WO2010119960A1 - Résine oléfine, résine époxy, composition de résine durcissable, et matériau résultant du durcissement de celle-ci - Google Patents

Résine oléfine, résine époxy, composition de résine durcissable, et matériau résultant du durcissement de celle-ci Download PDF

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WO2010119960A1
WO2010119960A1 PCT/JP2010/056869 JP2010056869W WO2010119960A1 WO 2010119960 A1 WO2010119960 A1 WO 2010119960A1 JP 2010056869 W JP2010056869 W JP 2010056869W WO 2010119960 A1 WO2010119960 A1 WO 2010119960A1
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epoxy resin
resin composition
curable resin
acid
reaction
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PCT/JP2010/056869
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English (en)
Japanese (ja)
Inventor
政隆 中西
健一 窪木
直房 宮川
義浩 川田
智江 佐々木
静 青木
瑞観 鈴木
正人 鎗田
敬夫 小柳
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日本化薬株式会社
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Priority to JP2011509369A priority Critical patent/JP5559154B2/ja
Priority to CN201080016851.5A priority patent/CN102395555B/zh
Publication of WO2010119960A1 publication Critical patent/WO2010119960A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • 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
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/34—Epoxy compounds containing three or more epoxy groups obtained by epoxidation of an unsaturated polymer
    • 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
    • C07D303/44—Esterified with oxirane-containing hydroxy compounds
    • 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
    • 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
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3218—Carbocyclic compounds
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • 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 epoxy resin, an olefin resin as a raw material thereof, and a curable resin composition suitable for electrical and electronic material applications using the epoxy resin.
  • 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 resins are superior to glycidyl ether type epoxy resins in terms of electrical insulation and transparency, and are used in various ways as transparent sealing materials. However, while this alicyclic epoxy resin has the above-mentioned excellent points, the problem that the cured product is hard and the toughness is inferior remains, and studies are being made to improve this defect (Patent Documents 1 and 2). .
  • the structure of the epoxy resin of the present invention is disclosed in Patent Document 5. Specifically, it is produced by transesterification of ethyl 3,4-epoxycyclohexanecarboxylate and ditrimethylolpropane.
  • the epoxy resin obtained by this production method has a low purity of the tetrafunctional epoxy resin.
  • the purity of the tetrafunctional tetraepoxy compound is 42.5%.
  • the remainder is a triepoxy body, diepoxy body, or monoepoxy body, and the alcohol structure remains and is of poor purity.
  • this reaction is a reaction at a high temperature, a polymerization reaction between epoxies also occurs, resulting in a resin having a high viscosity, which may cause a problem in workability.
  • the reaction with the acid anhydride occurs at the room temperature level when the solution is made into a single solution, and the storage stability becomes very poor. Arise.
  • the crosslink density is lowered, which affects the cured properties, which is not preferable.
  • An object of the present invention is to provide a novel epoxy resin that provides a highly transparent cured product having excellent curability and excellent heat resistance and light resistance.
  • An olefin resin characterized by being represented by: (2) An epoxy resin obtained by oxidizing the olefin resin according to item (1), (3) The epoxy resin according to item (2), which is epoxidized using hydrogen peroxide or peracid, (4) A curable resin composition comprising the epoxy resin according to the item (2) or (3) and a curing agent and / or a curing catalyst; (5) A cured product obtained by curing the curable resin composition according to item (4), About.
  • the olefin resin of the present invention is a raw material for an epoxy resin (epoxy resin of the present invention) that gives a cured product having excellent heat resistance and light resistance.
  • the curable resin composition of the present invention containing the epoxy resin of the present invention is excellent in curability and has little influence on the environment.
  • the curable fat 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 the present invention does not have an aromatic ring and is excellent in transparency, it is extremely useful as an optical material.
  • the olefin resin of the present invention has the following formula (1)
  • R and P are independently present and each represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. It is represented by
  • the olefin resin represented by the formula (1) is obtained by a reaction between a cyclohexene carboxylic acid derivative and ditrimethylolalkanes.
  • the cyclohexene carboxylic acid derivative the following formula (2)
  • P represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms.
  • X represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.
  • cyclohexene carboxylic acid cyclohexene carboxylate methyl, cyclohexene carboxylate ethyl, cyclohexene carboxylate propyl, cyclohexene carboxylate butyl, cyclohexene carboxylate hexyl, (cyclohexenylmethyl) cyclohexene carboxylate, cyclohexene Octyl carboxylate, cyclohexene carboxylic acid chloride, cyclohexene carboxylic acid bromide, methyl cyclohexene carboxylic acid, methyl methyl cyclohexene carboxylate, ethyl methyl cyclohexen
  • the ditrimethylolalkanes in the present invention are represented by the following formulae:
  • R represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms.
  • R represents a compound represented by these. Specific examples include ditrimethylolpropane, ditrimethylolbutane, ditrimethylolpentane, ditrimethylolhexane, ditrimethylolheptane, and ditrimethyloloctane.
  • a method for producing such a compound can be obtained by reacting formaldehyde (or paraformaldehyde, metaformaldehyde, etc.) with a compound having 1 to 15 carbon atoms having a formyl group at the terminal.
  • formaldehyde or paraformaldehyde, metaformaldehyde, etc.
  • a general esterification method can be applied as a reaction between the cyclohexenecarboxylic acid derivative and the ditrimethylolalkane.
  • general esterification reactions can be applied, such as Fischer esterification using an acid catalyst, acid halide under basic conditions, alcohol reaction, condensation reaction using various condensing agents (ADVANCED ORGANIC CHEMISTRY, etc.) Part B: Reaction and Synthesis p135, 145-147, 151, etc.).
  • Specific examples include esterification reaction of alcohol and carboxylic acid (Tetrahedron vol. 36 p. 2409 (1980), Tetrahedron Letter p. 4475 (1980)), and further ester exchange reaction of carboxylic acid ester ( Japanese Patent Application Laid-Open No. 2006-052187) can also be used.
  • a preferred structure of the olefin resin of the formula (1) synthesized in this way is that in the formula (1), P is a hydrogen atom and an alkyl group having 1 to 15 carbon atoms, preferably a hydrogen atom, methyl Group, ethyl group, or butyl group.
  • P bonded to the olefin is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
  • the substituent R is an alkyl group having 1 to 15 carbon atoms, preferably 2 to 10 carbon atoms.
  • the preferred substituent R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and an ethyl group, a propyl group, and a butyl group are particularly preferable, and an ethyl group is more preferable. is there.
  • the olefin resin thus obtained is a tetracyclohexene having at least a main component of a tetrafunctional olefin, and its purity is preferably 80 area% (gel permeation chromatography or less, GPC) or more. More preferably, it is 90 area% or more, and particularly preferably 95 area% or more.
  • the purity is less than 80 area%, problems such as being easily hydrolyzed in the subsequent epoxidation step occur, and when the resulting epoxy resin is an epoxy resin composition, particularly with a curing agent such as an acid anhydride If one-component is used, the reaction between the acid anhydride and the hydroxyl group remaining in the epoxy resin at the normal temperature level is affected, which causes problems such as poor storage stability.
  • the measurement conditions for GPC in the olefin resin of the present invention were 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.
  • the detection was performed by RI
  • a standard polystyrene made by Shodex was used for the calibration curve.
  • the olefin 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. Can be adapted.
  • the olefin resin, polyacids and quaternary ammonium salt of the present invention are reacted with each other in an emulsion state of an organic substance and hydrogen peroxide water.
  • 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.
  • the amount of the polyacid used is 0.5 to 20 mmol in terms of metal element (tungstenic acid is tungsten atom, molybdic acid is molybdenum atom) with respect to 1 mol (functional group equivalent) of the olefin of the present invention, preferably 1.0 to 20 mmol, more preferably 2.5 to 15 mmol.
  • quaternary ammonium salt used in the reaction a quaternary ammonium salt having a total carbon number of 10 or more, more preferably 25 to 55, can be preferably used, and in particular, those whose alkyl chains are all aliphatic chains are preferred.
  • tridecanylmethylammonium salt dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (a mixed type of a compound in which the alkyl group is an octyl group and a compound in which the decanyl group is a compound) ammonium salt
  • trihexa examples include decylmethylammonium salt, trimethylstearylammonium salt, tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, and di-cured tallow alkyldimethylammonium salt. It is not limited to.
  • 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 number of carbon atoms exceeds 100, the hydrophobicity becomes too strong, and the solubility of the quaternary ammonium salt in the organic layer may deteriorate.
  • the number of carbon atoms is less than 10, the hydrophilicity is increased, and the compatibility of the quaternary ammonium salt with the organic layer is similarly deteriorated.
  • the amount of quaternary ammonium salt used is desirably determined by the valence of the polyacids (preferably tungstic acids) used, and is preferably 0.01 to 10 times the valence of the polyacids. 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.
  • 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 polyacids which are catalysts are 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 5.0, more preferably 0.5 to 2.5 by weight with respect to the olefin resin 1 as the reaction substrate. It is. When the weight ratio exceeds 10, the progress of the reaction is extremely slow, which is not preferable.
  • organic solvents that can be used include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, and alcohols such as methanol, ethanol, isopropanol, butanol, hexanol and cyclohexanol. It is done.
  • ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone
  • ethers such as diethyl ether, tetrahydrofuran and dioxane
  • ester compounds such as ethyl acetate, butyl acetate and methyl formate
  • nitriles such as acetonitrile Compounds and the like
  • Particularly preferred solvents are alkanes such as hexane, cyclohexane and heptane, and aromatic hydrocarbon compounds such as toluene and xylene.
  • reaction operation method for example, when the reaction is performed in a batch-type reaction vessel, an olefin resin, hydrogen peroxide (aqueous solution), polyacids (catalyst), a buffer solution, a 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.
  • buffer solution or water and phosphate
  • polyacids were added to adjust pH
  • quaternary ammonium salt organic solvent and olefin compound were added
  • hydrogen peroxide was added dropwise to the mixture after stirring in two layers.
  • the technique of doing is used.
  • stirring water, organic solvent and olefin compound, polyacids 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.
  • the reaction temperature is not particularly limited, but is preferably 0 to 90 ° C, more preferably 0 to 75 ° C, and particularly preferably 15 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.
  • the treatment may be carried out after separation of an aqueous layer and an organic layer described later.
  • the organic layer and the aqueous layer are not separated at this point, or if the reaction is carried out without using an organic solvent, add the aforementioned organic solvent. Then, the reaction product is extracted from the aqueous layer.
  • the organic solvent used at this time is 0.5 to 10 times, preferably 0.5 to 5 times by weight with respect to the raw material olefin resin. 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.
  • clay minerals especially, lamellar viscosity minerals such as montmorillonite are preferred
  • 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 (3).
  • the compounds of various structures as shown in FIG. Depending on the reaction conditions, compounds having an alcohol structure such as a monomethylol body and dimethylol body derived from raw materials, a high molecular weight polymer in which epoxy groups are polymerized, and other by-products are generated.
  • the epoxy resin of the present invention has a structure represented by the formula (3) as a main component, and its purity is preferably 80 area% or more, more preferably 90 area% or more, further preferably 95, in GPC measurement. Area% or more.
  • the measurement conditions of GPC in the epoxy resin of the present invention were 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.
  • the detection was performed by RI
  • a standard polystyrene made by Shodex was used for the calibration curve.
  • 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.
  • 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 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 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.
  • 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 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. When less than 0.7 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. 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-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, for example, a function of forming white light by absorbing a part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed.
  • fluorescent substance A conventionally well-known fluorescent substance can be used, For example, the rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated.
  • phosphors such as YAG phosphors, TAG phosphors, orthosilicate phosphors, thiogallate phosphors, sulfide phosphors, and the like can be mentioned.
  • YAlO 3 Ce, Y 3 Al 5 O 12 : Ce, Y 4 Al 2 O 9 : Ce, Y 2 O 2 S: Eu, Sr 5 (PO 4 ) 3 Cl: Eu, (SrEu) O.Al 2 O 3 and the like are exemplified.
  • the particle diameter of the phosphor those known in this field are used, and the average particle diameter is preferably 1 to 250 ⁇ m, particularly preferably 2 to 50 ⁇ m.
  • the addition amount is 1 to 80 parts by weight, preferably 5 to 60 parts by weight, based on 100 parts by weight of the resin component.
  • the curable resin composition A of the present invention can be obtained by uniformly mixing 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 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.
  • 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 epoxy resin-based compositions are difficult to be completely cured only by light irradiation. Therefore, in applications requiring heat resistance, it is necessary to complete the reaction by heating after light irradiation.
  • 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 obtained.
  • 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.
  • the 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 resin etc. as a hardening
  • curing 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 viscosity at 25 ° C.
  • the analysis conditions in gas chromatography were as follows: HP5-MS (0.25 mm IDx 15 m, thickness 0.25 ⁇ m) was used for the separation column, and the column oven temperature was set to the initial temperature of 100. The temperature was set at 0 ° C., and the temperature was raised at a rate of 15 ° C. per minute and held at 300 ° C. for 90 minutes. Helium was used as a carrier gas.
  • the measurement in gel permeation chromatography is as follows.
  • the column is a Shodex® SYSTEM-21 column (KF-803L, KF-802.5 ( ⁇ 2), KF-802), the coupled eluent is tetrahydrofuran, and the flow rate is 1 ml / min.
  • the column temperature was 40 ° C.
  • the detection was performed by RI
  • a standard polystyrene made by Shodex was used for the calibration curve.
  • Example 1 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, the following formula (5)
  • 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 form a tungstic acid catalyst, and then 90 parts of toluene and 85 parts of the olefin resin D-1 obtained in Example 1 were added.
  • the mixed solution was heated to 50 ° C., and with vigorous stirring, 55 parts by weight of 35 wt% hydrogen peroxide water was added, and the mixture was stirred at 50 ° C. for 13 hours.
  • 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.
  • 25 parts of a 20% by weight aqueous sodium thiosulfate solution was added, stirred for 30 minutes, and allowed to stand.
  • 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).
  • the physical property was tested as follows, and the result was combined with Table 1 and shown.
  • the curing conditions in the heat resistance property test and the thermomechanical property test are 150 ° C. ⁇ 3 hours after 120 ° C. ⁇ 1 hour pre-curing.
  • 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.
  • thermomechanical property test The curable resin compositions obtained in Examples and Comparative Examples were subjected to vacuum defoaming for 20 minutes, then cast in a Teflon (registered trademark) ⁇ 2 mm tube, and the cast was cured under the conditions described above and tested. I got a piece. Using this test piece, a thermomechanical property test (TMA measurement test) was performed under the following conditions. Measurement conditions Dynamic viscoelasticity measuring instrument: TM-7000 manufactured by Vacuum Riko Co., Ltd. Measurement temperature range: 40 ° C-250 ° C Temperature increase rate: 2 ° C./min Test piece size: ⁇ 2 mm A material cut into 15 mm was used.
  • Thermal durability transmission test The curable resin compositions obtained in Examples and Comparative Examples were subjected to vacuum defoaming for 20 minutes, and then gently cast on a glass substrate on which a dam was created with 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. Using these test pieces, the transmittance (measurement wavelength: 465 nm) before and after being left in a 150 ° C. oven for 96 hours was measured with a spectrophotometer, and the transmittance retention was calculated.
  • the epoxy resin of the present invention gives a curable resin composition having excellent curing characteristics such as a short gel time, and gives a cured product having excellent heat resistance (heat resistance characteristics, thermomechanical characteristics, heat resistance colorability).
  • 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, 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 epoxy resin of the present invention has a good curability and gives a cured product having excellent transparency (transparency). Moreover, from the results of the illuminance retention rate, it can be seen that the cured product of the epoxy resin of the present invention is excellent in heat deterioration resistance and deterioration resistance, and has excellent aptitude for LED applications.

Abstract

La présente invention concerne une nouvelle résine époxy alicyclique qui est hautement durcissable et, lorsqu'elle est durcie, est hautement transparente et a une excellente résistance à la chaleur et à la lumière. Ladite résine époxy alicyclique est obtenue par époxydation du matériau de départ de celle-ci, qui est une résine oléfine représentée par la formule (1). (Dans la formule, les multiples occurrences de R et P représentent chacune indépendamment des atomes d'hydrogène ou des groupes alkyle en C1–15).
PCT/JP2010/056869 2009-04-17 2010-04-16 Résine oléfine, résine époxy, composition de résine durcissable, et matériau résultant du durcissement de celle-ci WO2010119960A1 (fr)

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CN201080016851.5A CN102395555B (zh) 2009-04-17 2010-04-16 环氧树脂、可固化树脂组合物及其固化物

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JP2011225711A (ja) * 2010-04-19 2011-11-10 Nippon Kayaku Co Ltd エポキシ樹脂の製造法、エポキシ樹脂、および硬化性樹脂組成物
JP2013112649A (ja) * 2011-11-29 2013-06-10 Showa Denko Kk 多価グリシジル化合物の製造方法
JP2015500468A (ja) * 2011-12-02 2015-01-05 センスエア アーベーＳｅｎｓｅａｉｒ Ａｂ 光学測定のためのエポキシ成形ガスセル及び形成方法
WO2016119848A1 (fr) * 2015-01-29 2016-08-04 Henkel Ag & Co. Kgaa Procédé de préparation de résines époxy cycloaliphatiques
WO2018083881A1 (fr) * 2016-11-07 2018-05-11 昭和電工株式会社 Méthode de production d'un composé glycidylique polyvalent

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WO2013183736A1 (fr) * 2012-06-07 2013-12-12 日本化薬株式会社 Composition de résine époxy, produit durci à base de celle-ci et composition de résine durcissable
CN103289326B (zh) * 2013-06-28 2015-10-07 山东科技大学 用于灌封料的无卤阻燃环氧树脂组合物
CN108649113A (zh) * 2018-04-28 2018-10-12 上海应用技术大学 一种提高led良品率的新型应用工艺
KR20210036119A (ko) * 2019-09-25 2021-04-02 주식회사 케이씨씨 분체도료 조성물

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JP2011225711A (ja) * 2010-04-19 2011-11-10 Nippon Kayaku Co Ltd エポキシ樹脂の製造法、エポキシ樹脂、および硬化性樹脂組成物
JP2013112649A (ja) * 2011-11-29 2013-06-10 Showa Denko Kk 多価グリシジル化合物の製造方法
JP2015500468A (ja) * 2011-12-02 2015-01-05 センスエア アーベーＳｅｎｓｅａｉｒ Ａｂ 光学測定のためのエポキシ成形ガスセル及び形成方法
JP2018021938A (ja) * 2011-12-02 2018-02-08 センスエア アーベーＳｅｎｓｅａｉｒ Ａｂ 光学測定のためのエポキシ成形ガスセル及び形成方法
WO2016119848A1 (fr) * 2015-01-29 2016-08-04 Henkel Ag & Co. Kgaa Procédé de préparation de résines époxy cycloaliphatiques
WO2018083881A1 (fr) * 2016-11-07 2018-05-11 昭和電工株式会社 Méthode de production d'un composé glycidylique polyvalent
JPWO2018083881A1 (ja) * 2016-11-07 2019-09-19 昭和電工株式会社 多価グリシジル化合物の製造方法

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CN102395555B (zh) 2015-01-21
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