alkyl chain may be branched from any carbon atom constituting the main chain, and includes, for example, a case where the branched alkyl chain is branched from a carbon to which an alcoholic hydroxyl group is bonded. Specific examples of such chain alkyl chain linkers are shown below.
• the linker P is bonded to the oxygen atom of the formula (1) with *.
• the linker P has a structure having an alkyl branched chain with respect to the main chain alkylene group and is not particularly limited as long as the total carbon number is 6 to 20, but the main chain carbon number is not limited. Is 3 or more, preferably 3 to 10, preferably having at least one alkyl branched chain, and particularly preferably having two or more alkyl branched chains.
• the alkyl branched chain preferably has 2 to 17 carbon atoms from the viewpoint of heat-resistant coloring.
• those having an alkyl branched chain from two or more carbon atoms having different main chain alkylene groups are particularly preferred. In this case, those having 2 or more carbon atoms in the branched chain are preferred.
• the olefin compound represented by the formula (1) includes a cyclohexene carboxylic acid derivative and a diol having a structure in which an alkyl chain to which an alcoholic hydroxyl group is bonded has an alkyl chain branched from the alkyl chain. Obtained by reaction.
• the cyclohexene carboxylic acid derivative the following formula (2)
• each R is independently present and represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• X represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms or a halogen atom.
• the compound of the formula (2) include cyclohexene carboxylic acid, methyl cyclohexene carboxylate, ethyl cyclohexenecarboxylate, propyl cyclohexenecarboxylate, butyl cyclohexenecarboxylate, hexylcyclohexenecarboxylate, and (cyclohexenylmethyl) cyclohexenecarboxylate.
• the diol in the present invention is a diol having a branched alkyl chain having a branched structure and having a total carbon number of 6 to 20. Specific examples of the compound include those described below.
• a general esterification method can be applied as a reaction between the cyclohexenecarboxylic acid derivative and the diol.
• general esterification reactions can be applied, such as Fischer esterification using acid catalysts, acid halides under basic conditions, alcohol reactions, condensation reactions using various condensing agents (ADVANCED ORGANIC CHEMISTRY) PartB: Reaction and Synthesis p135, 145-147, 151 etc.).
• Specific examples include esterification reactions between alcohols and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), and transesterification of carboxylic acid esters (Japan) It can also be produced by using Japanese Patent Laid-Open No. 2006-052187.
• R is preferably any one of a hydrogen atom, a methyl group, an ethyl group, and a butyl group.
• R is preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom, in order to improve the reactivity.
• the olefin compound 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 Japanese Patent Application Laid-Open No. 2006-52187.
• Various methods can be applied to the epoxidation method using hydrogen peroxide solution. Specifically, Japanese Patent Application Laid-Open No. 59-108793, Japanese Patent Application Laid-Open No.
• the olefin compound of the present invention polyacids, and quaternary ammonium salt are reacted with an organic substance in an emulsion state of hydrogen peroxide.
• the polyacid used in the present invention is not particularly limited as long as it is a compound having a polyacid structure, but polyacids containing tungsten or molybdenum are preferred, polyacids containing tungsten are more preferred, and tungstates are particularly preferred.
• Specific examples of polyacids and polyacid salts include tungsten acid, molybdic acid and phosphomolybdic acid selected from tungstic acid, 12-tungstophosphoric acid, 12-tungstoboric acid, 18-tungstophosphoric acid, 12-tungstosilicic acid, and the like. And molybdenum-based acids selected from the above, and salts thereof.
• Examples of the counter cation of these salts include quaternary ammonium ions, alkaline earth metal ions, and alkali metal ions. Among them, particularly preferable counter cations include sodium ion, potassium ion, calcium ion, and ammonium ion.
• Alkaline earth metal ions sodium, potassium, cesium, etc. Although such metal ions include, but are not limited to.
• the polyacid is used in an amount of 0.5 to 20 mmol, preferably 1.0 to 20 in terms of metal element (tungsten acid: tungsten atom, molybdic acid: molybdenum atom) with respect to 1 mol of the olefin compound of the present invention.
• Mmol more preferably 2.5 to 15 mmol.
• quaternary ammonium salt As the quaternary ammonium salt used in the reaction, a quaternary ammonium salt having a total carbon number of 10 or more, preferably 25 to 100, more preferably 25 to 55 can be preferably used. In particular, all of the alkyl chains are aliphatic chains. Some 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.
• anionic species of these salts include halide ions, nitrate ions, sulfate ions, hydrogen sulfate ions, acetate ions, carbonate ions, and the like, but are not limited thereto.
• the amount of quaternary ammonium salt used is preferably 0.01 to 10 times the valence of the tungstic acid used. More preferably, it is 0.05 to 6.0 times equivalent, and still more preferably 0.05 to 4.5 times equivalent.
• 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 for tungstophosphoric acid, it is similarly 0.03 to 30 mol, and for tetratungstic acid, it is tetravalent, so 0.04 to 40 mol is preferable.
• the amount of quaternary ammonium salt used is lower than 0.01 times the valence of tungstic acids, the epoxidation reaction is difficult to proceed (in some cases, the reaction proceeds faster), and by-products The problem that it is easy to do occurs.
• 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.
• a buffer solution In the reaction, it is preferable to use a buffer solution. 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 4 and 10, more preferably pH 5-9. When the pH is less than 4, the hydrolysis reaction and polymerization reaction of the epoxy group easily proceed. Moreover, when pH10 is exceeded, reaction will become extremely slow and the problem that reaction time is too long will arise. In particular, in the present invention, it is preferable to adjust the pH to be between 5 and 9 when the tungstic acid as a catalyst is dissolved.
• a phosphoric acid-phosphate aqueous solution which is a preferable buffer
• 0.1 to 10 mol% equivalent of phosphoric acid or a phosphate such as sodium dihydrogen phosphate
• a method of adjusting pH with a basic compound for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, etc.
• a basic compound for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, etc.
• the pH is added so that the above-mentioned pH is obtained when hydrogen peroxide is added.
• the preferred phosphate concentration is 0.1 to 60% by weight, preferably 1 to 45% by weight.
• a buffer solution is not used, and a phosphate such as disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate or 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 epoxy resin hydrolyzate 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 olefin compound 1 which is a reaction substrate. . 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.
• buffer solution or water and phosphate
• tungstic acid were added to adjust pH
• quaternary ammonium salt organic solvent and olefin compound were added and hydrogen peroxide was added dropwise to the mixture after stirring in two layers.
• the technique of doing is used.
• stirring water, an organic solvent and an olefin compound, tungstic acid and phosphoric acid (or phosphates) are added, pH is adjusted, quaternary ammonium salt is added, and the mixture is stirred in two layers.
• a method of dropping hydrogen peroxide may be used.
• reaction operation method for example, when the reaction is performed in a batch-type reaction kettle, an olefin compound, hydrogen peroxide (aqueous solution), polyacid (catalyst), buffer solution, quaternary ammonium salt and an organic solvent are added. 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.
• the reducing agent examples include sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, vitamin C and the like.
• the reducing agent is used in an excess amount of hydrogen peroxide of usually 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. is there. These are preferably added as an aqueous solution, and the concentration is preferably 0.5 to 30% by weight.
• 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 reaction product is extracted from the aqueous layer.
• the above organic solvent is added and the operation is performed. Perform extraction.
• 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 olefin compound. This operation is repeated several times as necessary, and then the organic layer is separated. If necessary, the organic layer is washed with water and purified.
• the obtained organic layer may be an ion exchange resin, a metal oxide (especially silica gel or alumina is preferred), activated carbon (especially chemical activated carbon is particularly preferred), or a complex metal salt (especially a basic complex metal salt).
• a metal oxide especially silica gel or alumina is preferred
• activated carbon especially chemical activated carbon is particularly preferred
• a complex metal salt especially a basic complex metal salt.
• a mineral with a viscosity especially a layered viscosity mineral such as montmorillonite is preferred
• the solvent is distilled off to obtain the desired epoxy resin.
• it may be further purified by distillation.
• distillation method distillation may be performed by a technique such as thin film or rotary molecular distillation.
• the epoxy resin thus obtained is represented by the formula (3)
• the main component is a molecule represented by formula (4)
• any combination of (A) to (D) may be used.
• R and P have the same meaning as in formula (1).
• the compounds of various structures as shown in FIG. Depending on the reaction conditions, polymerized high molecular weight polymer of epoxy groups and other side reaction products are formed.
• the obtained epoxy resin can be used as various resin raw materials such as epoxy acrylate and derivatives thereof, oxazolidone compounds or 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-hydroxyacetophenone, -Hyd
• halogenated bisphenols such as tetrabromobisphenol A, glycidyl ethers derived from alcohols, fats Cyclic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain, cyclic, ladder, or a mixed structure of at least two of these glycidyl groups and siloxane structures) // Epoxy resin having epoxycyclohexane structure), etc.
• halogenated bisphenols such as tetrabromobisphenol A, glycidyl ethers derived from alcohols, fats Cyclic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain, cyclic, ladder, or a mixed structure of at least two of these glycidyl groups and siloxane structures) // Epoxy resin having epoxycyclohexane structure), etc.
• the epoxy resin of the present invention is preferably used in combination with an alicyclic epoxy resin or an epoxy resin having a silsesquioxane structure.
• 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.
• esterification reaction of cyclohexene carboxylic acid and alcohol or esterification reaction of cyclohexene methanol and carboxylic acid (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980) Or the Tyshenko reaction of cyclohexene aldehyde (method described in Japanese Patent Application Laid-Open No. 2003-170059, Japanese Patent Application Laid-Open No. 2004-262871, etc.), and further transesterification of cyclohexene carboxylic acid ester
• Examples thereof include compounds that can be produced by the method described in Japanese Patent Application Laid-Open No. 2006-052187.
• 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 such as 1,6-hexanediol and cyclohexanedimethanol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol, etc.
• carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.
• examples of the compound having a cyclohexene structure other than the above include an acetal compound obtained by an acetal reaction between a cyclohexene aldehyde derivative and an alcohol.
• a reaction method it can be produced by applying a general acetalization reaction.
• a method of carrying out a reaction while azeotropically dehydrating using a solvent such as toluene or xylene as a reaction medium US Pat. No. 2,945,008
• concentrated hydrochloric acid A method in which polyhydric alcohol is dissolved in the mixture and then the reaction is carried out while gradually adding aldehydes (Japanese Patent Laid-Open No.
• 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.
• each curable resin composition will be referred to.
• Thermal curing with a curing agent (curable resin composition A)
• 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 nitrogen-containing compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and a polyamide resin synthesized from ethylenediamine.
• Examples of the compound having an acid anhydride structure include methyltetrahydrophthalic anhydride, methylnadic 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-anhydride And 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, etc.
• methylhexahydrophthalic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, 2,4-cyclohexanetricarboxylic acid-1,2-anhydride is particularly preferred.
• a compound having an acid anhydride structure is preferable, and used as a curing agent.
• the compound having a carboxylic acid structure (hereinafter referred to as polycarboxylic acid) is particularly preferably a bi- to tetra-functional polycarboxylic acid, and more preferably an addition reaction of a bi- to tetra-functional polyhydric alcohol with an acid anhydride.
• the polycarboxylic acid obtained by this is preferable. It is preferable to use polycarboxylic acid as the curing agent from the viewpoint that the curing agent is less volatile, poor curing is difficult to occur, and a tough composition is easily obtained.
• the bi- to tetrafunctional polyhydric 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.
• Diols such as methanol, dicyclopentadiene dimethanol, norbornenediol
• triols such as glycerin, trimethylolethane, trimethylolpropane, trimethyl
• bifunctional to tetrafunctional polyhydric alcohols are cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, Branched and cyclic alcohols such as cyclopentadienedimethanol and norbornenediol.
• Examples of acid anhydrides for producing polycarboxylic acids include methyltetrahydrophthalic anhydride, methylnadic 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-anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride and the like are preferable.
• the conditions for the addition reaction are not particularly specified, but one specific reaction condition is that the acid anhydride and polyhydric alcohol are reacted while heating at 40 to 150 ° C. under the conditions of no catalyst and no solvent. In this method, the reaction is taken out after completion of the reaction. However, it is not limited to this reaction condition.
• the acid anhydride and polycarboxylic acid may be used alone or in combination of two or more.
• the weight ratio of the acid anhydride to the polycarboxylic acid is 90/10 to 20/80, particularly preferably 80/20 to 30/70.
• 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.
• the curing accelerator that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole.
• the curing accelerator is usually used in the range of 0.01 to 5.0 parts by weight 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 A of the present invention. Part.
• 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-tert-butylphenol), 2,2′-methylenebis (4-ethy
• 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 include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like.
• the present invention is not limited to these. These may be used alone or in combination of two or more.
• the content of these inorganic fillers is used in an amount of 0 to 95% by weight in the curable resin composition A of the present invention.
• the curable resin composition A of the present invention includes a silane coupling agent, stearic acid, palmitic acid, calcium stearate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate).
• zinc compounds such as zinc phosphate phosphate (octyl zinc phosphate, zinc stearyl phosphate, etc.), various compounding agents such as surfactants, dyes, pigments, UV absorbers, and various thermosetting resins can be added. it can.
• 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 a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO 3 : Ce, Y 3 Al 5 O1 2 : 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 as necessary, and the curable resin composition varnish.
• the curable resin composition of the present invention is obtained by hot press-molding a prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating. It can be set as the hardened
• the solvent is used in an amount usually accounting for 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition A of the present invention and the solvent. Moreover, if it is a liquid composition, the epoxy resin hardened
• 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 characteristics in the B stage.
• the curable resin composition A of the present invention is applied onto a release film as the curable resin composition varnish, the solvent is removed under heating, and then B-stage is performed. Thus, it is obtained as a sheet-like adhesive.
• This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.
• Curable resin composition B (cationic curing with acidic curing catalyst)
• the curable resin composition B of the present invention that is cured using an acidic curing catalyst contains a photopolymerization initiator or a thermal polymerization initiator as an acidic curing catalyst.
• a photopolymerization initiator or a thermal polymerization initiator as an acidic curing catalyst.
• a cationic polymerization initiator is preferable, and a 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.
• 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, but the amount of ultraviolet irradiation varies depending on the blending of the curable resin composition, and thus is determined by the respective curing conditions.
• the photocurable curable resin composition is cured and the irradiation amount is sufficient to improve the adhesive strength of the cured product. Since it is necessary for light to be transmitted through the details during the curing, the epoxy resin and the curable resin composition B of the present invention are desired to be highly transparent. Also. In these epoxy resin-based photocuring, it is difficult to cure completely only by light irradiation, and in applications where heat resistance is required, it is necessary to complete reaction curing by heating after light irradiation.
• the temperature is preferably from room temperature to 150 ° C. for 30 minutes to 7 days.
• the higher the temperature range the more effective the curing is after light irradiation, and the short heat treatment is effective. Further, the lower the temperature, the longer the heat treatment. By performing such heat after-curing, an effect of aging treatment is obtained.
• the shape of the cured product obtained by curing these curable resin compositions B can be variously selected depending on the application, it is not particularly limited. For example, it may be a film shape, a sheet shape, a bulk shape, or the like.
• the molding method varies depending on the applicable part and member, for example, molding methods such as casting method, casting method, screen printing method, spin coating method, spray method, transfer method, dispenser method, etc. can be applied, It is not limited to these.
• polishing glass, hard stainless steel polishing plate, polycarbonate plate, polyethylene terephthalate plate, polymethyl methacrylate plate, or the like can be applied.
• a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyimide film, or the like can be applied in order to improve releasability from the mold.
• the photo cation curable resin composition B of the present invention dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or ⁇ -butyrolactone is used as a copper-clad laminate
• a coating film is formed on a substrate such as a ceramic substrate or a glass substrate with a film thickness of 5 to 160 ⁇ m by a method such as screen printing or spin coating.
• the coating film is preliminarily dried at 60 to 110 ° C., and then irradiated with ultraviolet rays (for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a laser beam, etc.) through a negative film having a desired pattern.
• ultraviolet rays for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a laser beam, etc.
• post-exposure baking is performed at 70 to 120 ° C.
• the unexposed part is dissolved and removed (developed) with a solvent such as polyethylene glycol monoethyl ether, and if necessary, sufficient by irradiation with ultraviolet rays and / or heating (eg, at 100 to 200 ° C. for 0.5 to 3 hours). Curing is performed to obtain a cured product. In this way, it is also possible to obtain a printed wiring board.
• the cured product obtained by curing the curable resin composition A and the curable resin composition B of the present invention can be used for various applications 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
• antireflection films antireflection films
• optical correction films housing materials
• front glass protective films front glass replacement materials
• adhesives and LED displays that are expected as next-generation flat panel displays
• LED molding materials LED sealing materials, front glass protective films, front glass substitute materials, adhesives, and substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, deflection plates , Phase difference plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various in field emission display (FED) Film substrate
• PLC plasma addressed liquid crystal
• 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 As sealing agents, potting, dipping, transfer mold sealing in applications such as capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, potting sealings, flipping in applications such as ICs, LSIs COB, COF, TAB, etc. Examples include underfill in applications such as chips, 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 A or the curable resin composition B is used.
• adhesives paints, coating agents, molding materials (sheets, films) , FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealants, additives to other resins, and the like.
• the curable resin composition A or B of the present invention is used as an additive to other resins, for example, when used as a curing agent for a sealant or a cyanate resin composition for a substrate, or as a resist curing agent.
• 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).
• 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 curable resin composition A and the curable resin composition B of the present invention are excellent in heat deterioration characteristics such as heat resistance and heat resistance, moisture resistance, light resistance, and the like, and are particularly suitable for LED device sealants and / or Alternatively, it is preferably used as a die bonding agent. Moreover, the curable resin composition A and the curable resin composition B of the present invention can be applied to a reflector of an LED device due to the above-described excellent characteristics.
• 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, stirrer, and Dean-Stark tube, 150 parts of toluene, 2-butyl-2-ethyl-1,3-propanediol (Kyowa Hakko Chemical Co., Ltd. 80 parts of ethyl propanediol), 126 parts of 3-cyclohexenecarboxylic acid and 2 parts of paratoluenesulfonic acid were added, and the reaction was carried out under heating and refluxing for 10 hours while removing water.
• the olefinic compound of the present invention is washed twice with 50 parts of a 10% by weight aqueous sodium hydrogen carbonate solution and the organic layer obtained is washed twice with 50 parts of water and then concentrated with a rotary evaporator. 182 parts of (D-1) was obtained.
• the shape was liquid and the purity by gas chromatography was 96%. Further, as a result of analysis by gel permeation chromatography, it was confirmed that the purity was> 98%.
• Example 2 A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen, 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, 0.78 parts of disodium hydrogen phosphate, di-cured tallow alkyldimethylammonium acetate 2.7 parts (50% hexane solution made by Lion Akzo, Acquard 2HT acetate) were added to produce a tungstic acid catalyst, 120 parts of toluene, and 94 parts of the olefin compound D-1 obtained in Example 1 were added. In addition, the mixture was further stirred to obtain a liquid in an emulsion state.
• the organic layer separated into two layers was taken out, and 10 parts of silica gel (Wakogel C-300, manufactured by Wako Pure Chemical Industries), 20 parts of activated carbon (CAP SUPER, manufactured by NORIT), and 20 parts of bentonite (Bengel SH, manufactured by Hojun) were added at room temperature. And stirred for 1 hour and then 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).
• silica gel Wangogel C-300, manufactured by Wako Pure Chemical Industries
• CAP SUPER activated carbon
• Bengel SH manufactured by Hojun
• Example 4 To a flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean-Stark tube, while purging with nitrogen, 150 parts of toluene and 2,4-diethyl-1,5-pentanediol (Kyowa Hakko Chemical Co., Ltd. Kyowa All PD9) ) 80 parts, 126 parts of 3-cyclohexenecarboxylic acid and 2 parts of paratoluenesulfonic acid were added, and the reaction was carried out under heating and refluxing for 10 hours while removing water.
• the olefinic compound of the present invention is washed twice with 50 parts of a 10% by weight aqueous sodium hydrogen carbonate solution and the organic layer obtained is washed twice with 50 parts of water and then concentrated with a rotary evaporator. 187 parts of (D-2) was obtained.
• the shape was liquid and the purity by gas chromatography was 96%. Further, as a result of analysis by gel permeation chromatography, it was confirmed that the purity was> 98%.
• Example 5 A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen, 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, 0.78 parts of disodium hydrogen phosphate, di-cured tallow alkyldimethylammonium acetate 2.7 parts (50% hexane solution made by Lion Akzo, Acquard 2HT acetate) were added to form a tungstic acid catalyst, and then 120 parts of toluene and 94 parts of the olefin compound D-2 obtained in Example 4 were added. In addition, the mixture was further stirred to obtain a liquid in an emulsion state.
• the organic layer separated into two layers was taken out, and 10 parts of silica gel (Wakogel C-300, manufactured by Wako Pure Chemical Industries), 20 parts of activated carbon (CAP SUPER, manufactured by NORIT), and 20 parts of bentonite (Bengel SH, manufactured by Hojun) were added at room temperature. And stirred for 1 hour and then 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 (6).
• Dynamic viscoelasticity measuring instrument TA-2 instruments, DMA-2980 Measurement temperature range: -30 ° C to 280 ° C Temperature increase rate: 2 ° C./min Test piece size: A material cut into 5 mm ⁇ 50 mm was used (thickness is about 800 ⁇ m). Analysis conditions Tg: The peak point of Tan- ⁇ in DMA measurement was defined as Tg.
• the obtained curable resin composition was vacuum-defoamed for 20 minutes, and then gently cast on a glass substrate on which a dam was created with a heat-resistant tape so as to be 30 mm ⁇ 20 mm ⁇ height 1 mm.
• the cast was cured at 120 ° C. for 1 hour after pre-curing at 120 ° C. for 3 hours to obtain a test piece for transmittance having a thickness of 1 mm.
• the transmittance (measurement wavelength: 375 nm or 400 nm) before and after being left for 96 hours in a 150 ° C. oven was measured with a spectrophotometer, and the rate of change was calculated.
• LED lighting test The curable resin compositions obtained in Examples and Comparative Examples were vacuum degassed for 20 minutes, filled in a syringe, and used a precision discharge device to mount a light emitting element having an emission wavelength of 465 nm, an outer diameter of 5 mm square surface It was cast into a mounting type LED package (inner diameter 4.4 mm, outer wall height 1.25 mm). Then, the LED for lighting test is obtained by making it harden
• the illuminance before and after lighting for 200 hours was measured using an integrating sphere, and the illuminance retention rate of the test LED was calculated.
• the curable resin composition of the present invention is more resistant to heat and heat than the curable resin composition using an epoxy resin having a similar chain linker. It can be seen that not only the heat deterioration characteristics such as colorability are excellent, but also the light resistance is excellent. It can be seen that the same tendency is observed even when the compounds having similar Tg are compared. From the above results, it can be seen that the epoxy resin of the present invention can provide a curable resin composition having excellent heat degradation characteristics and optical characteristics.
• Synthesis example 7 To a flask equipped with a stirrer, reflux condenser, and stirrer, while purging with nitrogen, 12 parts of dicyclopentadiene dimethanol, methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Spaincid MH or less, acid anhydride) 73 parts of 1, 2,4-cyclohexanetricarboxylic acid-1,2-anhydride (hereinafter referred to as H-TMAn hereinafter referred to as H4) manufactured by Mitsubishi Gas Chemical Co., Ltd., and then at 40 ° C.
• H-TMAn 1, 2,4-cyclohexanetricarboxylic acid-1,2-anhydride
• Curing agent composition which is a mixture of polycarboxylic acid and acid anhydride by heating and stirring at 60 ° C. for 1 hour (GPC confirmed that dicyclopentadiene dimethanol was 0.5% or less). 100 parts of (HA-1) was obtained. The functional group equivalent of the obtained compound was 171 g / eq. (Carboxylic acid and acid anhydride are considered as one functional group each).
• Synthesis example 8 A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 10 parts of 2,4-diethylpentanediol (Kyowa Hakko Chemical Kyowadiol PD-9) and 50 parts of acid anhydride (H3) while purging with nitrogen. In addition, heating and stirring at 40 ° C. for 2 hours and then at 60 ° C. for 1 hour (confirmed that 2,4-diethylpentanediol was 0.5% or less by GPC), polycarboxylic acid and acid 60 parts of a curing agent composition (HA-2) which was a mixture with an anhydride was obtained. The functional group equivalent of the obtained compound was 201 g / eq. Met.
• Example 10 A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen and 75.2 parts of the olefin compound D-2 obtained in Example 4, 75 parts of toluene, 10 parts of water, 12-tungstorin 0.4 part of acid, 0.60 part of sodium tungstate, 0.60 part of disodium hydrogenphosphate, 0.54 part of trioctylmethylammonium acetate (50% xylene solution from Lion Akzo, TOMAA-50), and this solution The temperature was raised to 48 ° C., and 44 parts of 35% hydrogen peroxide was added while stirring, and the mixture was stirred at 48 ° C. for 16 hours.
• the substrate conversion after the completion of the reaction was> 99%, and the raw material peak was ⁇ 1%.
• the pH was adjusted to 9 with a 30 wt% aqueous sodium hydroxide solution, 20 parts of a 20 wt% aqueous sodium thiosulfate solution was added, and the mixture was stirred for 30 minutes and allowed to stand.
• the organic layer separated into two layers was taken out, and 8 parts of montmorillonite (Kunimine Industries Kunipia F) and 9 parts of activated carbon (CP-1 manufactured by Ajinomoto Fine-Techno) were added thereto, followed by stirring at room temperature for 3 hours and filtration.
• Example 9 75.2 parts of the olefin compound (D-2) was synthesized by dehydration esterification of 1,4-cyclohexanedimethanol and 3-cyclohexenecarboxylic acid.
• Synthesis Example 10 Synthesis was performed in the same manner as in Example 10 except that 75.2 parts of the olefin compound (D-2) was changed to 66.9 parts of the olefin compound (D-4), and the skeleton of the formula (8) was used as the main component. As a result, 67.0 parts of a comparative epoxy resin (EP-11) was obtained. Epoxy equivalent was 196 g / eq. Met.
• Example 11 Comparative Examples 3, 4, 5
• the epoxy resin (EP-9) of the present invention obtained in Example 10 and, as comparative examples, the epoxy resins (EP-10, EP-11, EP-12) obtained in Synthesis Examples 9, 10, and 11 were cured.
• LED lighting test A The resulting curable resin composition was vacuum degassed for 20 minutes, then filled into a syringe, and using a precision discharge device, an outer diameter 5 mm square surface mount LED package (inner diameter 4) mounted with a chip having a central emission wave of 465 nm. 4 mm, outer wall height 1.25 mm). Thereafter, a test LED was obtained by curing under predetermined curing conditions. In the lighting test, a lighting test was performed at a specified current of 30 mA. Detailed conditions are shown below. As measurement items, the illuminance before and after lighting for 400 hours, 600 hours, and 800 hours was measured using an integrating sphere, and the illuminance retention rate of the test LED was calculated.
• the epoxy resin (EP-9) of the present invention obtained in Example 10 and the curing agent compositions (HA-1) (HA-2) and additives obtained in Synthesis Examples 7 and 8 as curing agent compositions, respectively.
• the zinc phosphate complex (XC-9206 manufactured by King Industries, hereinafter referred to as AD-1) and a hindered amine compound (LA-77 manufactured by ADEKA, hereinafter referred to as AD-2) were used as the mixing ratio (weight) shown in Table 3 below. Part) to obtain a curable composition of the present invention.
• the obtained curable resin composition was vacuum-defoamed for 20 minutes, and then gently cast on a glass substrate on which a dam was created with a heat-resistant tape so as to be 30 mm ⁇ 20 mm ⁇ height 1 mm.
• the cast was cured at 110 ° C. for 3 hours and then cured at 150 ° C. for 3 hours to obtain a transmittance test piece having a thickness of 1 mm.
• the transmittance (measurement wavelength: 400 nm) before and after being left in a 150 ° C. oven for 96 hours was measured with a spectrophotometer, and the rate of change was calculated.
• Example 14 Comparative Example 6 Epoxy resin (EP-9) of the present invention obtained in Example 10 and 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate (Nippon Kayaku SEJ-01R epoxy equivalent) as a comparative example 130 g / eq., Hereinafter referred to as an epoxy resin (EP-13)), an acid anhydride (H3) is used as a curing agent, and an imidazole compound (2E4MZ manufactured by Shikoku Chemicals, hereinafter referred to as C3) is used as a curing accelerator.
• the curable resin composition of the present invention was obtained by blending at a blending ratio (parts by weight) shown in Table 4 below.
• the obtained curable resin composition was cast into a mold (a disk having a diameter of 50 mm and a thickness of 3 mm), and the cast was cured at 160 ° C. for 5 hours after pre-curing at 120 ° C. for 2 hours.
• Test specimens were obtained.
• a moisture absorption / water absorption test was performed under the following conditions, and the weight increase rate was confirmed. The results are shown in Table 4 below.
• Moisture resistance test 1 In a thermostatic chamber, at a temperature of 85 ° C and a humidity of 85% for 24 hours (Moisture resistance test 2) 24 hours in a pressure vessel at a temperature of 121 ° C and humidity of 100%
• Water resistance test 1 Boiled in water at about 100 ° C for 24 hours
• the epoxy resin composition using the epoxy resin of the present invention has not only high moisture and water resistance properties but also high optical properties.
• the curable resin composition using the epoxy resin of the present invention has not only good moisture resistance properties, but also has better moisture resistance than those using a simple chain structure ( In the LED lighting test B), the illuminance retention rate of the LED has not only a chain structure but also a high illuminance retention rate as compared with a compound having a cyclic structure, and it can be seen that the LED has high characteristics.

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• 2010
  • 2010-04-02 WO PCT/JP2010/056074 patent/WO2010114122A1/ja active Application Filing
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