WO2010119960A1 - Olefin resin, epoxy resin, curable resin composition, and material resulting from curing same - Google Patents
Olefin resin, epoxy resin, curable resin composition, and material resulting from curing same Download PDFInfo
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- 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
Description
またコンポジット材、車の車体や船舶の構造材として、近年、その製造法の簡便さからRTM(Resin Transfer Molding)が使用されている。このような組成物においてはカーボンファイバー等への含浸のされやすさから低粘度のエポキシ樹脂が望まれている。 Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., adhesives, paints, laminates, moldings It is used in a wide range of fields such as materials, casting materials and resists. In recent years, especially in the field of semiconductor-related materials, electronic devices such as mobile phones with cameras, ultra-thin liquid crystals, plasma TVs, and light-weight notebook computers have become key to light, thin, short, and small. Very high characteristics have been demanded for packaging materials represented by resins. In particular, the structure of the tip package is complicated, and there are an increasing number of things that are difficult to seal without liquid sealing. For example, a cavity down type structure such as Enhanced BGA needs to be partially sealed and cannot be handled by transfer molding. For these reasons, the development of highly functional liquid epoxy resins has been demanded.
In recent years, RTM (Resin Transfer Molding) has been used as a composite material, a car body, and a structural material for a ship because of its simplicity of manufacturing method. In such a composition, a low-viscosity epoxy resin is desired because it is easily impregnated into carbon fiber or the like.
しかしながら、本製法により得られるエポキシ樹脂は、4官能のエポキシ樹脂の純度が低く、例えば同文献の段落0032に記載される例8においては4官能のテトラエポキシ体の純度は42.5%となっており、残りはトリエポキシ体や、ジエポキシ体、モノエポキシ体であり、アルコール構造が残存する純度の悪いものである。
また、本反応は高温での反応であるため、エポキシ同士の重合反応も起こることから粘度の高い樹脂となってしまい、作業性に問題が生じる場合もある。
また、前述のアルコール構造の残存は、例えば酸無水物での硬化であれば、一液化した際に酸無水物との反応が室温レベルで起こってしまい、貯蔵安定性がすこぶるわるくなるという問題が生じる。また架橋密度も低くなり、硬化物性に影響を及ぼすことから好ましくない。 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.
However, the epoxy resin obtained by this production method has a low purity of the tetrafunctional epoxy resin. For example, in Example 8 described in paragraph 0032 of the same document, 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.
Moreover, since 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.
In addition, if the alcohol structure remains as described above, for example, when cured with an acid anhydride, 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. In addition, the crosslink density is lowered, which affects the cured properties, which is not preferable.
すなわち本発明は
(1)
下記式(1) As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention provides (1)
Following formula (1)
で表されることを特徴とするオレフィン樹脂、
(2)
前項(1)に記載のオレフィン樹脂を酸化することにより得られることを特徴とするエポキシ樹脂、
(3)
過酸化水素または過酸を用いてエポキシ化されたことを特徴とする前項(2)に記載のエポキシ樹脂、
(4)
前項(2)または(3)に記載のエポキシ樹脂と、硬化剤および/または硬化触媒とを含有することを特徴とする硬化性樹脂組成物、
(5)
前項(4)に記載の硬化性樹脂組成物を硬化してなることを特徴とする硬化物、
に関する。 (In the formula, a plurality of R and P are independently present and each represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms.)
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.
で表される。 (In the formula, a plurality of 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
で表される化合物で、具体的にはシクロヘキセンカルボン酸、シクロヘキセンカルボン酸メチル、シクロヘキセンカルボン酸エチル、シクロヘキセンカルボン酸プロピル、シクロヘキセンカルボン酸ブチル、シクロヘキセンカルボン酸ヘキシル、(シクロヘキセニルメチル)シクロヘキセンカルボキシレート、シクロヘキセンカルボン酸オクチル、シクロヘキセンカルボン酸クロライド、シクロヘキセンカルボン酸ブロマイド、メチルシクロヘキセンカルボン酸、メチルシクロヘキセンカルボン酸メチル、メチルシクロヘキセンカルボン酸エチル、メチルシクロヘキセンカルボン酸プロピル、(メチルシクロヘキセニルメチル)メチルシクロヘキセンカルボキシレート、メチルシクロヘキセンカルボン酸クロライド等が挙げられるが、これらに限定されるものではない。これらは単独で用いてもよく、2種以上併用してもよい。 (In the formula, 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.)
In particular, 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 cyclohexene carboxylate, propyl methyl cyclohexene carboxylate, (methyl cyclohexenyl methyl) methyl cyclohexene carboxylate, methyl cyclohexene Carboxylic acid chloride etc. are mentioned, but these The present invention is not limited. These may be used alone or in combination of two or more.
で表される化合物である。具体的には、例えば、ジトリメチロールプロパン、ジトリメチロールブタン、ジトリメチロールペンタン、ジトリメチロールヘキサン、ジトリメチロールヘプタン、ジトリメチロールオクタン等が挙げられる。このような化合物の製造方法としては、末端にホルミル基を有する炭素数1~15の化合物に対し、ホルムアルデヒド(もしくはパラホルムアルデヒド、メタホルムアルデヒド等)を反応させることで、得ることができる。(例えば、参考特許文献としては、日本国特開2005-023067号公報、日本国特開2003-335717号公報、日本国特開平09-268150号公報、日本国特開2002-047224号公報などが挙げられる。) (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms.)
It is 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. (For example, as reference patent documents, Japanese Patent Application Publication No. 2005-023067, Japanese Patent Application Publication No. 2003-335717, Japanese Patent Application Publication No. 09-268150, Japanese Patent Application Publication No. 2002-047224, and the like. Can be mentioned.)
具体的に好ましい置換基Rとしては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基が挙げられるが、特にエチル基、プロピル基、ブチル基が好ましく、より好ましくはエチル基である。 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. In particular, when the substituent P is bonded to an olefin, in order to improve the reactivity, 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.
Specific examples of 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.
その純度が80面積%未満である場合、後のエポキシ化工程で加水分解されやすい等の問題が生じる他、得られるエポキシ樹脂をエポキシ樹脂組成物とした際、特に酸無水物等の硬化剤と一液化すると、常温レベルで酸無水物とエポキシ樹脂に残存する水酸基が反応することが影響し、貯蔵安定性が悪くなるなどの問題が生じるため好ましくない。
尚、本発明のオレフィン樹脂におけるGPCの測定条件は下記の通りとした。カラムは、Shodex SYSTEM-21カラム(KF-803L、KF-802.5(×2本)、KF-802)、連結溶離液はテトラヒドロフラン、流速は1ml/min.、カラム温度は40℃、また検出はRIで行い、検量線はShodex製標準ポリスチレンを使用した。 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.
When 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, and a standard polystyrene made by Shodex was used for the calibration curve.
過酸によるエポキシ化の手法としては具体的には日本国特開2006-52187号公報に記載の手法などが挙げられる。使用できる過酸としては、例えばギ酸、酢酸、プロピオン酸、マレイン酸、安息香酸、m-クロロ安息香酸、フタル酸などの有機酸およびそれらの酸無水物が挙げられる。これらの中でも、過酸化水素と反応して有機過酸を生成する効率、反応温度、操作の簡便性、経済性などの観点からは、ギ酸、酢酸、無水フタル酸を使用するのが好ましく、特に反応操作の簡便性の観点から、ギ酸または酢酸を使用するのがより好ましい。
過酸化水素水によるエポキシ化の手法においては種々の手法が適応できるが、具体的には、日本国特開昭59-108793号公報、日本国特開昭62-234550号公報、日本国特開平5-213919号公報、日本国特開平11-349579号公報、特公平1―33471号公報、日本国特開2001-17864号公報、日本国特公平3-57102号公報等に挙げられるような手法が適応できる。 The olefin resin of the present invention represented by the formula (1) can be oxidized to form the epoxy resin of the present invention. Examples of the oxidation method include, but are not limited to, a method of oxidizing with a peracid such as peracetic acid, a method of oxidizing with a hydrogen peroxide solution, and a method of oxidizing with air (oxygen).
Specific examples of the epoxidation method using peracid include the method described in Japanese Patent Application Laid-Open No. 2006-52187. Examples of 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. Among these, it is preferable to use 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.
まず、本発明のオレフィン樹脂、ポリ酸類及び4級アンモニウム塩を、有機物と過酸化水素水のエマルジョン状態の下で反応させる。 Hereinafter, a particularly preferable method for obtaining the epoxy resin of the present invention will be exemplified.
First, 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.
具体的なポリ酸およびポリ酸塩としては、タングステン酸、12-タングスト燐酸、12-タングストホウ酸、18-タングスト燐酸および12-タングストケイ酸等から選ばれるタングステン系の酸、モリブデン酸およびリンモリブデン酸等から選ばれるモリブデン系の酸、ならびにそれらの塩等が挙げられる。
これらの塩のカウンターカチオンとしては、4級アンモニウムイオン、アルカリ土類金属イオン、アルカリ金属イオンなどが挙げられる。 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.
具体的にはトリデカニルメチルアンモニウム塩、ジラウリルジメチルアンモニウム塩、トリオクチルメチルアンモニウム塩、トリアルキルメチル(アルキル基がオクチル基である化合物とデカニル基である化合物の混合タイプ)アンモニウム塩、トリヘキサデシルメチルアンモニウム塩、トリメチルステアリルアンモニウム塩、テトラペンチルアンモニウム塩、セチルトリメチルアンモニウム塩、ベンジルトリブチルアンモニウム塩、ジセチルジメチルアンモニウム塩、トリセチルメチルアンモニウム塩、ジ硬化牛脂アルキルジメチルアンモニウム塩などが挙げられるがこれらに限定されない。 As the 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.
Specifically, tridecanylmethylammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (a mixed type of a compound in which the alkyl group is an octyl group and a compound in which the decanyl group is a compound) ammonium salt, trihexa Examples include decylmethylammonium salt, trimethylstearylammonium salt, tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, and di-cured tallow alkyldimethylammonium salt. It is not limited to.
炭素数が100を上回ると疎水性が強くなりすぎて、4級アンモニウム塩の有機層への溶解性が悪くなる場合がある。炭素数が10未満であると親水性が強くなり、同様に4級アンモニウム塩の有機層への相溶性が悪くなり、好ましくない。 There are no particular limitations on the anionic species of these salts, and specific examples include halide ions, nitrate ions, sulfate ions, hydrogen sulfate ions, acetate ions, carbonate ions, and the like, but are not limited thereto.
When 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. When the number of carbon atoms is less than 10, the hydrophilicity is increased, and the compatibility of the quaternary ammonium salt with the organic layer is similarly deteriorated.
例えば、タングステン酸であればH2WO4で2価であるので、タングステン酸1モルに対し、4級アンモニウム塩は0.02~20モルの範囲が好ましい。またタングストリン酸であれば3価であるので、同様に0.03~30モル、ケイタングステン酸であれば4価であるので0.04~40モルが好ましい。
4級アンモニウム塩の使用量が、ポリ酸類の価数倍の0.01倍当量よりも低い場合、エポキシ化反応が進行しづらい(場合によっては反応の進行が早くなる)、また、副生成物ができやすいという問題が生じる。10倍当量よりも多い場合、後処理が大変であるばかりか、反応を抑制する働きがあり、好ましくない。 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.
For example, since tungstic acid is divalent with H 2 WO 4 , the quaternary ammonium salt is preferably in the range of 0.02 to 20 mol with respect to 1 mol of tungstic acid. In addition, since it is trivalent for tungstophosphoric acid, it is similarly 0.03 to 30 mol, and for tetratungstic acid, it is tetravalent, so 0.04 to 40 mol is preferable.
When the amount of the quaternary ammonium salt used is lower than 0.01 times the valence of the polyacid, the epoxidation reaction is difficult to proceed (in some cases, the reaction proceeds faster), and a by-product The problem that it is easy to do occurs. When the amount is more than 10 times equivalent, not only is the post-treatment difficult, but there is a function of suppressing the reaction, which is not preferable.
特に本発明においては触媒であるポリ酸類を溶解した際に、pH5~9の間になるように調整されることが好ましい。 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.
あるいは水、有機溶剤およびオレフィン化合物を撹拌している中に、ポリ酸類、燐酸(あるいは燐酸塩類)を加え、pH調整を行った後、4級アンモニウム塩を添加し、二層で撹拌したところに、過酸化水素を滴下するという手法を用いるという方法でも構わない。 At this time, buffer solution (or water and phosphate) and polyacids were added to adjust pH, then quaternary ammonium salt, organic solvent and olefin compound were added, and hydrogen peroxide was added dropwise to the mixture after stirring in two layers. The technique of doing is used.
Alternatively, while 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. Alternatively, a method of dropping hydrogen peroxide may be used.
これらは水溶液として加えることが好ましく、その濃度は0.5~30重量%が好ましい。 Examples of the reducing agent 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.
その使用量としては水、あるいは有機溶剤(例えば、トルエン、キシレン等の芳香族炭化水素、メチルイソブチルケトン、メチルエチルケトン等のケトン類、シクロヘキサン、ヘプタン、オクタン等の炭化水素、メタノール、エタノール、イソプロピルアルコール等のアルコール類等の各種溶剤)に溶解するものであれば、その使用量は過剰分の過酸化水素のモル数に対し、通常0.01~20倍モル、より好ましくは0.05~10倍モル、さらに好ましくは0.05~3倍モルである。これらは水、あるいは前述の有機溶剤の溶液として添加しても単体で添加しても構わない。 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.
で表される分子を主成分とするが、式(4) (In the formula, a plurality of R and P are independently present and each represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms.)
The main component is a molecule represented by formula (4)
に示すような各種の構造の化合物が混在する。また、反応条件によっては、原料由来のモノメチロール体、ジメチロール体等のアルコール構造を有する化合物、エポキシ基同士の重合した高分子量体やその他副反応物が生成する。
本発明のエポキシ樹脂は、式(3)で表される構造を主成分として有し、その純度はGPC測定において好ましくは80面積%以上であり、より好ましくは90面積%以上、さらに好ましくは95面積%以上である。
尚、本発明のエポキシ樹脂におけるGPCの測定条件は下記の通りとした。カラムは、Shodex SYSTEM-21カラム(KF-803L、KF-802.5(×2本)、KF-802)、連結溶離液はテトラヒドロフラン、流速は1ml/min.、カラム温度は40℃、また検出はRIで行い、検量線はShodex製標準ポリスチレンを使用した。 (In the formula, 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, and a standard polystyrene made by Shodex was used for the calibration curve.
本発明の硬化性樹脂組成物は本発明のエポキシ樹脂を必須成分として含有する。本発明の硬化性樹脂組成物においては、硬化剤による熱硬化(硬化性樹脂組成物A)と酸を硬化触媒とするカチオン硬化(硬化性樹脂組成物B)の二種の方法が適応できる。 Hereinafter, it describes about the curable resin composition of this invention containing the epoxy resin of this invention.
The curable resin composition of the present invention contains the epoxy resin of the present invention as an essential component. In the curable resin composition of the present invention, two methods of heat curing with a curing agent (curable resin composition A) and cationic curing with an acid as a curing catalyst (curable resin composition B) can be applied.
シクロヘキセン構造を有する化合物としては、シクロヘキセンカルボン酸とアルコール類とのエステル化反応あるいはシクロヘキセンメタノールとカルボン酸類とのエステル化反応(Tetrahedron vol.36 p.2409 (1980)、Tetrahedron Letter p.4475 (1980)等に記載の手法)、あるいはシクロヘキセンアルデヒドのティシェンコ反応(日本国特開2003-170059号公報、日本国特開2004-262871号公報等に記載の手法)、さらにはシクロヘキセンカルボン酸エステルのエステル交換反応(日本国特開2006-052187号公報等に記載の手法)によって製造できる化合物が挙げられる。
アルコール類としては、アルコール性水酸基を有する化合物であれば特に限定されないがエチレングリコール、プロピレングリコール、1,3-プロパンジオール、1,2-ブタンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、シクロヘキサンジメタノールなどのジオール類、グリセリン、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、2-ヒドロキシメチル-1,4-ブタンジオールなどのトリオール類、ペンタエリスリトールなどのテトラオール類などが挙げられる。またカルボン酸類としてはシュウ酸、マレイン酸、フマル酸、フタル酸、イソフタル酸、アジピン酸、シクロヘキサンジカルボン酸などが挙げられるがこれに限らない。 In particular, when the curable resin composition of the present invention is used for optical applications, 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. Particularly in the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.
As compounds having a cyclohexene structure, 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. And tetraols. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.
これらエポキシ樹脂の具体例としては、ERL-4221、UVR-6105、ERL-4299(全て商品名、いずれもダウ・ケミカル製)、セロキサイド2021P、エポリードGT401、EHPE3150、EHPE3150CE(全て商品名、いずれもダイセル化学工業製)及びジシクロペンタジエンジエポキシドなどが挙げられるがこれらに限定されるものではない(参考文献:総説エポキシ樹脂 基礎編I p76-85)。
これらは単独で用いてもよく、2種以上併用してもよい。 Furthermore, as a compound having a cyclohexene structure other than the above, an acetal compound obtained by an acetal reaction between a cyclohexene aldehyde derivative and an alcohol is exemplified. As a reaction method, it can be produced by applying a general acetalization reaction. For example, 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. 48-96590), a method using water as a reaction medium (US Pat. No. 3,092,640), reaction A method using an organic solvent as a medium (Japanese Patent Laid-open No. 7-215979), a method using a solid acid catalyst (Japanese Patent Laid-Open No. 2007-230992), and the like are disclosed. A cyclic acetal structure is preferable from the viewpoint of structural stability.
Specific examples of these epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celoxide 2021P, Epolide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel) (Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited thereto (Reference: Review Epoxy Resin Basic Edition I p76-85).
These may be used alone or in combination of two or more.
硬化性樹脂組成物A(硬化剤による熱硬化)
本発明の硬化性樹脂組成物Aが含有する硬化剤としては、例えばアミン系化合物、酸無水物系化合物、アミド系化合物、フェノール系化合物、カルボン酸系化合物などが挙げられる。用いうる硬化剤の具体例としては、ジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルスルホン、イソホロンジアミン、ジシアンジアミド、リノレン酸の2量体とエチレンジアミンより合成されるポリアミド樹脂などの含窒素化合物(アミン、アミド化合物);無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、無水ナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ブタンテトラカルボン酸無水物、ビシクロ[2,2,1]ヘプタン-2,3-ジカルボン酸無水物、メチルビシクロ[2,2,1]ヘプタン-2,3-ジカルボン酸無水物、シクロヘキサン-1,3,4-トリカルボン酸-3,4-無水物、などの酸無水物;各種アルコール、カルビノール変性シリコーン、と前述の酸無水物との付加反応により得られるカルボン酸樹脂;ビスフェノールA、ビスフェノールF、ビスフェノールS、フルオレンビスフェノール、テルペンジフェノール、4,4’-ビフェノール、2,2’-ビフェノール、3,3’,5,5’-テトラメチル-[1,1’-ビフェニル]-4,4’-ジオール、ハイドロキノン、レゾルシン、ナフタレンジオール、トリス-(4-ヒドロキシフェニル)メタン、1,1,2,2-テトラキス(4-ヒドロキシフェニル)エタン、フェノール類(フェノール、アルキル置換フェノール、ナフトール、アルキル置換ナフトール、ジヒドロキシベンゼン、ジヒドロキシナフタレン等)とホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、p-ヒドロキシベンズアルデヒド、o-ヒドロキシベンズアルデヒド、p-ヒドロキシアセトフェノン、o-ヒドロキシアセトフェノン、ジシクロペンタジエン、フルフラール、4,4’-ビス(クロロメチル)-1,1’-ビフェニル、4,4’-ビス(メトキシメチル)-1,1’-ビフェニル、1,4’-ビス(クロロメチル)ベンゼン又は1,4’-ビス(メトキシメチル)ベンゼン等との重縮合物及びこれらの変性物、テトラブロモビスフェノールA等のハロゲン化ビスフェノール類、テルペンとフェノール類の縮合物などのポリフェノール類;イミダゾール、トリフルオロボラン-アミン錯体、グアニジン誘導体の化合物などが挙げられるが、これらに限定されるものではない。これらは単独で用いてもよく、2種以上を用いてもよい。
本発明においては特に前述の酸無水物系化合物、カルボン酸系化合物に代表される、酸無水物構造及び/またはカルボン酸構造を有する化合物が好ましい。 Hereinafter, each curable resin composition will be referred to.
Curable resin composition A (thermal curing with curing agent)
Examples of the curing agent contained in the curable resin composition A of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, 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-dicarboxylic anhydride, Cyclohe Acid anhydrides such as sun-1,3,4-tricarboxylic acid-3,4-anhydrides; carboxylic acid resins obtained by addition reaction of various alcohols, carbinol-modified silicones and the aforementioned acid anhydrides; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol) , Naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphth ) And formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1 Polycondensation with '-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene or 1,4'-bis (methoxymethyl) benzene And modified products thereof, polyphenols such as halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols; imidazole, trifluoroborane-amine complexes, guanidine derivative compounds, etc. Also limited to Not. These may be used alone or in combination of two or more.
In the present invention, compounds having an acid anhydride structure and / or a carboxylic acid structure represented by the above-mentioned acid anhydride compounds and carboxylic acid compounds are particularly preferable.
光安定剤としては、ヒンダートアミン系の光安定剤、特にHALS等が好適である。HALSとしては特に限定されるものではないが、代表的なものとしては、ジブチルアミン・1,3,5-トリアジン・N,N’―ビス(2,2,6,6-テトラメチル-4-ピペリジル-1,6-ヘキサメチレンジアミンとN-(2,2,6,6-テトラメチル-4-ピペリジル)ブチルアミンの重縮合物、コハク酸ジメチル-1-(2-ヒドロキシエチル)-4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン重縮合物、ポリ〔{6-(1,1,3,3-テトラメチルブチル)アミノ-1,3,5-トリアジン-2,4-ジイル}{(2,2,6,6-テトラメチル-4-ピペリジル)イミノ}ヘキサメチレン{(2,2,6,6-テトラメチル-4-ピペリジル)イミノ}〕、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)〔〔3,5-ビス(1,1-ジメチルエチル)-4-ヒドリキシフェニル〕メチル〕ブチルマロネート、ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)セバケート、ビス(1-オクチロキシ-2,2,6,6-テトラメチル-4-ピペリジル)セバケート、2-(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)-2-n-ブチルマロン酸ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)、等が挙げられる。HALSは1種のみが用いられても良いし、2種類以上が併用されても良い。 Furthermore, you may add a light stabilizer to the curable resin composition A of this invention as needed.
As the light stabilizer, hindered amine-based light stabilizers, particularly HALS and the like are suitable. HALS is not particularly limited, but typical examples include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4- Polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate -2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (1,2,2, 6,6-Pentamethyl-4-pi Peridyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di -T-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), etc. Only one HALS is used. Two or more types may be used in combination.
酸性硬化触媒を用いて硬化させる本発明の硬化性樹脂組成物Bは、酸性硬化触媒として光重合開始剤あるいは熱重合開始剤を含有する。さらに、希釈剤、重合性モノマー、重合性オリゴマー、重合開始補助剤、光増感剤等の各種公知の化合物、材料等を含有していてもよい。また、所望に応じて無機充填材、着色顔料、紫外線吸収剤、酸化防止剤、安定剤等、各種公知の添加剤を含有してもよい。 Curable resin composition B (cationic curing with acidic curing catalyst)
The curable resin composition B of the present invention that is cured using an acidic curing catalyst contains a photopolymerization initiator or a thermal polymerization initiator as an acidic curing catalyst. Furthermore, you may contain various well-known compounds, materials, such as a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization start adjuvant, a photosensitizer. Moreover, you may contain various well-known additives, such as an inorganic filler, a color pigment, a ultraviolet absorber, antioxidant, a stabilizer, as needed.
活性エネルギー線カチオン重合開始剤の例は、金属フルオロホウ素錯塩および三フッ化ホウ素錯化合物(米国特許第3379653号)、ビス(ペルフルアルキルスルホニル)メタン金属塩(米国特許第3586616号)、アリールジアゾニウム化合物(米国特許第3708296号)、VIa族元素の芳香族オニウム塩(米国特許第4058400号)、Va族元素の芳香族オニウム塩(米国特許第4069055号)、IIIa~Va族元素のジカルボニルキレート(米国特許第4068091号)、チオピリリウム塩(米国特許第4139655号)、MF6 -陰イオンの形のVIb族元素(米国特許第4161478号;Mはリン、アンチモンおよび砒素から選択される。)、アリールスルホニウム錯塩(米国特許第4231951号)、芳香族ヨードニウム錯塩および芳香族スルホニウム錯塩(米国特許第4256828号)、およびビス[4-(ジフェニルスルホニオ)フェニル]スルフィド-ビス-ヘキサフルオロ金属塩(Journal of Polymer Science, Polymer Chemistry、第2巻、1789項(1984年))である。その他、鉄化合物の混合配位子金属塩およびシラノール-アルミニウム錯体も使用することが可能である。
また、具体例としては、「アデカオプトマーSP150」、「アデカオプトマーSP170」(いずれも旭電化工業社製)、「UVE-1014」(ゼネラルエレクトロニクス社製)、「CD-1012」(サートマー社製)、「RP-2074」(ローディア社製)等が挙げられる。
該カチオン重合開始剤の使用量は、エポキシ樹脂成分100重量部に対して、好ましくは、0.01~50重量部であり、より好ましくは、0.1~10重量部である。 As the acidic curing catalyst, a cationic polymerization initiator is preferable, and a photocationic polymerization initiator is particularly preferable. Examples of the cationic polymerization initiator include those having an onium salt such as an iodonium salt, a sulfonium salt, and a diazonium salt, and these can be used alone or in combination of two or more.
Examples of active energy ray cationic polymerization initiators include metal fluoroboron complex salts and boron trifluoride complex compounds (US Pat. No. 3,379,653), bis (perfluoroalkylsulfonyl) methane metal salts (US Pat. No. 3,586,616), aryldiazonium Compounds (US Pat. No. 3,708,296), aromatic onium salts of group VIa elements (US Pat. No. 4,058,400), aromatic onium salts of group Va elements (US Pat. No. 4069055), dicarbonyl chelates of group IIIa to Va elements (U.S. Pat. No. 4,068,091), thiopyrylium salts (U.S. Pat. No. 4,139,655), MF 6 - VIb group element in the form of anions,, (U.S. Pat. No. 4,161,478 M is selected from phosphorus, antimony and arsenic.) Arylsulfonium complex salts (US Pat. No. 42319) 1), aromatic iodonium complex salts and aromatic sulfonium complex salts (US Pat. No. 4,256,828), and bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluorometal salts (Journal of Polymer Science, Polymer Chemistry, Volume 2, Section 1789 (1984)). In addition, mixed ligand metal salts of iron compounds and silanol-aluminum complexes can also be used.
As specific examples, “Adekaoptomer SP150”, “Adekaoptomer SP170” (all manufactured by Asahi Denka Kogyo Co., Ltd.), “UVE-1014” (manufactured by General Electronics Co., Ltd.), “CD-1012” (Sartomer Company) And "RP-2074" (manufactured by Rhodia).
The amount of the cationic polymerization initiator used is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin component.
重合開始補助剤の具体例としては、ベンゾイン、ベンジル、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル、アセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン、1,1-ジクロロアセトフェノン、1-ヒドロキシシクロヘキシルフェニルケトン、2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノールプロパン-1-オン、N,N-ジメチルアミノアセトフェノン、2-メチルアントラキノン、2-エチルアントラキノン、2-tert-ブチルアントラキノン、1-クロロアントラキノン、2-アミルアントラキノン、2-イソプロピルチオキサトン、2,4-ジメチルチオキサントン、2,4-ジエチルチオキサントン、2,4-ジイソプロピルチオキサントン、アセトフェノンジメチルケタール、ベンゾフェノン、4-メチルベンゾフェノン、4,4’-ジクロロベンゾフェノン、4,4’-ビスジエチルアミノベンゾフェノン、ミヒラーズケトン等の重合開始剤が挙げられる。重合開始剤等の重合開始補助剤の使用量は、光ラジカル重合可能な樹脂成分100質量部に対して0.01~30質量部、好ましくは0.1~10質量部である。 In the curable resin composition B of the present invention, one or more polymerization initiation assistants and, if necessary, a photosensitizer can be used in combination with the cationic polymerization initiator.
Specific examples of 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, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl Ketal, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis-diethylamino benzophenone, and a polymerization initiator such as Michler's ketone. The amount of the polymerization initiation assistant such as a polymerization initiator 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 resin component capable of photoradical polymerization.
本発明の硬化性樹脂組成物Bは、加熱及び/または紫外線照射により硬化できる(例えば、参考文献:総説エポキシ樹脂 第1巻 基礎編I p82-84)が、その際の熱量及び/または紫外線照射量は硬化性樹脂組成物Bの組成に依存して異なるため、それぞれの組成に合わせて硬化条件が決定される。基本的には、硬化物が使用目的において必要とされる強度を発現できる硬化条件であれば良い。通常、これらエポキシ樹脂系組成物は光照射のみで完全に硬化させることが難しいため、耐熱性が求められる用途においては光照射後に加熱により完全に反応を終了させる必要がある。また、光硬化の際の照射光を細部まで透過させることが必要なため、本発明のエポキシ樹脂および硬化性樹脂組成物Bにおいては透明性の高い化合物および組成物が望まれる。 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 γ-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). Since the amount varies depending on the composition of the curable resin composition B, 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. Usually, 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. Moreover, since it is necessary to permeate | 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.
撹拌機、還流冷却管、撹拌装置、ディーンスターク管を備えたフラスコに、窒素パージを施しながらトルエン150部、下記式(5) 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)
撹拌機、還流冷却管、撹拌装置を備えたフラスコに、窒素パージを施しながら水15部、12-タングストリン酸0.95部、燐酸水素二ナトリウム0.78部、ジ硬化牛脂アルキルジメチルアンモニウムアセテート2.7部(ライオンアクゾ製 50%ヘキサン溶液、アカード2HTアセテート)を加え、タングステン酸系触媒を生成させた後、トルエン90部、実施例1で得られたオレフィン樹脂D-1を85部加え、この混合溶液を50℃に昇温し、激しく攪拌しながら、35重量%過酸化水素水55部を加え、そのまま50℃で13時間攪拌した。GCにて反応の進行を確認したところ、反応終了後の基質のコンバ-ジョンは>99%であり、原料ピークは消失していた。
ついで1重量%水酸化ナトリウム水溶液で中和した後、20重量%チオ硫酸ナトリウム水溶液25部を加え30分攪拌を行い、静置した。2層に分離した有機層を取り出し、ここにシリカゲル(ワコーゲル C-300 和光純薬工業製)10部、活性炭(NORIT製 CAP SUPER)20部、ベントナイト(ホージュン製 ベンゲルSH)20部を加え、室温で1時間攪拌後、ろ過した。得られたろ液を水100部で3回水洗を行い、得られた有機層より、有機溶剤を留去することで、下記式(6) 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. 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.
Next, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 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).
得られたエポキシ樹脂(EP-1)15部に対し、シリカゲル(ワコーゲル C-300 和光純薬製)105部を使用し、酢酸エチル:ヘキサン=1:3の展開溶媒を用い、カラムクロマトグラフィーにより精製を行った。得られたエポキシ樹脂(EP-2)は10部であり、得られたエポキシ樹脂の純度はGPCの測定結果より、前記式(6)の骨格の化合物を98%以上含有していることを確認した。さらに、GC測定においては純度約99%であった。また、エポキシ当量は189g/eq.であった。 Example 3
By column chromatography using 105 parts of silica gel (Wakogel C-300, manufactured by Wako Pure Chemical Industries, Ltd.) and developing solvent of ethyl acetate: hexane = 1: 3 with respect to 15 parts of the obtained epoxy resin (EP-1). Purification was performed. The obtained epoxy resin (EP-2) was 10 parts, and the purity of the obtained epoxy resin was confirmed by GPC measurement results to contain 98% or more of the skeleton compound of the formula (6). did. Furthermore, in the GC measurement, the purity was about 99%. The epoxy equivalent was 189 g / eq. Met.
実施例2において、オレフィン樹脂D-1 85部を、日本国特開平7-17917号公報に記載の手法により、製造した下記式(7) Synthesis example 1
In Example 2, 85 parts of olefin resin D-1 was produced by the method described in JP-A-7-17917 of the following formula (7)
得られたエポキシ樹脂(EP-4)は7部であり、該エポキシ樹脂の純度はGPCの測定結果より、下記式(8) Synthesis was performed in the same manner except that 60 parts of the olefin resin (D-2) represented by the following formula was obtained, and 52 parts of a comparative epoxy resin (EP-3) was obtained. Furthermore, 210 parts of silica gel (Wakogel C-300, manufactured by Wako Pure Chemical Industries, Ltd.) is used for 30 parts of the obtained epoxy resin (EP-3), and a developing solvent of ethyl acetate: hexane = 1: 4, 2: 5 is used. Purification was performed by column chromatography.
The obtained epoxy resin (EP-4) was 7 parts, and the purity of the epoxy resin was determined by the following formula (8) from the GPC measurement result.
実施例2、3で得られた本発明のエポキシ樹脂(EP-1、EP-2)、合成例1で得られた比較用のエポキシ樹脂(EP-4)について、硬化剤として、メチルヘキサヒドロフタル酸無水物(新日本理化(株)製、リカシッドMH700G、以下、H1と称す)、硬化促進剤(硬化触媒)としてヘキサデシルトリメチルアンモニウムヒドロキシド(東京化成工業(株)製 25%メタノール溶液、C1と称す)を使用し、下記表1に示す配合比(重量部)で配合し、20分間脱泡を行い、本発明及び比較用の硬化性樹脂組成物を得た。得られた硬化性樹脂組成物につき、下記のとおり物性を試験し、結果を表1にあわせて示した。なお、耐熱特性試験並びに熱機械特性試験における硬化条件は120℃×1時間の予備硬化の後150℃×3時間である。 Examples 4 and 5 and Comparative Example 1
For the epoxy resins (EP-1, EP-2) of the present invention obtained in Examples 2 and 3 and the comparative epoxy resin (EP-4) obtained in Synthesis Example 1, methyl hexahydro Phthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH700G, hereinafter referred to as H1), hexadecyltrimethylammonium hydroxide as a curing accelerator (curing catalyst) (25% methanol solution, manufactured by Tokyo Chemical Industry Co., Ltd.) C1) was used and blended at a blending ratio (parts by weight) shown in Table 1 below, followed by defoaming for 20 minutes to obtain a curable resin composition for comparison with the present invention. About the obtained curable resin composition, 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.
実施例及び比較例で得られた硬化性樹脂組成物を真空脱泡20分間実施後、横7mm、縦5cm、厚み約800μmの試験片用金型に静かに注型し、その後、上からポリイミドフィルムでフタをした。その注型物を前述の条件で硬化させ動的粘弾性用試験片を得た。これらの試験片を用い、下記に示した条件で、動的粘弾性試験(DMA測定試験)を実施した。
測定条件
動的粘弾性測定器:TA-instruments製、DMA-2980
測定温度範囲:-30℃~280℃
昇温速度:2℃/分
試験片サイズ:5mm×50mmに切り出した物を使用した(厚みは約800μm)。
解析条件
Tg:DMA測定に於けるTan-δのピーク点をTgとした。 (Heat resistance test)
The curable resin compositions obtained in the examples and comparative examples were vacuum degassed for 20 minutes, and then gently poured into a test piece mold having a width of 7 mm, a length of 5 cm, and a thickness of about 800 μm. Covered with film. The cast was cured under the above conditions to obtain a dynamic viscoelastic test piece. Using these test pieces, a dynamic viscoelasticity test (DMA measurement test) was performed under the conditions shown below.
Measurement conditions 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 μm).
Analysis conditions Tg: The peak point of Tan-δ in DMA measurement was defined as Tg.
実施例及び比較例で得られた硬化性樹脂組成物を真空脱泡20分間実施後、テフロン(登録商標)製のφ2mmチューブにて注形し、その注型物を前述の条件で硬化させ試験片を得た。この試験片を用い、下記に示した条件で、熱機械特性試験(TMA測定試験)を実施した。
測定条件
動的粘弾性測定器:真空理工(株)製 TM-7000
測定温度範囲:40℃~250℃
昇温速度:2℃/分
試験片サイズ:φ2mm 15mmに切り出した物を使用した。 (Thermo-mechanical 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) φ2 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: φ2 mm A material cut into 15 mm was used.
実施例及び比較例で得られた硬化性樹脂組成物を真空脱泡20分間実施後、30mm×20mm×高さ1mmになるように耐熱テープでダムを作成したガラス基板上に静かに注型した。その注型物を、120℃×3時間の予備硬化の後150℃×1時間で硬化させ、厚さ1mmの透過率用試験片を得た。
これらの試験片を用い、150℃オーブン中96時間放置前後における透過率(測定波長:465nm)を分光光度計により測定し、その透過率の保持率を算出した。 (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.
実施例及び比較例で得られた硬化性樹脂組成物を1mL取り、150℃におけるゲルタイムを測定した。
測定機器
ゲルタイマー:No.153 Geltime Tester(安田精機製作所製) (Curing test)
1 mL of the curable resin composition obtained in Examples and Comparative Examples was taken and the gel time at 150 ° C. was measured.
Measuring instrument Gel timer: No. 153 Geltime Tester (manufactured by Yasuda Seiki Seisakusho)
実施例2で得られた本発明のエポキシ樹脂(EP-2)、3,4-エポキシシクロヘキサンカルボン酸=3,4-エポキシシクロヘキシルメチル(ダウケミカル製 ERL-4221(以下、エポキシ樹脂(EP-5)))について、硬化剤(H1)、硬化促進剤(硬化触媒)(C1)を使用し、下記表2に示す配合比(重量部)で配合し、20分間脱泡を行い、本発明及び比較用の硬化性樹脂組成物を得た。得られた硬化性樹脂組成物につき、下記のとおり物性を試験し、結果を表2にあわせて示した。 Example 6 and Comparative Example 2
Epoxy resin (EP-2) of the present invention obtained in Example 2, 3,4-epoxycyclohexanecarboxylic acid = 3,4-epoxycyclohexylmethyl (ERL-4221 manufactured by Dow Chemical (hereinafter referred to as epoxy resin (EP-5)) ))), Using a curing agent (H1) and a curing accelerator (curing catalyst) (C1), blended at a blending ratio (parts by weight) shown in Table 2 below, defoamed for 20 minutes, A comparative curable resin composition was obtained. About the obtained curable resin composition, the physical property was tested as follows and the result was combined with Table 2 and shown.
実施例及び比較例で得られた硬化性樹脂組成物を真空脱泡20分間実施後、30mm×20mm×高さ1mmになるように耐熱テープでダムを作成したガラス基板上に静かに注型した。その注型物を、120℃×3時間の予備硬化の後150℃×1時間で硬化させ、厚さ1mmの透過率用試験片を得た。分光光度計によりその透過率を比較した。(測定波長:400nm) (Transmittance 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. The transmittance was compared with a spectrophotometer. (Measurement wavelength: 400 nm)
実施例及び比較例で得られた硬化性樹脂組成物を真空脱泡20分間実施後、シリンジに充填し精密吐出装置を使用して、発光波長465nmを持つ発光素子を搭載した外径5mm角表面実装型LEDパッケージ(内径4.4mm、外壁高さ1.25mm)に注型した。その後、所定の硬化条件で硬化させることで、点灯試験用LEDを得る。点灯試験は、規定電流である30mAでの点灯試験を行った。詳細な条件は下記に示した。測定項目としては、200時間点灯前後の照度を積分球を使用して測定し、試験用LEDの照度の保持率を算出した。
点灯詳細条件
発光波長:465nm
駆動方式:定電流方式、30mA(発光素子規定電流は30mA)
駆動環境:85℃、85%
評価:照度保持率 (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 | cure on predetermined hardening conditions. In the lighting test, a lighting test was performed at a specified current of 30 mA. Detailed conditions are shown below. As a measurement item, 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.
Detailed lighting conditions Light emission wavelength: 465nm
Drive system: constant current system, 30 mA (light emitting element specified current is 30 mA)
Driving environment: 85 ° C, 85%
Evaluation: Illuminance retention
なお、本出願は、2009年4月17日付で出願された日本特許出願(特願2009-100638)に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。 Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
The present application is based on a Japanese patent application (Japanese Patent Application No. 2009-1000063) filed on April 17, 2009, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.
Claims (5)
- 下記式(1)
(式中、複数存在するR、Pはそれぞれ独立して存在し、水素原子、もしくは炭素数1~15のアルキル基を表す。)
で表されることを特徴とするオレフィン樹脂。 Following formula (1)
(In the formula, a plurality of R and P are independently present and each represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms.)
The olefin resin characterized by being represented by these. - 請求項1に記載のオレフィン樹脂を酸化することにより得られることを特徴とするエポキシ樹脂。 An epoxy resin obtained by oxidizing the olefin resin according to claim 1.
- 過酸化水素または過酸を用いてエポキシ化されたことを特徴とする請求項2に記載のエポキシ樹脂。 The epoxy resin according to claim 2, which is epoxidized using hydrogen peroxide or peracid.
- 請求項2または3に記載のエポキシ樹脂と、硬化剤および/または硬化触媒とを含有することを特徴とする硬化性樹脂組成物。 A curable resin composition comprising the epoxy resin according to claim 2 and 3, a curing agent and / or a curing catalyst.
- 請求項4に記載の硬化性樹脂組成物を硬化してなることを特徴とする硬化物。 A cured product obtained by curing the curable resin composition according to claim 4.
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JP2011509369A JP5559154B2 (en) | 2009-04-17 | 2010-04-16 | Olefin resin, epoxy resin, curable resin composition and cured product thereof |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2011225711A (en) * | 2010-04-19 | 2011-11-10 | Nippon Kayaku Co Ltd | Method for producing epoxy resin, epoxy resin, and curable resin composition |
JP2013112649A (en) * | 2011-11-29 | 2013-06-10 | Showa Denko Kk | Method for producing multivalent glycidyl compound |
JP2015500468A (en) * | 2011-12-02 | 2015-01-05 | センスエア アーベーSenseair Ab | Epoxy molded gas cell and method for optical measurement |
WO2016119848A1 (en) * | 2015-01-29 | 2016-08-04 | Henkel Ag & Co. Kgaa | Method for the preparation of cycloaliphatic epoxy resins |
WO2018083881A1 (en) * | 2016-11-07 | 2018-05-11 | 昭和電工株式会社 | Method for producing polyvalent glycidyl compound |
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SG11201408155RA (en) * | 2012-06-07 | 2015-01-29 | Nippon Kayaku Kk | Epoxy resin composition and cured product thereof and curable resin composition |
CN103289326B (en) * | 2013-06-28 | 2015-10-07 | 山东科技大学 | For the halogen-free flame retardant epoxy resin composition of potting compound |
CN108649113A (en) * | 2018-04-28 | 2018-10-12 | 上海应用技术大学 | A kind of new application technique improving LED yields |
KR20210036119A (en) * | 2019-09-25 | 2021-04-02 | 주식회사 케이씨씨 | Powder coating composition |
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- 2010-04-16 WO PCT/JP2010/056869 patent/WO2010119960A1/en active Application Filing
- 2010-04-16 JP JP2011509369A patent/JP5559154B2/en not_active Expired - Fee Related
- 2010-04-16 CN CN201080016851.5A patent/CN102395555B/en not_active Expired - Fee Related
- 2010-04-16 KR KR1020117024431A patent/KR20120026035A/en not_active Application Discontinuation
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JPH05213919A (en) * | 1992-02-04 | 1993-08-24 | Tosoh Corp | Epoxidization of alicyclic olefin |
WO1998045349A2 (en) * | 1997-04-10 | 1998-10-15 | Sartomer Company, Inc. | Cycloaliphatic epoxides and the method for making the same |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2011225711A (en) * | 2010-04-19 | 2011-11-10 | Nippon Kayaku Co Ltd | Method for producing epoxy resin, epoxy resin, and curable resin composition |
JP2013112649A (en) * | 2011-11-29 | 2013-06-10 | Showa Denko Kk | Method for producing multivalent glycidyl compound |
JP2015500468A (en) * | 2011-12-02 | 2015-01-05 | センスエア アーベーSenseair Ab | Epoxy molded gas cell and method for optical measurement |
JP2018021938A (en) * | 2011-12-02 | 2018-02-08 | センスエア アーベーSenseair Ab | Epoxy molded gas cell for optical measurement and forming method |
WO2016119848A1 (en) * | 2015-01-29 | 2016-08-04 | Henkel Ag & Co. Kgaa | Method for the preparation of cycloaliphatic epoxy resins |
WO2018083881A1 (en) * | 2016-11-07 | 2018-05-11 | 昭和電工株式会社 | Method for producing polyvalent glycidyl compound |
JPWO2018083881A1 (en) * | 2016-11-07 | 2019-09-19 | 昭和電工株式会社 | Method for producing polyvalent glycidyl compound |
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CN102395555B (en) | 2015-01-21 |
TW201040203A (en) | 2010-11-16 |
TWI455949B (en) | 2014-10-11 |
KR20120026035A (en) | 2012-03-16 |
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JPWO2010119960A1 (en) | 2012-10-22 |
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