WO2011145733A1 - Composé de dioléfine, résine époxy, composition de résine durcissable et article durci - Google Patents

Composé de dioléfine, résine époxy, composition de résine durcissable et article durci Download PDF

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WO2011145733A1
WO2011145733A1 PCT/JP2011/061678 JP2011061678W WO2011145733A1 WO 2011145733 A1 WO2011145733 A1 WO 2011145733A1 JP 2011061678 W JP2011061678 W JP 2011061678W WO 2011145733 A1 WO2011145733 A1 WO 2011145733A1
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Prior art keywords
resin composition
curable resin
epoxy resin
acid
reaction
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PCT/JP2011/061678
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English (en)
Japanese (ja)
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政隆 中西
健一 窪木
智江 佐々木
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日本化薬株式会社
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Priority to CN201180023913.XA priority Critical patent/CN102892745B/zh
Priority to JP2012515950A priority patent/JP5878865B2/ja
Priority to KR1020127028378A priority patent/KR20130093473A/ko
Publication of WO2011145733A1 publication Critical patent/WO2011145733A1/fr

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    • 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
    • C07C69/753—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 polycyclic acids
    • 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
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl 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
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/14—All rings being cycloaliphatic
    • C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
    • C07C2602/28—Hydrogenated naphthalenes

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.
  • 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 resistance, optical properties, and toughness.
  • the present invention (1) Following formula (1) (In the formula, a plurality of R 1 and R 2 each independently exist, and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
  • the epoxy resin of the present invention gives a cured product having excellent mechanical properties (particularly toughness).
  • the curable fat composition 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. Moreover, since the epoxy resin of this invention does not have an aromatic ring, the curable resin composition containing it is very useful for an optical material.
  • the present invention is the following formula (1)
  • R 1 and R 2 each independently exist, and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the diolefin compound represented by the formula (1) is obtained by a reaction between a cyclohexene methanol derivative and a decahydronaphthalenedicarboxylic acid derivative.
  • the cyclohexene methanol derivative is not particularly limited as long as it is a cyclohexene having a hydroxymethyl group, and preferably 3-cyclohexene methanol, 3-methyl-3-cyclohexene methanol, 4-methyl-3-cyclohexene methanol, 2-methyl-3- Examples thereof include cyclohexene methanol, and 3-cyclohexene methanol is particularly preferable, but is not limited thereto. These may be used alone or in combination of two or more.
  • decahydronaphthalenedicarboxylic acid derivatives include hydrogenation of naphthalenedicarboxylic acid or its ester by nuclear hydrogenation, and hydroformylation of tetrahydronaphthalene excluding the resulting compound and tetralin, followed by oxidation with carboxylic acid. Or by further esterification with alcohol.
  • decahydronaphthalenedicarboxylic acid excluding tetralin dicarboxylic acid may be acid halided.
  • decahydronaphthalenedicarboxylic acid dimethyl decahydronaphthalenedicarboxylate, diethyl decahydronaphthalenedicarboxylate, dipropyl decahydronaphthalenedicarboxylate, dibutyl decahydronaphthalenedicarboxylate, dicyclohexyl decahydronaphthalenedicarboxylate, methyl decahydronaphthalenedicarboxyl Dimethyl acid, cyclohexyldecahydronaphthalenedicarboxylate, and the like.
  • a general esterification method can be applied as a reaction between the cyclohexene methanol derivative and the decahydronaphthalenedicarboxylic acid derivative.
  • Specific examples include Fischer® esterification using an acid catalyst, acid halide under basic conditions, alcohol reaction, condensation reaction using various condensing agents (ADVANCED®ORGANIC®CHEMISTRY Part B: Reaction and Syntehsis®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) (Japanese Patent Laid-Open No. 2006-052187) may be used.
  • R 1 in the formula (1) is any one of a hydrogen atom, a methyl group, an ethyl group, and a butyl group.
  • R 1 bonded to the olefin is preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom.
  • the substituent R 2 directly connected to the decahydronaphthalene structure is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or the like.
  • the diolefin compound of the formula (1) is preferably 2,6-substituted, 1,4-substituted, 2,3-substituted, 1,8-substituted, and particularly preferably 2,6-substituted.
  • the diolefin resin 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 hydrogen peroxide solution a method of oxidizing with air (oxygen).
  • oxygen oxygen
  • Specific examples of the epoxidation method using peracid include the method described in Japanese Patent Application Laid-Open No. 2006-52187.
  • peracids that can be used include organic acids such as formic acid, acetic acid, propionic acid, maleic acid, benzoic acid, m-chlorobenzoic acid, and phthalic acid, and acid anhydrides thereof.
  • formic acid, acetic acid, and phthalic anhydride from the viewpoint of the efficiency of reacting with hydrogen peroxide to produce an organic peracid, the reaction temperature, the ease of operation, and the economy.
  • Formic acid or acetic acid is more preferably used from the viewpoint of simplicity of reaction operation.
  • 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. 62-234550, Japanese Patent Application Laid-Open No. No. 5-291919, Japanese Patent Application Laid-Open No. 11-349579, Japanese Patent Publication No. 1-33341, Japanese Patent Publication No. 2001-17864, Japanese Patent Publication No. 3-57102, etc. Various methods can be applied.
  • the diolefin compound, polyacid and quaternary ammonium salt of the present invention are reacted in two layers of an organic solvent and hydrogen peroxide solution.
  • 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 polyacids and polyacid salts included in the polyacids include tungsten acids selected from tungstic acid, 12-tungstophosphoric acid, 12-tungstoboric acid, 18-tungstophosphoric acid, 12-tungstosilicic acid, and the like. Examples thereof include molybdenum-based acids selected from molybdic acid and phosphomolybdic acid, and salts thereof.
  • Examples of the counter cation of these salts include ammonium ions, alkaline earth metal ions, and alkali metal ions. Specific examples include alkaline earth metal ions such as calcium ions and magnesium ions, 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 of the polyacid used is 1.0 to 20 mmol in terms of metal element (tungstenic acid is tungsten atom, molybdic acid is molybdenum atom) to 1 mol of olefin (functional group equivalent) in the diolefin compound of the present invention. , Preferably 2.0 to 20 mmol, more preferably 2.5 to 10 mmol.
  • 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, and in particular, the alkyl chain is preferably an aliphatic chain. .
  • 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.
  • the anion species of these salts use carboxylate ions.
  • carboxylate ion acetate ion, carbonate ion and formate ion are preferable. In particular, acetate ion is preferred.
  • acetate ion is preferred.
  • the quaternary ammonium salt has more than 100 carbon atoms, the hydrophobicity may become too strong and the solubility in the organic layer may deteriorate.
  • the carbon number of the quaternary ammonium salt is less than 10, the hydrophilicity becomes strong, and the compatibility with the organic layer may be similarly deteriorated. In general, halogen remains in the quaternary ammonium salt.
  • the present invention in particular, it is 1% by weight or less, more preferably 1000 ppm or less, and still more preferably 700 ppm or less.
  • the amount of tungstic acid and quaternary ammonium carboxylate used is preferably 0.01 to 0.8 times equivalent, or 1.1 to 10 times equivalent to the valence of the tungstic acid used. More preferably 0.05 to 0.7 times equivalent, or 1.2 to 6.0 times equivalent, still more preferably 0.05 to 0.5 times equivalent, or 1.3 to 4.5 times equivalent. is there.
  • tungstic acid is divalent with H 2 WO 4
  • the quaternary ammonium carboxylate is 0.02 to 1.6 mol, or 2.2 to 20 mol per mol of tungstic acid. A range is preferred.
  • tungstophosphoric acid is trivalent, it is similarly 0.03 to 2.4 mol, or 3.3 to 30 mol, and in the case of silicotungstic acid, it is tetravalent, so 0.04 to 3.2. Mole or 4.4 to 40 mol is preferred.
  • the amount of the quaternary ammonium carboxylate is lower than 1.1 times equivalent of the valence of tungstic acids, the epoxidation reaction is difficult to proceed (in some cases, the reaction proceeds faster), and a by-product is produced.
  • the problem is that things are easy to make.
  • the amount is more than 10 times the equivalent, not only is the treatment of the excess quaternary ammonium carboxylate difficult, but it also serves to suppress the reaction, which is not preferable.
  • the quaternary ammonium salt having a carboxylate ion as an anion a commercially available product may be used.
  • the raw material quaternary ammonium salt is treated with a metal hydroxide or an ion exchange resin to be converted into a quaternary ammonium hydroxide. Further, it may be produced by a method of reacting with various carboxylic acids. Examples of the raw material quaternary ammonium salt include quaternary ammonium halides and various metal salts. If there is a suitable quaternary ammonium hydroxide, it may be used.
  • 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.
  • the pH is preferably adjusted to be between 5 and 9.
  • a buffer solution is used in an amount of 0.1 to 10 mol% of phosphoric acid (or phosphorous such as sodium dihydrogen phosphate) with respect to hydrogen peroxide.
  • Acid salt and adjusting the 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.
  • the preferred phosphate concentration is 0.1 to 60% by weight, preferably 5 to 45% by weight.
  • a buffer such as disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate or sodium tripolyphosphate (or its hydrate) is used without adjusting the pH. It may be added directly. In the sense of simplifying the process, there is no troublesome pH adjustment, and direct addition is particularly preferred.
  • the amount of phosphate used 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. It is. At this time, 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 bad 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 can also be used.
  • 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 preferred 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.
  • 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.
  • 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 above-mentioned organic solvent is added and the operation is performed.
  • the reaction product is extracted from the layer.
  • 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 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 or a metal oxide (especially silica gel or alumina is preferred), activated carbon (especially a chemical activated carbon is particularly preferred), or a composite metal salt (especially a basic composite metal salt).
  • a metal oxide especially silica gel or alumina is preferred
  • activated carbon especially a chemical activated carbon is particularly preferred
  • a composite metal salt especially a basic composite 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 compound. 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)
  • R 1 and R 2 each independently exist, and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the main structure is the structure represented by the formula, but a hydrolyzate, an unreacted product, a polymerized polymer obtained by polymerizing epoxy groups, and other by-products are produced depending on the reaction conditions.
  • the obtained epoxy resin of the present invention can be used as a raw material for various resins 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.
  • the curable resin composition of the present invention two types of heat curing with a curing agent (curable resin composition A) and cationic curing (curable resin composition B) using an acid as a curing accelerator (curing catalyst).
  • curable resin composition A two types of heat curing with a curing agent
  • curable resin composition B cationic curing
  • the method can be adapted.
  • 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 mass or more, particularly preferably 40% by mass or more.
  • the epoxy resin of the present invention is used as a modifier of the curable resin composition, it may be added in a proportion of 1 to 30% by mass.
  • 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
  • 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.
  • an acetal compound obtained by an acetal reaction between a cyclohexene aldehyde derivative and an alcohol is exemplified.
  • a reaction method it can be produced by applying a general acetalization reaction.
  • a method of performing a reaction while azeotropically dehydrating using a solvent such as toluene or xylene as a reaction medium US Pat. No. 2,945,008
  • a method in which polyhydric alcohol is dissolved in hydrochloric acid 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.
  • Curable resin composition A thermo curing with curing agent
  • 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.
  • the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and nitrogen-containing compounds such as polyamide resins synthesized from ethylenediamine and amine compounds (amines, Amide compound); phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydro Phthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxy
  • the amount of the curing agent used in the curable resin composition A of the present invention is preferably 0.6 to 1.2 equivalents, and preferably 0.7 to 1.2 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. When less than 0.6 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete, and good cured properties may not be obtained.
  • a curing accelerator (curing catalyst) may be used in combination with the curing agent.
  • curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol and 1,8-diaza-bicyclo ( 5,4,0) tertiary amines such as undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, hexadecyltrimethyl Quaternary ammonium salts such as ammonium hydroxide, quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, tetra
  • the curable resin composition A of the present invention can also contain a phosphorus-containing compound as a flame retardant 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 ( Phosphate esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate) and 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide and 10 (2,5-dihydroxyphenyl) -10H-9-ox
  • Phosphate esters, phosphanes, or phosphorus-containing epoxy resins are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy resins are particularly preferred.
  • content of a phosphorus containing compound 0.6 times or less is preferable with respect to the total amount of the epoxy resin component in the curable resin composition A of this invention. If it exceeds 0.6 times, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.
  • 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 A in the curable resin composition of the present invention. .
  • 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
  • a binder resin can be added to the curable resin composition A of the present invention 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 100 parts by weight with respect to 100 parts by weight of the resin component in the curable resin composition A of the present invention. 50 parts by weight, preferably 0.05 to 20 parts by weight are used as required.
  • 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.
  • an amount occupying 95% by mass or less in A in the curable resin composition of the present invention is used.
  • 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 a function of forming white light by absorbing 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, 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 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 size of the phosphor those having a particle size known in this field are used, and the average particle size 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 the above components.
  • the curable resin composition A of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, until the epoxy resin 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 uniform using an extruder, a kneader, a roll, or the like as necessary Mix well to obtain a curable resin composition. After potting and melting the curable resin composition (without melting in the case of liquid), it is molded using a casting or transfer molding machine, and further 80-200 The cured product of the present invention can be obtained by heating at a temperature of 2 to 10 hours.
  • the curable resin composition A of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone as necessary.
  • a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone as necessary.
  • the prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber and paper, and drying by heating is formed into a curable resin composition varnish by hot press molding. It can be set as the hardened
  • the solvent is used in an amount usually accounting for 10 to 70% by mass, preferably 15 to 70% by mass in the mixture of the curable resin composition of the present invention and the solvent A. Moreover, if it is a liquid composition, the epoxy resin hardened
  • the curable resin composition A of the present invention when used in the form of a film or a sheet, it has characteristics such as excellent flexibility characteristics in the B stage.
  • Such a film or sheet-shaped resin composition is applied to the release film using the curable resin composition A of the present invention as the curable resin composition varnish, and after removing the solvent under heating, it is made into a B-stage. Is obtained.
  • This film or sheet-shaped resin composition can be used as an adhesive (interlayer insulating layer) in a multilayer substrate or the like.
  • Curable resin composition B (cationic curing with acidic curing accelerator (curing catalyst))
  • the curable resin composition B of the present invention that is cured using an acidic curing accelerator contains a photopolymerization initiator or a thermal polymerization initiator as an acidic curing accelerator.
  • a photopolymerization initiator or a thermal polymerization initiator as an acidic curing accelerator.
  • 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.
  • the active energy ray cationic polymerization initiator include metal fluoroboron complex and boron trifluoride complex (US Pat. No. 3,379,653), bis (perfluoroalkylsulfonyl) methane metal salt (US Pat. No. 3,586,616). ), Aryldiazonium compounds (US Pat.
  • Adekaoptomer SP150 As manufactured by Asahi Denka Kogyo Co., Ltd.
  • UVE-1014 manufactured by General Electronics Co., Ltd.
  • CD-1012 Siliconomer Company
  • 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 epoxy resin component.
  • one or more polymerization initiation assistants and, if necessary, a photosensitizer can be used in combination with the cationic polymerization initiator.
  • the polymerization initiation aid include 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-chloro Anthraquinone, 2-amylanthraquinone, 2-isopropylthioxatone
  • the photosensitizer include anthracene, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acridine orange, acridine yellow, phosphine R Benzoflavine, cetoflavin T, perylene, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine and the like.
  • the amount of the photosensitizer used is 0.01 to 30 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin component.
  • the curable resin composition B of the present invention includes various compounding agents such as an inorganic filler, a silane coupling material, a release agent, and a pigment, and various compounding agents for various thermosetting resins as necessary. Can be added. 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 use the curable resin composition B of the present invention after uniformly dissolving it in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone or ⁇ -butyrolactone, and then removing the solvent by drying.
  • the solvent at this time is usually 10 to 70% by mass, preferably 15 to 70% by mass 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 heating and / or ultraviolet irradiation (for example, Reference: Review Epoxy Resin Vol. 1, Fundamental Edition I p82-84).
  • the curing conditions are determined according to each composition. Basically, it is sufficient that the cured product has curing conditions that can express the strength required for the purpose of use.
  • these curable resin compositions are difficult to be completely cured only by light irradiation, it is necessary to completely complete the reaction by heating after light irradiation in applications requiring heat resistance.
  • transmit the irradiation light in the case of photocuring to detail the highly transparent compound and composition are desired in the epoxy resin and curable resin composition B of this invention.
  • 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 also exhibited.
  • the shape of the cured product obtained by curing these curable resin compositions B can be various depending on the application, it is not particularly limited. For example, it can 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, a casting method, a casting method, a screen printing method, a spin coating method, a spray method, a transfer method, a dispenser method, and the like can be mentioned. An appropriate method may be employed to obtain the shape.
  • polishing glass, a hard stainless steel polishing plate, a polycarbonate plate, a polyethylene terephthalate plate, a polymethyl methacrylate plate, or the like can be used.
  • 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 is used. Can do.
  • a curable resin composition B dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or ⁇ -butyrolactone is used as a copper-clad laminate, a ceramic substrate, or a glass.
  • a substrate such as a substrate is applied with a film thickness of 5 to 160 ⁇ m by a method such as screen printing or spin coating, and the coating film is preliminarily dried at 60 to 110 ° C.
  • the curable resin composition B on the obtained substrate is irradiated with ultraviolet rays (for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a laser beam, etc.) through a negative film having a desired pattern drawn thereon, and then 70 Perform post-exposure baking at ⁇ 120 ° C. Thereafter, the unexposed portion 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). A cured product is obtained by curing. In this way, it is also possible to obtain a printed wiring board.
  • the above-mentioned method is a case of a negative resist
  • the curable resin composition B of this invention can also be used as a positive resist.
  • 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 in which light such as visible light, infrared light, ultraviolet light, X-rays, and lasers passes through the material.
  • liquid crystal display substrate materials such as lamp types and SMD types
  • light guide plates such as lamp types and SMD types
  • prism sheets in display-related fields
  • liquid crystal display substrate materials liquid crystal display substrate materials, light guide plates, prism sheets, deflection plates, retardation plates, viewing angle correction films
  • Liquid crystal films including adhesives and polarizer protective films are expected to be used as next-generation flat panel displays for color PDP (plasma display) sealing materials, antireflection films, optical correction films, housing materials, front surfaces Glass protective film, front glass substitute material and adhesive, etc. are LED mold materials used in LED display devices, LED sealing material, front glass protective film, front glass substitute material and adhesive, etc. are plasma Substrate materials, light guide plates, prism sheets, deflector plates, etc.
  • front glass protective films in organic EL (electroluminescence) displays are various in field emission displays (FED). Examples thereof include a film substrate, a front glass protective film, a front glass substitute material, and an adhesive.
  • VD video disc
  • a pickup lens, a protective film, a sealing material, an adhesive, and the like can be given.
  • steel camera lens materials, finder prisms, target prisms, finder covers and light-receiving sensor parts, etc., video camera photographic lenses, finder, etc., projection TV projection lenses, protective films, sealing materials, etc.
  • adhesives include materials for lenses of optical sensing devices, sealing materials, adhesives, and films.
  • fiber materials, lenses, waveguides, element sealing materials and adhesives around optical switches in optical communication systems optical fiber materials, ferrules, sealing materials and adhesives around optical connectors, etc.
  • lenses, waveguides, LED sealing materials, CCD sealing materials and adhesives are used as substrate materials, fiber materials, and device sealing materials around optoelectronic integrated circuits (OEIC).
  • optical fibers In the field of optical fibers, lighting for decorative displays, light guides, etc., sensors for industrial use and displays / signs, etc., optical fibers for communication infrastructure and for connecting digital devices in the home, etc. can be mentioned.
  • peripheral materials for semiconductor integrated circuits include resist materials for microlithography for LSI and VLSI materials.
  • 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 plates, interior panels, interior materials, protective / bundling wire harnesses, fuel hoses, automotive lamps and glass replacements, multilayer glass for railway vehicles, etc., toughening agents for aircraft structural materials, engine peripheral members Protective / bundling wire harnesses and corrosion resistant coatings.
  • interior and processing materials electrical covers, sheets, glass interlayers, glass substitutes, solar cell peripheral materials, and the like can be mentioned.
  • a film for house covering is exemplified.
  • 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 And a sealing material and an adhesive.
  • sealing agents potting used for capacitors, transistors, diodes, light emitting diodes, ICs and LSIs, dipping and transfer mold sealing, potting sealing used for ICs and LSIs such as COB, COF and TAB, flip An underfill used for a chip or the like, and sealing (reinforcing underfill) when mounting IC packages such as BGA and CSP can be given.
  • optical material examples include general uses in which the curable resin composition A or the curable resin composition B is used.
  • curable resin composition A or curable resin composition B of the present invention as an additive to other resins, for example, when used as a curing agent to a sealant or a cyanate resin composition for a substrate, The case where it uses for acrylic ester-type resin etc. as a hardening agent for resists is mentioned.
  • adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, semiconductor adhesives such as die bonding agents and 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
  • semiconductor adhesives such as die bonding agents and underfills
  • BGA reinforcing underfills such as anisotropic conductive films ( ACF)
  • ACP anisotropic conductive paste
  • the epoxy equivalent was measured using an E-type viscometer at JIS K-7236 and the viscosities at 25 ° C. and 30 ° 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., and the temperature was raised at a rate of 15 ° C. per minute and held at 300 ° C. for 90 minutes.
  • GPC gel permeation chromatography
  • 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.
  • the detection was performed by RI
  • a standard polystyrene made by Shodex was used for the calibration curve.
  • Example 1 A flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean-Stark tube was purged with nitrogen, while 178 parts of dimethyl 2,6-decahydronaphthalenedicarboxylate (H-NDCM, manufactured by Mitsubishi Gas Chemical), cyclohexene-4 -314 parts of methanol and 0.07 part of tetrabutoxytitanium were added and the reaction was carried out while removing methanol produced by the reaction at 120 ° C for 1 hour, 150 ° C for 1 hour, 170 ° C for 1 hour, 180 ° C for 15 hours, Cooled to ° C.
  • H-NDCM dimethyl 2,6-decahydronaphthalenedicarboxylate
  • Example 2 In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 212 parts of the diolefin compound of the present invention obtained in Example 1, 212 parts of toluene, 15 parts of water, 1.8 parts of 12-tungstophosphoric acid, phosphorus Add 1.6 parts disodium oxyhydrogen and 5.4 parts trioctylmethylammonium acetate (Lion Akzo 50% xylene solution, TOMAA-50). 113 parts of hydrogen water was added and the mixture was stirred at 50 ⁇ 3 ° C. for 9 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 (1% or less).
  • the obtained epoxy resin (EP-2) of the present invention was 16 parts, and the purity of the obtained epoxy resin contained 98% or more of the skeleton compound of the formula (4) based on the GPC measurement result. It was confirmed. Furthermore, in the GC measurement, the purity was about 98%. Epoxy equivalent was 229 g / eq. Met.
  • Examples 4, 5, and 6 About the epoxy resin (EP-1) of the present invention obtained in Examples 1 and 2, as a curing agent, methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH700G, hereinafter referred to as H1) Bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid HNA-100, hereinafter referred to as H2), hexadecyltrimethylammonium hydroxide as a curing accelerator (The Tokyo Chemical Industry Co., Ltd. 25% methanol solution, referred to as C1) is blended at the blending ratio (parts by weight) shown in Table 1 below, and then defoamed for 20 minutes to cure the present invention. Sex composition was obtained.
  • Dynamic viscoelasticity measuring device manufactured by TA-instruments, DMA-2980 Measurement temperature range: -30 ° C to 280 ° C Temperature rate: 2 ° C./min Test piece size: 5 mm ⁇ 50 mm cut out (thickness is about 800 ⁇ m).
  • Analysis condition Tg Tan- ⁇ peak point in dynamic viscoelasticity (DMA) measurement was defined as Tg.
  • Elastic modulus at 25 ° C . The elastic modulus at 25 ° C. was measured.
  • the LED encapsulated with the curable resin composition (F-1) using the epoxy resin of the present invention had almost no dent, whereas the comparative curable resin composition (F-2).
  • the LED wire encapsulated in (1) had exposed LED wires, and dents were observed intensely.
  • Example 8 Comparative Examples 2, 3 Epoxy resin (EP-2) of the present invention obtained in Examples 2 and 3, epoxy resin (EP-3), bis (3,4-epoxycyclohexylmethyl) adipate (epoxy equivalent 195 g / eq. Viscosity) as comparative examples
  • EP-4 epoxy resin
  • EP-4 bis (3,4-epoxycyclohexylmethyl) adipate
  • a curing accelerator H1
  • PX4MP quaternary phosphonium salt
  • 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 of each cured product at 400 nm was compared.
  • the obtained test piece was heat-treated at 150 ° C. for 96 hours, and the degree of coloring was evaluated based on the thermal history (transmittance at 400 nm was measured and compared).
  • Example 9 Comparative Example 4
  • the epoxy resin (EP-2) of the present invention obtained in Example 3 and, as a comparative example, the epoxy resin (EP-6) obtained in Synthesis Example 1 the acid anhydride (H1), curing as a curing agent
  • a curing accelerator (C1) is used as an accelerator, blended at a blending ratio (parts by weight) shown in Table 3 below, defoamed for 20 minutes, and the curable resin composition of the present invention, a comparative curable resin.
  • a composition was obtained.
  • the LED test results are shown in Table 3 in the following manner.
  • the curing conditions are 140 ° C. ⁇ 3 hours after 110 ° C. ⁇ 2 hours of preliminary curing.
  • Example 10 and Comparative Examples 5 and 6 EP2 as an epoxy resin for examples, EP3 and EP6 as comparative examples, and methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH, hereinafter referred to as H3) as a curing agent.
  • the epoxy resin of the present invention is an epoxy resin excellent in impact resistance and water resistance.

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Abstract

La présente invention concerne une nouvelle résine époxy alicyclique à l'origine d'un article durci présentant d'excellentes propriétés de résistance à la chaleur et optiques et une robustesse. La résine époxy comprend un composé de dioléfine représenté par la formule (1) en tant que substance de départ et elle est obtenue par l'époxydation du composé. Dans la formule (1), plusieurs R1 et R2 représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle contenant 1 à 6 atomes de carbone.
PCT/JP2011/061678 2010-05-21 2011-05-20 Composé de dioléfine, résine époxy, composition de résine durcissable et article durci WO2011145733A1 (fr)

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JP2012515950A JP5878865B2 (ja) 2010-05-21 2011-05-20 ジオレフィン化合物、エポキシ樹脂、硬化性樹脂組成物及びその硬化物
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WO2016119848A1 (fr) * 2015-01-29 2016-08-04 Henkel Ag & Co. Kgaa Procédé de préparation de résines époxy cycloaliphatiques

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