TW201038549A - Diolefin compound, epoxy resin and composition thereof - Google Patents

Abstract

Provided is a novel alicyclic epoxy resin which provides a cured material having excellent heat resistance, optical properties, and toughness. The epoxy resin comprises a diolefin compound represented by formula (1) as a starting material and is obtained by the epoxidation of the compound. In formula (1), a plurality of R's each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and P represents an alkylene group having 1 to 6 carbon atoms or a direct bond.

Description

201038549 VI. Description of the Invention: [Technical Field to Which the Invention Is Applicable] The present invention relates to a novel diene compound and epoxy resin suitable for use in electrical and electronic materials. [Prior Art]

Epoxy resin is hardened by using various hardeners, and is usually used as a hardener for 'water resistance, chemical resistance, heat resistance, electrical properties, etc.' for use in adhesives, coatings, laminates, Forming materials, sapphire materials, photoresist (4) a wide range of fields. In recent years, especially in the field of semiconductor-related materials, such as mobile phones with cameras, ultra-thin LCD or plasma TV (TV), lightweight notebook PCs, etc. Small electronic devices that become keywords, and therefore require very high characteristics for packaging materials represented by oxygen resins. In particular, the structure of the end package becomes complicated, and if it is not a liquid seal, it is difficult to increase the seal. For example, Enhanced BGA (Enhanced BaU (5) people, increase the ball grid array), etc., is formed as a concave area ((10) d_) type knot: those who need partial sealing, transfer molding can not cope. For this reason, the industry has demanded the development of a highly functional liquid epoxy resin. In addition, RTM (Resin Transfer (4) (8)) has been used in the J industry in recent years as a composite material, a car body or a ship structural material. In such a composition, it is easy to be impregnated with carbon fibers or the like, and it is expected to develop a low-viscosity epoxy resin. In addition, in the field of optoelectronics, especially with the recent capitalization, in order to smoothly transmit and process huge information, 201038549 kinds of filling tools using optical signals have been developed to replace the previous use of electric wiring. Signal transmission. Among them, in the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, it is desired to develop a resin material excellent in transparency. For these requirements, alicyclic epoxy compounds have received attention. The alicyclic epoxy compound is superior in electrical insulating properties and transparency to a glycidyl ether type epoxy compound, and thus is used as a material. However, in the field of high heat and light characteristics such as (10) use, an alicyclic epoxy compound which is further improved in heat resistance and light resistance is required (see Patent Documents 1 to 3). CITATION LIST Patent Literature Patent Literature 1: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] Optical Characteristics An object of the present invention is to provide a novel alicyclic epoxy resin which forms a cured product excellent in heat resistance and toughness. [Technical means for solving the problem] The present invention The present invention has completed the present invention in view of the results of the nine. That is, (1) a two-dilute combination of Yang said: The actual situation described above is studied. The present invention relates to: 'It is characterized by the following formula 201038549 (1) " π Where is the bamboo sap, indicating hydrogen progeny or an alkyl group having a carbon number of 1 to 6; in addition, ρ represents a carbon number of 丨~6 or a direct bond). % (2) An epoxy resin obtained by oxidizing the above (1) monoene compound. — (3) The epoxy resin according to (7) above, which is epoxidized using a peracid. (4) An epoxy resin composition comprising the epoxy resin and the curing agent and/or the curing catalyst according to any one of the above items (2) and (3). 〇

(5) A hardened material characterized by the above (4 resin composition is hardened. [Effect of the invention] The epoxy resin of Ltl can form mechanical properties (especially, the property) And the product b contains the hardening tree of the present invention (4), and the product can be effectively used for the second== [Embodiment] 201038549 The present invention relates to a feature of the following formula (丨):

An alkylene represented by hydrogenogen 6 (wherein R is present independently in the plural, and the alkyl group has an alkyl group having 1 to 6 carbon atoms. In addition, P represents a carbon number as a base or a direct bond) An epoxy resin obtained by epoxidation of a diene compound and a diene compound represented by the above formula (i) by oxidation can be obtained by a reaction of a derivative with a diol containing a cyclic acetal . As the hexanoic acid derivative, the following formula (2) can be cited

(In the formula, R in the plural is present independently, and represents a hydrogen atom or an alkyl group having a carbon number of 4 and 6. Further, X represents a hydroxyl group, and the carbon number is an alkoxy group or a halogen atom of the group 10) 201038549

Specific examples of the compound represented include cyclohexenecarboxylic acid, methyl cyclohexenecarboxylate, ethyl cyclohexene decanoate, propyl cyclohexenecarboxylate, butyl cyclohexenecarboxylate, and cyclohexenecarboxylic acid. Ester, cyclohexenecarboxylic acid (cyclohexenyl fluorenyl) vinegar, octyl cyclohexene carboxylic acid, cyclohexene methyl hydrazine chloride, cyclohexene methyl hydrazine, methyl cyclohexenecarboxylic acid, methyl cyclohexenecarboxylic acid Methyl ester, ethyl methylcyclohexylcarboxylate, propyl methylcyclohexenecarboxylate, methylcyclohexene decanoic acid (methylcyclohexenylmethyl) s, methylcyclohexene methyl hydrazine, etc. , but not limited to these. These may be used singly or in combination of two or more. Further, the above-mentioned ring-containing dilute fermentation can be obtained, for example, by a reaction of a triterpene-based hydrocarbon derivative with a hydroxyl group-containing carbon aldehyde. Examples of the trimethylol alkane derivative include trimethylolpropane, trimethylolethane, hydroxymethylethane, trimethylolbutane, and the like, but only three hydrogen atoms of the alkane are used. The compound substituted with a methylol group is not limited to these. These may be used alone or in combination of two or more. Further, the hydroxyl group-containing aldehyde is not particularly limited as long as it has a hydroxyl group and a fluorenyl group in its molecular structure. Wherein the group other than the hydroxyl group and the mercapto group is preferably a aliphatic alkyl group. Specific examples of the compound include, but are not limited to, methyl group, propionaldehyde, hydroxypivalaldehyde, and the like. : It can be used alone or in combination of two or more. Such a compound can be easily produced, for example, by an aldol reaction or the like. For example, if it is hydroxypivalaldehyde, it can be obtained by reacting isobutyric acid with formic acid (Japanese Patent Publication No. 2007-70339). For example, a reaction of a carbon aldehyde is known as a trihydroxydecyl alkane derivative and a conventional cyclic acetalization reaction using a base method, 201038549. Method: Toluene is used on one side of the reaction medium. A method in which a solvent such as xylene is subjected to azeotropic dehydration and a reaction is carried out (U.S. Patent No. 2,945,8), and a method in which a aldehyde is slowly added after dissolving a polyhydric alcohol in concentrated hydrochloric acid (Japanese Patent Laid-Open) Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei 7-215979 The method of the medium (Japanese Patent Laid-Open Publication No. 2007-230992) and the like.

As the reaction of the cyclohexenecarboxylic acid derivative with the cyclic acetal-containing diol, a usual esterification method can be employed. Specifically, a general esterification method can be employed, which can be exemplified by Fisher's esterification using an acid catalyst (esterification), acid halide and alcohol reaction under alkaline conditions, and various condensing agents. Condensation reaction, etc. (ADVANCEd 〇 RGANIC CHEMISTRY Part B: Reaction and Synthsis pl 35, 145-147, 151, etc.). Further, as a specific example, an esterification reaction of an alcohol with a carboxylic acid can be utilized (Tetrahedron v〇l. 36 ρ· 2409 (1980), Tetrahedron

Letter 4475 (1980)), in turn, can also utilize a transesterification reaction of a carboxylic acid ester (Japanese Patent Laid-Open No. 2006-052187). A preferred structure of the diene compound of the above formula (丨) synthesized in the above manner is preferably that in the above formula (1), r is a hydrogen atom, a fluorenyl group, an ethyl group or a butyl group, especially In the case where the substituent R is bonded to the olefin, in order to enhance the reactivity, R bonded to the olefin is preferably any of a hydrogen atom and a fluorenyl group, and particularly preferably a hydrogen atom. Since the substituent R directly bonded to the cyclic acetal deforms the structure of the cyclic acetal 201038549, the substituent R is preferably a methyl group, an ethyl group, a propyl group or the like. Further, in terms of easiness of obtaining raw materials on the market, it is preferred that the substituent r is ethyl. Among them, since the structure can be easily synthesized by the reaction of the equivalent of the thiophenone and the cytosine, it can be synthesized as needed (U.S. Patent No. 3,097,245). . The bond group Ρ is an alkylene group having a carbon number of 6, preferably a carbon number. The stretching base may be any of a linear chain, a branching shape or a ring shape. ο =, the main element of the structure system which acts on the properties of the final hardened material, preferably having a carbon number of 2 to 4. The bonding group ρ can also be directly bonded, and there is also a structure in which the structural instability is 2 to 6 and the stretching base 1 is too large (the carbon number exceeds 6), and the cured product cannot be maintained sufficiently. Heat resistance. 3 The olefinic compound of the present invention which is made by the above formula (1) can be oxidized by I:::::::::, One uses air (oxygen =::::: water-gas in the above. < 10,000, etc., but is not limited to the method of epoxidation using peracid, and this patent is open 2006_521 〇体吕, can be For example, the peracid used in β described in the Japanese Patent Publication No. 187旎, for example, can be used as a method. For example, formic acid, acetic acid, ', benzoic acid, m-chlorobenzoic acid, ortho-benzene: Sodium diacid anhydride. Among these, organic acids and the like* react with hydrogen peroxide to produce a female compound, reaction temperature, ease of operation, economy, etc. From the viewpoint of acetic acid, etc., the preferred ortho-dicarboxylic acid needle is more preferably used in view of the simplicity of the reaction operation 201038549. Or 酉 酉 酉 酉 酉 酉 酉 酉 酉 过 过 过 过 过 过 过 过 过 过 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 Kaiping 5-213919 No. #昭62_23 伽号公^49579号*, Japanese Patent Special Fair ι, Japanese Patent Unexamined Patent Special Open 2001_17864, 曰:唬 曰, 曰本公告, etc. 和特公平3-57102 No. 例 例 用于 用于 用于 用于 用于 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢The polyacid used in the present invention is not particularly limited as long as it has a polymer, and is more preferably a polyacid containing f (tetra) of tungsten, more preferably a polyacid of tungsten, and particularly preferably a tungstate. The acid of the specific polyacid and polyacid salt contained in the polyacid, tungstic acid, 1 2-tungstophosphoric acid, j 2 Kai +, etc., selected from the group consisting of _^ dish acid and 12_heshixi acid Salt, etc., molybdenum-based acid from steel acid and phosphorus acid, and the like Examples of the counter cation include a genus ion, a metal ion, etc. Alkaline earth metal ions such as calcium ions and magnesium ions, and alkali metal ions such as sodium, potassium, and cesium are stagnation of a counter ion as a sodium ion. The early use of potassium ions, dance ions, ammonium ions. The use of polyacids relative to the dilute compound of the present invention 1 Mo, 10 201038549 converted to metal ruthenium (if tungstic acid, then Taking the tungsten atom as the indium acid, the number of moles of the I mesh atom is 1〇~2〇 if it is 2.0~2. Milligram, more preferably 25~1〇 millim, ear As a quaternary ammonium salt, it is preferred to use a total carbon number of 10 or more. Dry: 25 to a quaternary ammonium salt.

Specific examples thereof include: trimethylmethylammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl& (alkyl group is an octyl group: a compound and an alkyl group are Mixed type of sulfhydryl compound) ammonium salt, tris(hexadecyl) decyl ammonium salt, tridecyl octadecyl ammonium salt, tetraamyl ammonium salt, cetyl trimethyl ketone salt The tributylammonium salt, the dimercapto dimethyl ketone salt, the lanthanide-based benzylamine di(hydrogenated tallow alkyl) dimethylammonium salt, and the like are not limited thereto. It is especially good for those with a carbon number of 25~1. Further, the anion source of the salt is not particularly limited, and specific examples thereof include a tooth ion, a nitrate ion, a sulfate ion, a hydrogen sulfate ion, an acetate ion, and a carbonate ion, but are not limited thereto. In these. When the carbon number of the quaternary ammonium salt exceeds 1 Torr, the hydrophobicity becomes too strong, and the solubility of the quaternary salt in the organic layer deteriorates. When the carbon number is less than 10, the hydrophilicity becomes strong, and similarly, the compatibility of the quaternary ammonium salt with the organic layer is deteriorated, which is not preferable. The amount of the quaternary ammonium salt used is preferably 价. 〇1 to 0.8 times equivalent or 1.1 to 10 times equivalent of the valence of the tungstic acid used. More preferably, it is 〇〇5~〇·7 times when it is or 1.2~6.0 times equivalent, and more preferably 〇5~〇 5 times equivalent or 13~4.5 times equivalent. 201038549 For example, if it is streptoic acid, it is 4 n & acid 1 苴 and Beihong H2W 〇 4 and is divalent, so the quaternary ammonium tartrate is preferably 0 02~ relative to tungstic acid 1 mol. 16 Mo Erhe 20 Mo Er range. In addition, if it is a taurine, it is trivalent, so ^: the carboxylic acid salt of the quaternary ammonium is preferably 0.03 to 2.4 mol or 3·3 to 3: the right is the tetravalent, so the tetravalent is The fourth-grade money tickrate is preferably ~3.2 moles or 4.4 to 40 moles. Any buffer may be used, and in the present reaction, an aqueous solution of a discate is preferably used. As the pH, it is preferably adjusted to a pH of between 4 and 5, more preferably a pH of 5 to 9. When the pH is less than 4, the epoxy group is easily subjected to a hydrolysis reaction or a polymerization reaction. In addition, when the pH exceeds 1 Torr, the reaction becomes extremely slow and the reaction time is too long. Particularly in the present invention, when the tungstic acid as a catalyst is dissolved, it is preferred to adjust the pH to between 5 and 9. The method of using the buffer may be exemplified by, for example, when using an aqueous solution of a linonic acid-phosphate as a preferred buffer, using 0.1 to 10 moles of acid (or squaric acid) relative to ruthenium peroxide. Sodium hydrogenate is used as the acid salt), and the pΗ value is adjusted by using a basic compound (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, acid arsenic, and niacin clock). Here, it is preferred to add so as to bring the pH to the above-described pH value when hydrogen peroxide is added. Further, it can also be adjusted using sodium dihydrogen phosphate or disodium hydrogen phosphate. The concentration of the preferred phosphate is 〇 1 to 60% by weight, more preferably 5 to 45% by weight. Further, in the present reaction, a buffer solution may not be used, and a phosphate such as disodium hydrogen phosphate, sodium dihydrogen phosphate 'sodium phosphate or sodium tripolyphosphate (or a hydrate thereof) may be directly added without adjusting the pH. In terms of the simplification of the steps, 12 201038549 is especially added directly for the trouble of no PH adjustment. The amount of phosphate used at this time is usually (M to 5 mol% equivalent) with respect to hydrogen peroxide, preferably 〇2 to 4 mol% equivalent, more preferably 〇3 to 3 mol% equivalent. If the amount of phosphate used is more than 5 mol% equivalent, it is necessary to adjust the value of 'in the case of not reaching the amount of Mo%%#, the resulting % of the latex is easily hydrolyzed. The reaction is slow or the reaction is slow. The reaction is epoxidized using hydrogen peroxide. As the dihydrogen peroxide used in the present reaction, the ease of use is preferably hydrogen peroxide/initiality. An aqueous solution having a concentration of 10 to 40% by weight. In the case where the concentration exceeds 4 Å, it is difficult to use it, and the resulting epoxy resin is easily decomposed, which is not preferable. The reaction uses an organic solvent. The amount of the organic solvent to be used is preferably in the weight ratio of the dilute compound i as the reaction substrate, more preferably (1) to 仏 in the ratio by weight of the organic solvent W. In the case of 1G, the progress of the reaction becomes extremely slow, so it is not Specific examples of the organic solvent that can be used include: burned tobaccos such as hexagram, cyclohexine, and heptane, aromatic smoke compounds such as toluene and diphenylbenzene, methanol, ethanol, isopropanol, and butanol. An alcohol such as hexanol or cyclohexanol. Alternatively, a ketone such as methyl ethyl 1 isopropyl ketone, cyclohexanone or cyclohexanone may be used, and diethyl ether, an acute 00 fufu, and a ketone may be used. σ, such as stagnation, acetal acetate, acetic acid, vinegar, vinegar, etc., etc. It is a compound, hydrogen peroxide (aqueous solution), heteropolymer (catalyst), buffer, quaternary ammonium salt and organic solvent, and is stirred with two layers of 13 201038549. The stirring speed is not specified. Due to the addition of hydrogen peroxide Although there are many cases of heat generation, it is also possible to use a method of slowly adding hydrogen peroxide after adding each component. The reaction temperature is not particularly limited, and is preferably 〇~9〇t, more preferably 〇~75 C, Good for 15 ° C ~ 6 〇〇 C. When the reaction temperature is too high, the hydrolysis reaction is easy, and if the reaction temperature is low, the reaction rate becomes extremely slow. In addition, the reaction time is also determined by the reaction temperature, the amount of catalyst, etc., but from the viewpoint of industrial production. Since the long-term reaction consumes a large amount of energy, it is not preferable. The preferred range is hourly, preferably SI hour, more preferably 4 to 24 hours. After the end, the excess hydrogen peroxide is quenched. The quenching is preferably carried out using a basic compound. Further, a reducing agent and an inspective compound are preferably used in combination. As a preferred treatment method, the neutralization of the pH is adjusted to 6 to 1 by using a compound: After that, the method of reduction === hydrogen feed cold is used. When the pH value is less than 6, the energy is still excessive, and the excess heat is generated when the hydrogen is heard, and the decomposition product is generated as a reducing agent.丨 和. Sodium sulfite, sodium thiosulfate, 肼 3夂, vitamin C, etc. As a helmet, I have a hydrogen peroxide/material, relative to over. ·. ...Γ, usually 0. 01~20 times Molar, more preferably; U ear' is further preferably GG5~3 times Mo. As an organic compound,

Gasification money... 歹 举 举 虱 虱 虱 虱 虱 、 、 虱 虱 虱 虱 虱 虱 虱 虱 虱 虱 虱 虱 虱 虱 虱 虱 虱 虱 虱 虱 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属, sodium sulphate, sodium sulphate and other sulphates, ion exchange resins, alumina and other alkaline solids. When the amount of the test compound is used, the test compound is dissolved in water or an organic solvent (for example, an aromatic hydrocarbon such as toluene or xylene, or a ketone such as methyl isobutyl ketone or methyl ethyl ketone; , Geng appearance, Xin Shao, etc., various solvents such as methanol, ethanol, isopropanol, etc.), the amount of molybdenum used in excess of hydrogen peroxide is usually 001 to 20 times moles. Ο Ο 々, lend the ear and then better 0.05 to 3 times the mole. These may be added as a solution of water or the above organic solvent, or may be added as a monomer. In the case of using a solid solution insoluble in water or an organic solvent, the amount of hydrogen peroxide in the system is preferably a solid amount of ~1 〇〇〇 times the amount by weight relative to the amount of hydrogen peroxide remaining in the system. The 舜乂土达 is preferably 10 to 500 times, and more preferably 2 to 300 times. In the case of using a solid solution insoluble in water or an organic solvent, it may be treated after separation of the aqueous layer and the organic layer described in τ. After quenching of hydrogen peroxide (or before quenching), at this time, if == is not separated or no organic solvent is used, the organic solvent τ aqueous layer is added to extract the reaction product. The organic solvent used at this time is 0.5 to 10 times more than the raw material diene compound, and more preferably, the organic layer is separated after several times of the operation, and the organic layer is separated as needed. The layer was washed with water and purified. Oxygen Lt household ^ obtained organic layer, if necessary, using ion exchange resin or Jin Tejia as a wonderful glue or oxidation, etc.), activated carbon (which makes, especially chemically activated carbon), composite metal salt (including Good for the test 15 201038549 composite metal salt), clay minerals (of which V 肀 肀, especially good for montmorillonite, etc.

The earth minerals and the like are removed from the impurities, and after the layered layer W is further subjected to water washing and filtration, the solvent is removed to obtain an oxygen compound as a target of ',, 'q. Purification may also be carried out by column chromatography or distillation, as the case may be. The epoxy resin of the present invention obtained in the above manner is of the formula (3):

(3) In the formula, the plural R-forms exist independently, and represent a hydrogen atom or an alkyl group having a carbon number of *1 to 6. Further, 'P represents a stretched alkyl group having a carbon number of 1 to 6 or a direct bond. The structure represented by the main structure is a main structure, and the mixture is represented by the formula (4): [Chemical 5] 16 201038549 Ο

(In the formula, the combination of (A) to (D) may be any combination. Further, R and P represent compounds of various structures which are not the same as those of the ruler and the formula (3). Further, depending on the reaction conditions, a high molecular weight body or other side reactant in which epoxy groups are polymerized with each other may be formed. The obtained epoxy resin can be used, for example, as various resin raw materials such as an epoxy acrylate and a derivative thereof, an acridone compound or a cyclic carbonate compound. Hereinafter, the curable resin composition of the present invention containing the epoxy resin of the present invention will be disclosed. The curable resin composition of the present invention contains the epoxy resin of the present invention as an essential component. The curable resin composition of the present invention can be applied by two methods of thermal curing (curable resin composition A) using a curing agent and cation curing (curable resin composition B) using an acid as a curing catalyst. 17 201038549 In the curable resin composition A and the curable group resin product B, the epoxy resin of the present invention can be used alone or in combination with other epoxy resins to form the If shape in combination. The proportion of the oxygen resin in the total epoxy resin is preferably 3% by weight or more, and particularly preferably the weight. More than one. In the case where the epoxy resin of the present invention is used as a modifier for the curable resin composition, it is added in a proportion of 1 to 3 % by weight. As another epoxy resin which can be used together with the epoxy resin of the present invention, it can be used as a phenolic phenolic lacquer type oxy-resin, bisphenol A type epoxy resin, biphenyl type 曰-phenylmethane type epoxy resin, phenol aryl Alkyl epoxy resin: Specifically, it can be exemplified by: double a, double 酴 (four) generation two years old, the first double, shouting two, M'-biphenol, 2,2'-biphenyl, biphenyl]m-phenyldihydroxyphenyl ) A burn, a (burning base substituted benzene, ',: diphenyl) E-house '(Benzene, naphthalene, etc.) and A plate, E knee, benzene; Γ 基 、, 二 经 基 基_B_,::; benzoquinone, · bis (gas methyl) _", dragon 4 Ben _, one% pentadiene, system, Μ 甲基 methyl) benzene modified substance, four 淳 double "etc. Polycondensate of benzene and the like, and such glycerin oxime, 4 self-forming bisphenols, condensed from alcohols, alicyclic epoxy resin, glycidylamine epoxy resin, glycidyl s Epoxy resin, halved ♦ oxygen r-based epoxy # 曰 ring, ladder or these... > Oxane 糸 氧 树 曰 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( An epoxy resin such as a solid or liquid epoxy dioxime or an epoxycyclohexanyl structure, which is not limited thereto. 18 201038549 In particular, the curable resin composition of the present invention For optical applications Preferably, the epoxy resin of the present invention is used in combination with an alicyclic epoxy resin or an epoxidized epoxy resin having a sesquiter-oxygen structure. Especially in the case of using an alicyclic epoxy resin, it is preferably The ruthenium having an epoxy ring-like structure in the skeleton is particularly preferably an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure. As an epoxy resin, it can be cited as Oxidation of sigma oxidized by the following reaction: vinegar reaction of cyclohexyl acid and alcohol or vinegarization of cyclohexene methanol and lysine (Μ-magnetic period (1_), Tetrahed_Leuerp 4475 (measured), etc.), or cycloheximic acid reflexology reaction (tishchenk〇tl〇I1) (Japanese Patent Laid-Open No. 2003-170059, Japanese Patent carboxy = 〇 04-262871 The method described in the gazette and the like, and the vinegar exchange reaction of cyclohexene (the method of the present invention is as follows): 〇 作 作 〇 : 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Is a compound having an alcoholic base group, such as lake butanediol, π pentanediol, hydrazine 31, 1,2· Alcohol, alcohol, glycerol, Sanjingjiaxiaoyi, Guangjidiol, Huanjiyuan Dimethanol, etc., Dibutyl, 2, Methyl-methylpropane, Tri-methyl, etc. Acids, such as tetraols such as pentaerythritol, phthalic acid, phthalic acid, chlorhexidine, cis-butane diacid, anti-f acid, etc. 'but are not limited thereto. - Formic acid, adipic acid, ring Further, the calcined product may be exemplified by the acetal compound formed by the reaction of cyclohexanthene derivative with an alcohol. The reaction method can be produced by applying a usual acetalization reaction, for example. It is revealed that the right sentence does not have the following method: a method in which a reaction is carried out by using toluene, dimethylhydrazine, ruthenium ruthenium, ruthenium 4, and a mixture in a reaction medium (US Patent No. 2945008 \ , ^ 08) In the method of dissolving a polyhydric alcohol in concentrated hydrochloric acid, a method of slowly adding an aldehyde-m-side enthalpy reaction (Japanese Patent Laid-Open No. 48-96590, Gong Hao, . ) US Patent No. 3092640) m) using an organic solvent as a reaction medium The method (Japanese Patent Publication No. 7 千 7 7-7丨5979), a method of using a solid acid catalyst (Japanese Patent No. 2007-230992). In terms of the stability of the structure, it is a % acetal structure. As a representative of the special epoxy resin, a "" system" can be cited as: ERL_4221, UVR-6105, ERL-4299 (All-Jiu helmet σ *, Ρ为商οσ名' are all manufactured by Dow Chemical) ' celloxlde 2021P, Ερ〇1_ gt4〇i, EHpE 3i5〇, ^HPE 315GCE (all are trade names, all made by the chemical industry: 〇 and ί 一 一 稀 稀 j j 衣 衣 ' ' ' ' ' ' ' ' ' ' Etc. (Reference: General Epoxy Resin Basics Ιρ76 85). These may be used singly or in combination of two or more. In addition, a sesquiterpene oxide epoxy resin (in chain or ring shape) is added. Solid or liquid lyohydric resin such as epoxy resin with a mixture structure of two or more types of oxy-and agglomerated structure and/or epoxy ring-fired structure) Each of the curable resin compositions will be described below. The heat curing (curable resin composition Α) by the curing agent is used as the curing agent contained in the curable resin composition of the present invention, 20 201038549 ❹ Ο Amine compound, acid anhydride compound, guanamine compound And a compound, a citric acid-based compound, etc. As a specific example of a hardener which can be used, exemplified. Diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, amine-phenyl-alloy, and different Buddha Ketone diamine, dicyanodiamine, polyamido resin synthesized from a polymer of threitol oleic acid and ethylenediamine, phthalic acid, trimellitic acid, anhydride, pyromellitic acid Anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylic acid anhydride, ceric anhydride, hexahydrophthalic anhydride, methylhexahydroortylene Diacetic anhydride, pentylene & C anhydride, bismuth [2,2,1]heptane 2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptadicarboxylic acid liver, Cyclohexanetricarboxylic acid _3,4_ dianhydride, bisphenol quinone, bisphenol F, bisphenol s, shuangling, Zhuang Erling, 4,4, _biphenyl age, ::2: 'benzene, 3,3 ,,5,tetramethyl-[U,-biphenylenediol, p-benzidine, m-benzoic acid, naphthalene di-presence, tris(4-cyanophenyl)-methyl, 1,1,2,2 -tetrakis(4-predylphenyl)ethene, (iv) (benzene, alkyl substituted (tetra), (iv), : substituted naphthol, dihydroxy stupid, dihydroxy Naphthalene, acetaldehyde, benzofuraldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-benzyl ethyl ketone, dicyclopentadiene, hydrazine, 4, 4 , _ bis (gas methyl) q polybiphenyl, M,-bis (methoxymethyl)], biphenyl, gas methyl) benzene, K bis (decyloxy fluorenyl) benzene and other polycondensates These modified substances, such as bisphenol hydrazine and other dentate double-conceived, taste saliva, three gas-burning-amine complex, pulse derivative, condensate of terpene and phenol, etc., but not limited to These may be used alone or in combination of two or more. In the present invention, a compound having an acid anhydride structure and/or a diacid structure represented by the above acid anhydride or a slow acid resin is particularly preferred. 21 201038549 As a compound having an acid anhydride structure, it is preferably methyltetraphthalic phthalic anhydride, methylic acid anhydride, ceric anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Butane tetracarboxylic anhydride, bicyclo[^丨]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexane 1'3, 4-Dicarboxylic acid _3,4- dianhydride, etc., particularly preferably decyl hexahydrophthalic anhydride or decane-1,3,4-tricarboxylic acid-3,4-dianhydride. From the viewpoint of improving hardness, insulation, heat resistance, or imparting high transparency, it is preferred to use a compound having an acid anhydride structure as a curing agent. It is preferably a compound having a carboxylic acid structure (hereinafter referred to as a polycarboxylic acid), a polytetracarboxylic acid having a 2:4 functional group, and more preferably an addition reaction of a γ-alcohol with an acid anhydride by a 2-4 function. And the polycarboxylic acid obtained. In the case where the volatilization of the hardener S ′ is hard to produce hardening m and it is easy to obtain a composition having a strong stagnation, it is preferred to use a polycarboxylic acid as a hardener. The 2 to 4 functional polyol is not particularly limited as long as it is an alcoholic hydroxyl group, and examples thereof include ethylene glycol, propylene glycol, and i, 3-propane dimer: 2 methylbutanediol and K Glycol, "5 · pentanedialdehyde, 1, hexane diol, , 疋 甲醇 methanol, 2,4-diethyl pentanediol, alcohol, Xinyet ethyl-2-butyl-1,3- Propylene di-tri-acid triol, tricycloanthracene dimethanol, norbornene diol, etc. diols 2-hydroxymethyl--mercaptoethane, trishydroxypropyl propane, trishydroxybutane, hydrazine, etc. Triols such as butanediol, pentaerythritol, di-trimethylolwo I tetraol, etc. 'Specially good pentanediol, calcined dimethanol, 2~4 functional polyol is cyclohexane dimethanol, 2 a branched or cyclic alcohol such as 4_diethyl 2-ethyl-2·butyl-; i'3-propanediol, neodecanediol, tricyclic indene norbornene glycol. 22 201038549 Acid acid in the case of poly-acidification, preferably methyltetrahydro-butanol::: methyl glutinous acid oxuan, Caidi acid porphyrin, six gas phthalic acid porphyrin, a ^ ^ tetracarboxylic anhydride, double ring [训庚烧#: Formic acid, methyl double ring [Xun Geng ^... Worker, 3,4-dicarboxylic acid-3,4-II ., Etc. As the addition reaction conditions, is not particularly specified as one of the specific types of reactive conditions, in the catalyst-free, solvent-free under the conditions - to face 4〇~

The method of reacting the acid liver with the polyol at 15 ° C and heating-side, and directly taking out after the reaction is completed. However, 'it is not limited to the reaction conditions. The acid anhydride and the polyphenolic acid may be used singly or in combination of two or more. In this case, the ratio of the acid field to the poly(iv) is 90/10 to 20/80 Å by weight ratio 80/20 to 30/70. In the curable resin composition A of the present invention, the curing agent is preferably used in an amount of from 0.5 to 1.5 equivalents based on the functional group equivalents based on the epoxy group equivalent of the epoxy resin. Preferably, it is (^~丨丨 equivalent, particularly preferably 〇8~1〇 equivalent. When it is less than 0.5 equivalents or more than 1.5 equivalents with respect to 1 equivalent of epoxy group, hardening is incomplete and cannot be obtained. In the curable resin composition A of the present invention, a curing accelerator may be used together with the curing agent. Specific examples of the curing accelerator which can be used include 2-methylimidazole. , 2-phenylimidazole, 2- Η"-alkylimidazole, 2-heptadecanylimidazole, 2-phenyl-4-f-imidazole, 1-pyryl-2-phenylimidazole, 1-block -2-methylimidazole, hydrazine-cyanoethyl-2-methylimidazole, hydrazine-cyanoethyl-2-phenyl sulphate, 1-cyanoethyl-2-undecylimidazole, 2,4_ Diamino _6_(2,_methyl meth 23 201038549 oxazole (1,)) ethyl-s-triazine, 2,4·diamino-6-(2·-undecylimidazole (Γ)) Ethyl-s-triazine, 2,4-diamino-6-(2'-ethyl-4-methyl-°°[()) ethyl-s-triazine, 2,4-diamino -6-(2i-methyl-flavored. Sit (1')) ethyl-s-trimethylene-iso-cyanuric acid adduct, 2-methyl-methyl 11 m olfactory isocyanuric acid 2. 3 addition , 2-phenyl-paste. Sit-isotrimeric gas acid adduct, 2_bens_3,5_-methyl methine, 2-phenyl-4-hydroxymethyl-5-methyl 15 Various imidazoles of thiazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the imidazoles and phthalic acid, isophthalic acid, and para-benzene a salt of a polycarboxylic acid such as dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, maleic acid or oxalic acid, or a guanamine such as dicyanodiamine, 1,8- ..... - a compound of the stagnation state and such salts as tetraphenylborate or phenol novolac, and salts of the above polycarboxylic acids or phosphinic acids, tetrabutyl bromide Base, ammonium cyanide trimethyl sulfonate, trioctylmethyl ammonium bromide, triphenylphosphine, tris(phenylphenyl)phosphine, tetraphenyl bromide, tetraphenylboronic acid Phosphine or scaly compound such as tetraphenyl scale, phenol such as 2,4,6-triaminomethyl phenol, amine adduct, carboxylic acid (zinc 2-ethylhexanoate, zinc stearate, Twenty-two acid words, nutmeg zinc citrate), phosphate vinegar words (phosphoric acid zinc citrate, octadecyl phosphate, etc.) and other zinc a compound such as a tin compound such as tin octylate, various metal compounds, and the like, and a microcapsule-type hardening accelerator obtained by microencapsulating the curing accelerator, etc. Which one of the curing accelerators is used is, for example, transparent Sex, hardening speed or working conditions are suitable for the characteristics required by the resin composition of the phase to be renewed. It is better to use it in comparison with the lesser color. The hardening resin composition A of the present invention may also contain a phosphorus-containing compound as a flame retardancy imparting component. The hardening resin composition A of the present invention may also be used as a flame retardancy imparting component. As the phosphorus-containing compound, it may be a reaction type scaly compound or an addition type phosphorus-containing compound. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate 'tricresyl linoleate, tris(phenylene) phenyl phosphate, decyl phenyl diphenyl phosphate, and phenyl phenyl phosphate- 2,6-bis(xylene) vinegar, 13-phenylene bis(phosphine di(dimethylbenzene) vinegar), M-phenylene bis(bis(xylene) vinegar), 4,4, _ Phosphate such as phenyl (2-(toluene) ester); 9,1 〇_dihydro_9_oxa-1〇_phosphaphenanthrene 〇_oxide, 10-(2,5 a phosphine such as -dihydroxyphenyl)-i〇H-9-oxa-10-phosphaphenanthrene-10-oxide; a phosphorus-containing epoxy obtained by reacting an epoxy resin with an active hydrogen of the above phosphine The compound 'red phosphorus, etc., preferably a phosphate ester, a phosphine or a phosphorus-containing epoxy compound, particularly preferably ruthenium, 3_phenylene bis(bis(diphenylene) vinegar), M-phenylene Double (di(xylylene) vinegar), 4,4, _biphenyl (linic acid) or filled with an oxygen compound. The content of the compound containing the filler is preferably 'phosphorus compound /All epoxy resin = () 1 ~ 〇 6 (weight ratio). Q Right less than 0.1, flame retardant If it is less than 〇6, it may adversely affect the hygroscopicity and dielectric properties of the cured product. Further, if necessary, a binder resin may be blended in the curable resin composition A of the present invention. Examples thereof include a butyraldehyde resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, a NBR (acrylonitrile nitriie-butadiene rubber) phenol resin, an epoxy-NBR resin, and a polyamine. The resin, the polyimide resin, the polyoxymethylene resin, and the like are not limited thereto. 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. The amount of the fat component is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the tree 25 201038549. If necessary, an inorganic filler may be added to the curable resin composition A of the present invention. As the inorganic filler, there may be mentioned, for example, crystalline cerium oxide, molten sulphur dioxide, oxidized smear, smectite, ashes, carbonic acid, carbonized stone, tantalum nitride, boron nitride, cerium oxide, Magnesium sapphire The talc, the spinel, the powder of the titanium oxide π sarcophagus, or the spheroidized beads, etc., are not limited thereto. These may be used singly or in combination of two or more. The content of the inorganic filler may be 〇 to 95% by weight based on the sclerosing resin composition of the present invention. Further, a decane coupling agent may be added to the curable sap composition A of the present invention. a release agent such as stearic acid, palmitic acid, zinc stearate or calcium stearate, various compounding agents such as pigments, and various thermosetting resins. The curable resin composition A of the present invention is used for an optical material. In particular, in the case of a photo-semiconductor encapsulant, by using a nano-sized filler as the particle diameter of the inorganic filler to be used, it is possible to prevent transparency, grounding, strong mechanical strength, and the like. As a standard of the nanometer level, in terms of transparency, it is preferred to use a filler having an average particle diameter of 5 Å nm or less, particularly an average particle diameter of 200 nm or less. When the curable resin composition A of the present invention is used for an optical material, particularly a calendered semiconductor encapsulant, a phosphor may be added as needed. The phosphor is, for example, a person who absorbs a portion of the blue light emitted from the blue LED element and emits wavelength-converted yellow light, thereby forming white light. The phosphor is previously dispersed in the curable resin composition and then sealed. The phosphor is not particularly limited, and a conventionally known phosphor can be used, and examples thereof include an aluminate of a rare earth element, a thiogallate, a raw acid salt, and the like. More specifically, YAG (yttrium aluminum garnet) phosphor, TAG (terbium aluminum garnet) phosphor, orthosilicate phosphor, thiogallate A phosphor such as a salt or a sulfide illuminant, and can be exemplified by: YA103: Ce, Y3Al5〇12: Ce, Y4Al2〇9: Ce, Y2〇2S: Eu, Sr5(P04)3Cl: EU, (SrEu ) 0-Al203 and the like. As the particles of the above-mentioned phosphor, the particle diameter f) can be a particle diameter known in the art, and an average particle diameter of 1 to 2 5 0 y m' is particularly preferably 2 to 50 em. In the case of using these phosphors, the amount thereof is preferably from 1 to 8 parts by weight, preferably from 5 to 60 parts by weight, per part by weight of the resin component.

When the curable resin composition A of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, in order to prevent precipitation of various phosphors upon hardening, fine powder of cerium oxide (also referred to as Aerosil) may be added. Or Ae_l) is a representative thixotropy imparting agent. Examples of such a fine powder of the silica fine powder include: Aerosil 5〇, Aer〇sil 9〇, Aer〇sii i3〇, A for fi 2〇〇> Aerosil 300 , Aerosil 380 . AerosU 0X50 ^ Aerosil TT600 ^ Aerosil R972 ^ Aerosil R974 ^ Aerosil R202 ^ Aerosil

Aerosil R812S ^ Aerosil R8〇5 ^ RY200 > RX2〇〇 (a manufactured by Aerosil) and others. In the case of an optical material, particularly a photo-semiconductor sealant, A (4) 1 In order to prevent coloring, an amine compound which is a first stabilizer and a phosphorus compound which is an antioxidant may be contained. 27 201038549 or a variety of compounds. As the above amine compound, 如 』 can be exemplified by: tetrakis(1,2,2,6,6-penta-4-piperidinyl)=: 1,2,3,4_uh,,, T & a certain U 7 1 λ carbamate, tetrakis(2,2,6,6-tetradecyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, 1,2, 3,4-butane tetradecanoic acid and 1,2,2,6,6-pentamethyl-4-piperidin, alcohol and 3,9-bis(2-hydroxy-1,1-didecyl Mixed) ester of 2,4,8,1〇-tetraoxaspiro", L"undecane, adipic acid bis(2,2,6,6-tetradecyl_4_piperazin I Azelaic acid ester, bis(budecyloxy-2,2,6,6-tetramethylhydrazine, butyl, & 4-yl) 3⁄4 acid ester, methacrylic acid 2, 2, 6 ,6-tetramethyl-4-piperidinyl ester, bis(2 叉^^,6,6-tetramethyl-4(piperidinyl) sebacate, bis (, '2, 6, 6 Pentamethyl-4-piperidinyl) sebacate, 4-benzophenoxy 2,2,6,6-tetradecylpyridine, 1[2_[3·(3,5二third Butyl-4, propyloxy)ethyl]-4-[3-(3,5-di-t-butyl-4-yl-phenylphenyl)propanyloxy]_2,2 , Μ _ 曱 曱 ° ° base, methacrylic acid -1,2,2,6,6-pentamethyl _4_ 0 bottom bite vinegar 'double (1,2,2,6,6-five 4--4-piperidinyl)[[3,5-bis(1,1-didecylethyl)-4-ylphenyl]indolyl]butylmalonate, azelaic acid bis(2 , 2,6,6-tetramethyl-indole-(octyloxy)_4_piperidinyl) ester, the reaction product of dimercaptoethyl hydroperoxide with octane, N, N,, N", N ",_4 (4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidine-4-yl)amino)triazin-2-yl)_4,7 -diazepine-1,10-diamine, dibutylamine-H5.triazine_Ν,Ν,_bis(2,2,6,6-tetramethyl-4-piperidinyl-l, Polycondensate of 6-hexanediamine and ν-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, poly[[6-(1,1,3,3-tetramethyl) Alkyl butyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetradecyl-4-branched alkyl)imido]hexamethylene Dimethyl [(2,2,6,6-tetradecyl-4-piperidyl)imido]]' succinate and 4-hydroxy-2,2,6,6-tetramethyl-1 - polymer of piperidine ethanol, 2,2,4,4-tetramethyl 28 201038549 -20-(cold-lauric oxycarbonyl)ethyl_7_oxa-3,2〇-diaza snail [5. 丄. U·2] hexadecane-21-ketone, no. Alanine, Ν·(2,2,6,6-tetramethyl-4-piperidyl)-undecyl ester /Tetradecyl Ester, oxime-ethenyl_3_dodecyl-1-(2,2,6,6-tetramethyl-4(piperidinyl)pyrrolidine-2,5-dione, 2,2, 4,4_tetradecyl-7-oxa-3,20-diazaspiro[5,1,11,2]icosane-21-one, 2,2,4,4-tetramethyl Base_21_oxa-3,2〇-diazabicyclohexadecane-2-indole propanoic acid dodecyl ester/tetradecyl ester, malonic acid [(4-methoxybenzene) ◎ base) fluorenyl]-bis (1,2,2,6,6-pentamethyl_4_0 bottom bite) 黯, advanced 2,2,6,6-tetramethyl-4-piperidinol Fatty acid esters, hydrazine, 3 - phthalimide, N, N, _ bis (2, 2, 6, 6-tetradecyl _4 - benzyl group) and other hindered amines, diphenyls such as octyl ketone Formamidine compound, 2-(2H_benzotriazol-2-yl^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ [2_经基_3_(3, 〇tetrahydrophthalene imine _methyl)_5_nonylphenyl]benzotriazole, tert-butyl-2-hydroxy_5_methyl stupid _5_Chlorobenzotriazole, 2(2-hydroxy-3,5-di-t-pentylphenyl)benzotriazole, methyl_3_(3_(2η_benzotriazole_2 〇 Reaction product of 5-)-tert-butyl-4-hydroxyphenyl)propionate with polyethylene glycol, 2-UH-benzene三嗤_2_基)_612院基_4_Methylbenzene and other benzotriazine compounds '2,4-di-t-butylphenyl-3-3,5-di-t-butyl _4_hydroxybenzoic acid is a benzoic acid series, a triazine compound such as ruthenium (4,6-diphenyltriazine-2-yl)-5-[(hexyl)oxy]phenol, etc. Amine compound. As the above amine compound as a photostabilizer, the following products can be used. The commercially available amine-based compound is not particularly limited, and is commercially available as, for example, TINOVIN765, TINUVIN770DF, TINUVIN144, TINUVIN123, TINUVIN622LD, TINUVIN152, CHIMASSORB944, as a commercially available product of the company.

A commercially available product manufactured by Adeka is exemplified by la_52, LA·, LA_62, LA-63P, LA-77Y, LA-81, LA-82, LA-87, etc. The phosphorus compound is not particularly limited. For example, 1'1,3-tris(2-mercapto-4-di-tridecylphosphite_5_t-butylphenyl)butane, dioctadecylpentaerythritol diphosphoric acid Ester, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite 'bis(2,6 di-t-butyl-4-methylphenyl)pentaerythritol diphosphite 'phenyl bisphenol A pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, tris(diethylphenyl) phosphite, tris(di-isopropylphenyl)phosphite, tris(di-n-butylbenzene) Phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(2,6-di-t-butylphenyl)phosphite, tris(2,6- Di-t-butylphenyl)phosphite, 2,2'-fluorenylene bis(4,6-di-t-butylphenyl) (2,4 di-t-butylphenyl) Phosphate, 2,2,-methylenebis(4,6-di-t-butylphenyl) (2-tert-butyl-4-methylphenyl) Phosphate, 2,2,-methylenebis(4-decylt-butylphenyl)(2-secondyl-4-methylphenyl)phosphite, 2,2, ethylene Bis(4_methyl-6-t-butylphenyl)(2_t-butyl-4-methylphenyl)phosphite vinegar, P,4-first butyl stylyl)_4,4,_ Biphenyldiphosphinate, tetrakis(2,4-mono-t-butylphenyl)-4,3,_biphenyldiphosphinate, tetrakis(2,4-di-t-butyl Phenyl)_3,3,_biphenyldiphosphinic acid vinegar, tetrakis(2,6-di-t-butylphenyl)-4,4'-extended biphenyl diphosphinate, four (2,6_二_三丁土笨基) 4,3 stretching as the base diphosphinate, tetrakis (2,6·di-t-butylbenzene 30 201038549 base)-3,3 _ stretch Biphenyldiphosphinate, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphinate, bis(2,4-di-t-butylphenyl) )_3-phenyl-phenylphosphinate, bis(2,6-di-n-butylphenyl)_3_phenyl-phenylphosphinate, bis(2,6-di-third Phenyl) _4_phenyl-phenylphosphinate, bis(2,6-di-t-butylphenyl)-3-phenyl-phenylphosphinic acid vinegar, four (2,4 Di-t-butyl-5-methylphenyl)-4,4'-extended biphenyl diphosphinate, tributyl sulphate, tridecyl phosphate, tridecyl phenyl phosphate, triphenyl phosphate Ester, triphenyl phenyl phosphate, triethyl phosphate, diphenyl toluene phosphate, diphenylmonoorthoxyl phosphate, tributoxyethyl acrylate, dibutyl phthalate, Dioctyl acid ester, diisopropyl acid ester and the like. Commercially available products can also be used as the phosphorus compound. The commercially available phosphorus-based compound is not particularly limited. For example, as a commercial product manufactured by Adeka, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-24G, Adekastab PEP-36, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP. The phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol and 3-(3,5-di-t-butyl-4-hydroxyphenyl). N-octadecyl propionate, tetrakis[-indenyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 2,4-di-third -6-methylphenol, 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], three (3,5-di Third butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4- Basal group) benzene, pentaerythritol-tetraki-[3-(3,5-di-31 201038549 tributyl-4-hydroxyphenyl)propionate], 3,9-bis-[2_[ 3-(3-Tertibutyl-4-hydroxy-5-mercaptophenyl)-propenyloxy]-1,1-dimercaptoethyl]_2,4,8,10-tetraoxaspiro [5,5]undecane, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 2,2'-butylene double (4,6-di-t-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 2,2·-indenyl bis (4-methyl) -6-tert-butylphenol), 2,2'-indenylene bis(4-ethyl-6-tributyl) Phenol), 2-t-butyl-6-(3-tert-butyl-2-hydroxy-5-mercaptobenzyl)-4-methylphenol acrylate, 2-[1-(2-hydroxyl) acrylate -3,5-di-t-pentylphenyl)ethyl]-4,6-di-third amylphenyl ester, 4,4'-thiobis(3-mercapto-6-tributyl) Phenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 2-tert-butyl-4-methylphenol, 2,4-di-t-butyl Phenol, 2,4-di-third amyl phenol, 4,4'-thiobis(3-mercapto-6-tert-butylphenol), 4,4·-butylene bis(3-indenyl) -6-t-butylphenol), bis-[3,3-bis-[4.-hydroxy-3'-t-butylphenyl)-butyric acid]-diol ester, 2,4-di- Tert-butylphenol, 2,4-di-p-pentylphenol, 2-[1-(2-hydroxy-3,5-di-tripentylphenyl)ethyl]-4,6- Di-t-amylphenyl ester, bis-[3,3-bis-(4,-hydroxy-3'-t-butylphenyl)-butyric acid]-diol ester, and the like. Commercially available products can also be used as the phenolic compound. The commercially available phenolic compound is not particularly limited. For example, as a commercial product of Ciba refined production, IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, IRGANOX245, IRGANOX259, IRGANOX295, IRGANOX3114, IRGANOX1098, IRGANOX1520L 'as Adeka Commercially available products can be listed as follows:

Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, 32 201038549

Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-90, Adekastab AO-330 'As a commercial product manufactured by Sumitomo Chemical Industries, Sumilizer GA-80, Sumilizer MDP -S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, etc. In addition to this, commercially available additives can be used as the anti-staining agent for the resin. For example, as a commercially available additive for Ciba Specialty Manufacturing, TINUVIN 328, TINUVIN 234, TINUVIN 326, TINUVIN 120, O TINUVIN 477, TINUVIN 479, CHIMASSO RB 2020 FDL, CHIMASSO RB FF, and the like can be cited. At least one or more selected from the group consisting of the above-mentioned bowl compound, the amine compound, and the compound are preferably contained, and the amount thereof is not particularly limited, and is in the range of 0.005 to 5.0% by weight based on the curable resin composition. The curable resin composition A of the present invention can be obtained by uniformly mixing the components. The curable resin composition A of the present invention can be easily made into a cured product by the same method as previously known. For example, it is necessary to sufficiently mix the epoxy resin of the present invention with a hardener, and optionally a hardening accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent, using an extruder, a kneader, a roll, or the like. The curable resin composition is obtained uniformly, and the curable resin composition is melted, molded by a die-casting or transfer molding machine, and further heated at 80 to 200 ° C for 2 to 10 hours, thereby obtaining the present invention. Hardened matter. Further, the curable resin composition A of the present invention can be dissolved in toluene, xylene, acetone, mercaptoethyl ketone, decyl isobutyl ketone, dimercaptopurine 33 201038549 amine, dimethyl acetamide In a solvent such as N-methylpyrrolidone, a curable resin composition varnish is formed and impregnated into a substrate such as glass fiber, carbon fiber, polycrystalline fiber, polyamide fiber, alumina fiber, or paper. After heating and drying, the obtained prepreg is subjected to hot press forming, whereby a cured product of the curable resin composition A of the present invention is produced. The solvent at this time is usually used in a mixture of the curable resin composition of the present invention and the solvent in an amount of from 1 to 7 Torr/min, preferably from 15 to 70% by weight/0. In addition, you can also use RTM (Resin Transfer) while maintaining the liquid composition.

Molding, resin transfer molding) obtained an epoxy tree Z hardened material containing carbon fibers. Further, the curable resin composition A of the present invention can also be used as a modifier for a film type composition. Specifically, it can be used when the situation of the Hexibinty characteristic in the B-stage (B_stay) is improved. The resin composition of the present invention can be formed into the above-mentioned curable resin composition material by applying the curable resin composition A of the present invention to the lanthanum 4, and after removing the solvent under heating, it is "B-staged" as a sheet. The adhesive of the form obtains the sheet-like adhesive which can be used as an interlayer insulating layer in a multilayer substrate or the like. With a second time, the pair will be ', y»r

The case where the sealing material or the die-bonding material of the A body is taken out by the J group is explained in detail _ the curing resin composition A of the present invention is used as a high-brightness white) sealing material or a viscous material of an optical semiconductor such as coffee In the case, the composition of the epoxy resin, the hardener, the bismuth 5 剤, the antioxidant, and the light-stable J J 4 additive of the present invention are sufficiently mixed to form a coating composition, and then 4 is used as the composition.岔 Sealing material, or viscous material fish 4 bamboo /, in the sealing material. As a method of mixing 7 34 201038549, a kneader, a three-roller, a universal mixer, a planetary mixer, a homomixer, a homodisperser, and a bead mill are used, which are mixed at room temperature or under heating. Optical semiconductor elements such as high-brightness white LEDs are usually GaAs, GaP, GaA1As, GaAsP, A1 (}a, Inp) laminated on substrates such as sapphire, spinel, Sic, germanium, etc. using an adhesive (adhesive material). , GaN, Ο Ο

The semiconductor wafer of InN, A1N, and InGaN f is then formed on the lead frame, the loose-rail plate, or the package to form a current flowing there. There is also a type in which a metal wire is connected. In order to protect the semiconductor wafer from heat or moisture and to function as a lens, a sealing material such as an epoxy resin is used for sealing. The sclerosing tree assay A of the present invention can be used as the sealing material or the viscous material. For the convenience of the step, it is preferable to use the curable resin composition A of the present invention as both a die-bonding material and a sealing material. As a method of adhering a semiconductor wafer to a substrate using the curable resin composition A of the present invention, it is possible to apply the curable resin composition 4 of the present invention by using a dispensing, infusion, or screen printing; The semiconductor wafer is further heated and hardened, whereby the semiconductor wafer is followed. Heating can be performed by means of private air circulation heating, infrared heating, high frequency heating, and the like. The heating condition is preferably, for example, heating at 80 to 230 ° C for about 1 minute to 24 hours. In order to reduce the internal stress generated during heat hardening, for example, it can be pre-hardened in the MM generation for 30 minutes to 5 hours, and then post-hardened under conditions of 12 〇 to i8 〇〇 c and 3 〇 minutes. As a method of forming the sealing material, the substrate or the like in which the semiconductor wafer is fixed as described above may be inserted into the mold frame, and after the sealing material is injected into the mold frame, the heat is hardened to make the heat 35. 201038549 Material forming; compression forming method 4. In the wind-only method, the material is pre-filled on the metal mold, and the semiconductor wafer fixed on the substrate is immersed in the ten-layer and subjected to force hardening 'released from the metal mold. Examples of the injection method include ',:,, a knife injection, a transfer molding, and an injection point report. Heating can be performed by using hot air circulation type, ", infrared heating, high frequency heating, etc. Heating conditions are preferably, for example, heated at 8 Torr to 战 minutes to about Μ hours. To reduce the internal heat generated during heat hardening. It can be pre-hardened for 3 minutes to 5 hours under ~Cong, and then post-hardened under conditions of 12 〇 to 18 〇C, 30 minutes to 10 hours. Further, the curable resin group of the present invention is used for making Specific examples of the thermosetting resin such as a resin include an adhesive, a coating material, a coating agent, and a molding material (including a sheet, a film, FRP (Fiber), and an insulating material). (including a printed circuit board, a wire coating, etc.) and a sealing material, and other resins such as an acrylic vine resin which is added to a sealing material, a cyanate resin composition for a substrate, or a curing agent for a photoresist. Additives, etc. As an adhesive, an adhesive for civil engineering, construction, automotive, general service, and medical use can be cited, and an adhesive for electronic materials can be cited. In the above-mentioned, an adhesive for an electronic material, an interlayer adhesive for a multilayer substrate such as a build-up substrate, an adhesive for a semiconductor such as a die bond or an underfill, an underfill for BGA reinforcement, and an anisotropic conductive film. (ACF 'Anisotropic Conductive Film), an adhesive conductive adhesive (ACP, Anisotropic Conductive Paste), etc., such as adhesive tape 36 201038549. Examples of the sealant include a capacitor, a transistor, a diode photodiode, and an IC ( Integrated Circuit, LSI (Large ❹ 〇

Scale integration, large integrated circuit), etc., perfusion, impregnation, transfer molding, sealing 1C, LSI-based COB (Chip On Board), COF (Chip 〇n Film) TAB (Tape Automated Bonding), etc., the bottom filler used for flip chip, etc., QFP (Qua Flat package, BGA, CSP (Chip Size Package)) Sealing in package-type packaging (including reinforcing underfill). The cured product of the present invention obtained by curing the curable resin composition A of the present invention can be used for various applications represented by optical component materials. The material for optics generally means a material for the purpose of passing light such as visible light, infrared rays, ultraviolet rays, X-rays, or laser light through the material. More specifically, a sealing material for LpD such as a lamp type or a SMD (surface-mount device) type may be used, and the following may be mentioned: a substrate material in the field of liquid crystal display, and a light guide plate. A material for a liquid crystal display device such as a liquid crystal film such as a film, a polarizing plate, a phase difference plate, a viewing angle correction 臈, an adhesive, or a polarizing element protective film.彳' can be cited as a next-generation flat panel display and is expected to be a color & pDp (piasma this coffee

The sealing material, the anti-reflection film, the optical correction film, the outer casing material, the protective film of the front glass, the front glass substitute material of the Pane Bu plasma display), and the mold material of the coffee used for the LED display, Sealing material, protective film for front glass, front glass substitute material, 37 201038549 The following is also referred to as a substrate material of a PIN (Addressed Liquid Crystal) display, a light guide plate, a prism sheet, a deflecting plate, The retardation film, the viewing angle correction film, the adhesive, and the polarizing element protective film include a protective film for a glass of an organic EL (electroluminescence) display, a front glass substitute material, and an adhesive. A variety of film substrates for field emission displays (FED, Field Emissi〇n), front glass protective films, front glass replacement materials, and follow-up agents. In the field of optical recording, VD (Vide〇Disc, CD), CD (Compact Disc), CD_R〇M (c〇mpact Disc-Read Only Memory), CD_R/RW (c〇) Mpact

DiSC-Recordable/ReWritable, recordable/rewritable disc), dvD-R (Digital Versatile Disc-Recordable, recordable digital versatile disc)/DVD-RAM (Digital Versatile Disc Rand〇m Access Memory' Repeated reading and writing of digital versatile discs, M〇 (Magnet〇Optica), MD (Mini Disc), pD (change) disc, optical discs for optical memory cards Materials, optical disk read heads, protective films, sealing materials, adhesives, etc. In the field of optical machines, a lens material for a still camera (stiUcamera), a viewfinder 稜鏡, a target 稜鏡 (Urget pdsm), a viewfinder cover, and a light receiving sensor unit are exemplified. In addition, a video camera and a viewfinder of a video camera can be cited. Further, a projection lens, a protective film, a sealing material, an adhesive, and the like of a projection television can be cited. Further, examples thereof include a material for a lens of a light sensing device, a sealing material, an adhesive, a film, and the like. In the field of optical parts, the fiber material around the optical switch in the optical communication system, the lens, the 38 201038549 waveguide tube, the sealing material of the element, and the adhesive are listed. Other examples include optical fiber materials, ferrules, sealing materials, and adhesives around the optical connector. Yu Guang Passive parts and optical circuit zeros include lenses, waveguides, LED sealing materials, CCD (Charge CQUpIed DeWee), sealing materials, and adhesives. Further, examples thereof include a substrate material fiber material around a photovoltaic integrated circuit (〇eic, 〇Pt〇eleCtr〇niC integrated Clrcuit), a sealing material for an element, an adhesive, and the like. In the field of optical fiber, it can be enumerated

Lighting, light guides for display, display sensors, display/identification for industrial use, etc. In addition, the communication infrastructure (—η-· wall _UetUre and digital machine connection in the home (4) Among the materials surrounding the semiconductor integrated circuit, there are (3) and super (3) materials for the use of Micr〇mhography to receive photo-resistance materials. In the field of automobiles and transporters, the lamp reflectors for automobiles are listed. , bearing retainer (beanng), gear parts, residual coating, switch parts, headlights, engine parts, electrical parts, various interior and exterior decorations, drive engines, brake oil tanks, cars A rust-proof steel plate, an interior panel, an interior material, a wire harness for protection/bundling, a fuel hose, an automobile lamp, and a glass substitute. A multilayer glass for a railway vehicle is also exemplified. The anchoring agent for the structural material, the engine peripheral member, the harness for protection/bundling, and the enamel-resistant layer. In the construction field, the interior decoration/processing material, the electronic cover, and the sheet can be cited. A glass interlayer film, a glass substitute, and a solar cell peripheral material. In the agricultural use, a ruthenium for house coating is exemplified. As a next-generation photoelectric functional organic material, an organic EL element peripheral material, an organic light refracting element, and light can be cited. - 39 201038549 Optical amplifying elements, optical computing elements, substrate materials around organic solar cells, fiber materials, sealing materials for components, adhesives, etc. Curable resin composition B (cation hardening with acidic curing catalyst) The curable resin composition B of the present invention which is cured by an acidic curing catalyst contains a photopolymerization initiator or a thermal polymerization initiator as an acid curing catalyst. Further, it may contain a diluent, a polymerizable monomer, and polymerization. Various known compounds, materials, and the like, such as an oligomer, a polymerization initiator, and a photosensitizer. Further, various known additives such as an inorganic filler, a coloring pigment, an ultraviolet absorber, an antioxidant, and a stabilizer may be contained as needed. As the acid hardening catalyst, a cationic polymerization initiator is preferred, and photocationic polymerization is particularly preferred. Examples of the cationic polymerization initiator include sulfonium salts such as sulfonium salts, phosphonium salts, and diazonium rust salts, and these may be used alone or in combination of two or more. Examples of active energy cation polymerization initiators may be used. Listed: metal fluoroborate stearate and boron trifluoride compound (U.S. Patent No. 3,375,653), bis(perfluoroalkylsulfonyl)methane metal salt (U.S. Patent No. 3,586,616), aryldiazonium rust compound (US Patent No. 37〇8296) 'Aromatic sulfonium salt of the Vh group element (U.S. Patent No. 4,584, )), aromatic sulfonium salt of the Va group element (US Patent No. 4〇69〇55), a carbonyl group of a nia~ group element (U.S. Patent No. 4,68,91), a thiopyranium salt (U.S. Patent No. 4,139,655), a group element of an MF〆 anion form (U.S. Patent No. 4,161,478; M series is selected from the group consisting of phosphorus, antimony and arsenic), aryl mis-salt salts (U.S. Patent No. 4,231,951), aromatic salts and 201038549 aromatic salts (US Patent No. 4256828), and double [4_(two) Phenyl fluorenyl) thiol-bis-hexafluorometal salt urnal polymer

Science, P〇lymer chemistry ‘Vol. 2, 1789 (1984)). In addition to this, a mixed ligand metal salt of an iron compound and a calcined alcohol-aluminum complex may also be used. In addition, as a specific example, "Adeka Optomer SP1 50" and "Adeka Optomer SP170" (all manufactured by Asahi Denki Kogyo Co., Ltd.), "UVE-1014" (manufactured by General Electronics Co., Ltd.), "CD-1012" ^ ( "RP-2074" (manufactured by Rhodia Co., Ltd.) manufactured by Sartomer. The amount of the cationic polymerization initiator to be used is preferably from 0.01 to 50 parts by mass, more preferably from 1 to 10 parts by mass, per 100 parts by mass of the epoxy resin component. Further, the photocationic polymerization initiator may be used together with one or more of a known polymerization initiator and a photosensitizer. Examples of the polymerization initiation aid include benzoin, benzoin, benzoin methyl ether, benzoin isopropyl ether, phenelzine, 2,2-dimethoxy-2-phenylacetophenone, 1, dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2 曱 丨 丨 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( N-didecylamino acetophenone, 2-methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl fluorene, 丨 蒽醌 gas, 2 pentyl broth, 2-iso Propyl thioxanthone, 2,4-dimercaptothioxanthone, 2,4-diethylthioketidone, 2,4-diisopropylthioxanthene, acetophenone dimethyl ketal, diphenyl Photoinitial polymerization of anthrone, 4_methyl- aconone, 4,4·-dichlorodibenzophenone, 4,4′-bisdiethylaminobiphenyl, 1 and rice ketone Starting agent. The photoradical polymerization is used in an amount of from 0.01 to 30 parts by weight, preferably from 1 to 1 part by weight, based on 100 parts by weight of the component capable of photoradical polymerization. . Specific examples of the photosensitizer include hydrazine, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4 diisopropyl. Thioxanthone, acridine orange, acridine yellow, phosphine R, benzoflavin, thioflavin, hydrazine, ethyl N,N-dimethylaminobenzoate, N,N_: methylaminobenzene Isovaleric acid monoethanolamine, diethylamine, and the like. The photosensitizer is used in an amount of from 0 to 10 parts by weight, preferably from 3 to 10 parts by weight, based on 100 parts by weight of the total of the epoxy resin component. Further, various additives such as an inorganic filler, a decane coupling agent, a release agent, and a pigment, and various thermosetting resins may be added to the curable resin composition B of the present invention as needed. Specifically, for example, as described above. The curable resin composition B of the present invention can be obtained by uniformly mixing the components. Further, each component may be dissolved in polyethylene glycol monoethyl ether or an organic solvent such as % ketone or r-butyrolactone to be uniformly mixed, and then the solvent is removed by drying to be used. The solvent at this time is usually used in an amount of from 1 to 7 % by weight, preferably from 15 to 70% by weight, based on 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 ultraviolet irradiation, but the amount of ultraviolet irradiation varies depending on the composition of the curable resin composition. Therefore, the amount of ultraviolet irradiation must be determined according to each curing condition. The irradiation amount may be sufficient to cure the curable resin composition, and the curing condition may be sufficient as long as the adhesive strength of the cured product is good. At the time of hardening, since light is required to be transmitted to the detail, 42 201038549 * Therefore, it is preferable that the epoxy resin of the present invention and the curable resin composition b have high transparency. Further, when the epoxy resin is photocured, it is difficult to completely cure only by light irradiation. Therefore, in applications requiring heat resistance, it is necessary to heat after light irradiation, thereby completely completing the reaction hardening. . When heating is performed after light irradiation, heating can be performed in the hardening temperature region of the usual curable resin composition B. For example, it is more suitable to be normal temperature ~ 150. (: the range of 30 minutes to 7 days. ^ will vary depending on the composition of the sclerosing tree blush composition B, but the more high temperature region, the more effective it is to promote hardening after light irradiation. Moreover, the heat treatment for a short period of time has an effect. In addition, the lower the temperature, the longer the heat treatment is required. By such heat-hardening, the effect of the aging treatment is also exhibited. The shape of the cured product obtained by curing the composition B may be various shapes depending on the application, and therefore, it is not particularly limited. For example, it may be formed into a film shape, a sheet shape, a block shape, or the like. The molding method is based on the corresponding portion. Different from the member, for example, a molding method such as a casting method, a casting method, a screen printing method, a spin coating method, a spray method, a transfer method, or a dispensing method can be applied, but the molding method is not limited thereto. Applications: ground glass, hard stainless steel grinding plates, polycarbonate sheets, polyethylene terephthalate sheets, polymethyl methacrylate sheets, etc. In addition, in order to improve the release property from the forming mold, Applicable to: polyethylene terephthalate film, polycarbonate film, polyethylene film, polyethylene film 'polytetrafluoroethylene film, polypropylene film, polyimide film, etc.. For example, when used as a cation In the case of a curable photoresist, first, the present invention is dissolved in an organic solvent such as polyethylene glycol monoethyl ether or cyclohexanone or τ-butyrolactone by a method such as printing or spin coating. The photo-cationic curable resin composition B is applied to a substrate such as a copper clad laminate, a ceramic substrate or a glass substrate at a film thickness of 5 to 160 to form a coating film. Next, the coating film is preliminarily prepared at 60 to 1 HTC. After drying, irradiate ultraviolet rays and wires through a negative film depicting a desired pattern (for example, a low mercury lamp, a sorghum mercury lamp, a super high mercury lamp, a xenon lamp, a laser light, etc.), followed by 7 〇 to 12 〇. After the exposure baking treatment, the unexposed portion is dissolved (developed) by a solvent such as polyethylene glycol monoethyl ether, and then irradiated with ultraviolet rays and/or heated as needed (for example, at 1 〇〇 2 〇 〇t under heating for 5~3 hours) to make it hard enough A cured circuit board can be obtained. The printed circuit board can also be obtained in such a manner. The cured product obtained by hardening the curable resin composition B of the present invention can be used for various purposes represented by optical component materials. The material used for the purpose of passing light such as visible light, infrared rays, ultraviolet rays, X-rays, and laser light through the material. More specifically, a sealing material for LEDs such as a lamp LSMD type can be cited as follows. That is, a liquid crystal display device such as a substrate material light plate, a phase difference plate, a viewing angle correction first plate, a cymbal sheet, a partial cavity m MG positive film, an adhesive, a polarizing element protective film, a liquid daily film, and the like in the field of liquid crystal display nRemaining materials. In addition, 'can be cited as a flat-panel display for people generations to be crying" 夕~, and j expecting color PDP (plasma display not fast) hunting material, anti-reflection film, ^ ^ _ first Learn to modify the film, the outer shell material, the protective film of the face glass, the front glass, the m τ 2 substitute, the adhesive, and

Listed as LED device, LE <tank material, led seal 44 201038549 material, front glass protective film, front glass substitute material, adhesive, and substrate material of plasma addressed liquid crystal (PALC) display , light guide plate, cymbal sheet, deflecting plate, phase difference plate, viewing angle correction film, adhesive, polarizing element protective film 'Alternatively, organic EL (electroluminescence) shows the protective film of the front glass, front glass substitute material Further, examples of the adhesive include a film substrate of a field emission display (fed), a protective film for the front glass, a front glass substitute material, and an adhesive. In the field of optical recording, VD (Video Disc), CD/CD_R〇M, CD_R/RW, 〇DVD_R/DVD-RAM, M〇/MD, PD (phase change disc), and optical memory card discs can be cited. Substrate material, optical disk drive head, protective film, sealing material, adhesive, and the like. The lens of the still-life camera is used in the field of optical equipment, material, viewfinder, target prism, viewfinder cover, and light-receiving sensor. In addition, a photographic lens and a viewfinder of a video camera can be cited. Further, a projection lens, a protective film, a sealing material, an adhesive, and the like of a projection television can be cited. Further, a material for a lens of a photo-sensing device, a sealing material, and the like can be cited. In the field of optical parts, the light in the optical communication system = the fiber around the periphery (four), the lens, the waveguide, the sealing material of the component, the denseness, the optical fiber material of the agent, the ferrule, the ferrule Fibre = material can be listed: In the field of the periphery of the optoelectronic integrated circuit, a sealing material, an adhesive, and the like can be cited. In the case of optical fiber, it is used for illumination, light guide, etc., for industrial use. 45 201038549 Detector class 'displayed/identified class, etc. In addition, the fiber for digital device connection in the home of communication is listed. In semi-electrical, lifting-, super-LSI materials for the following engraving =; '• in the field of 'flying vehicles, transport aircraft, can be cited for automotive lamp cover, bearing retainer, gear parts, corrosion resistant coating , switch part, head strict: inside the lead: parts, 'electric parts, various interior and exterior decorations, drive engine, brake stolen oil phase' 'vehicle rust-proof steel plate, interior panel, interior decoration material' protection / strapping harness In addition, the fuel hose, the automobile lamp, and the glass substitute, and the physical property imparting agent for the multi-layered material for the railway vehicle, and the engine 2_in addition, may include the structural sub-cover of the aircraft, the material for processing the inner wire, and the electric material. In the case of agricultural use, the glass intermediate material, the glass substitute, and the solar cell peripheral material 2 can be cited as a film for house coating. As a second-generation functional organic material, the organic EL element peripheral material 'organic light is used as light- Optical amplifying element, optical arithmetic element, and machine of the optical conversion device: substrate material around the battery, fiber material, sealing material of the element, adhesive, etc. π j Ho: for the sealant, a capacitor, a crystal , diodes, light-emitting diodes, 1C, LSI, etc., used in (3), (3), (3) F, TAB, etc., impregnation, transfer molding, sealing, part filling, BWwd perfusion sealing, flip chip The underfill is used in the case of the package. The sealing for the package type (the other use of the reinforcing bottom composition t-light material) may be a general use of a curable resin, and examples thereof include an adhesive, a coating, and a coating agent. 46 201038549 Forming materials (including sheets, films, substrates, wire-clad, 1st, etc.), insulating materials (including printing, and good-covering 4) 1 material, in addition to other resins, etc.' ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Examples of the adhesive for the electronic material include an interlayer adhesive for a multilayer substrate such as a build-up substrate, an adhesive for a semiconductor such as a die bond or an underfill, and an underfill 枓, an anisotropic conductive film (ACF), Anisotropic conductive adhesive (ACp) The adhesive for encapsulation, etc. [Examples] Next, unless otherwise specified, the specific examples are given. The present invention will be more specifically described. In the following description, the parts are parts by weight. In the examples, the epoxy equivalent is measured in accordance with JIS κ-7236, and the viscosity is measured at 251 using an E-type viscometer. In addition, 'as a gas chromatography method (hereinafter referred to as r Gc ( Gas

The analytical conditions in Chromatography)") were HP5-MS (0.25 mm ID xl5 m, thickness 0.25 /zm) as the separation column, and the initial temperature of the column oven temperature was set to 1 〇〇, per minute. The temperature was raised at 15 ° C and maintained at 300 ° C for 60 minutes. In addition, helium gas is used as a carrier gas. Further, the measurement of gel permeation chromatography (hereinafter referred to as "GPC (Gel Permeation Chromatography)") is as follows. The column is connected to the shodex SYSTEM-21 column (KF-803L, KF-802.5 (x2 root), KF-802). The solution is tetrahydrogen cough, the flow rate is 1 ml/min, and the column temperature is 47. 201038549 40 ° C, and the detection system was carried out using UV (254 nm), and the calibration curve was made using standard polystyrene manufactured by Shodex. Example 1 In a flask equipped with a stirrer, a reflux cooling tube, a stirring device, and a Dean-Stark tube, 150 parts of benzene was added while performing nitrogen purge, and the following formula (5) was used.

HaCHOH2C

(6)

(Manufactured according to Japanese Patent Laid-Open Publication No. 2007-126447, GPC area 99% (detector RI)) 1〇9 parts, 126 parts of 3-cyclohexene decanoic acid, and 曱 尹 尹 ''acid 2 injury' in heat transfer The next side removes water and reacts for 1 hour. After completion of the reaction, the organic layer was washed twice with water in an amount of 1% by weight of aqueous sodium hydrogen carbonate solution, and the obtained organic layer was washed twice with water, and then the organic solvent was concentrated by k-transvaporation H to obtain the second invention. Dilute compound (Dl) 20Q, wide object. It was confirmed that the shape of the diene compound was liquid, and the purity measured by the chromatographic method was 96%, which was analyzed by gel permeation chromatography. Fruit, its purity > 98%. The viscosity is 2070 mPa . s (E-type viscometer at 25 °C). Example 2 In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, a 48, 2010, 385, 490 surface was subjected to a nitrogen purge, and 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, and 0.78 parts of 'dihydrogenated tallow were added. 2.7 parts of dimethyl acetate (50% of the solution made by Lion Akzo, Arquad 2HT-Acetate), after the formation of the tartaric acid catalyst, 12 parts of toluene and 1 〇9 parts were added in Example 1 The obtained diene compound D-1 was further stirred again to thereby prepare a solution in an emulsion state. The solution was warmed to 5 Torr, and 35 parts of hydrogen peroxide water was added for 35 parts while stirring vigorously, and then the mixture was stirred directly under 5 Torr.

hour. The progress of the reaction was confirmed by GC, and as a result, the conversion of the substrate after the completion of the reaction was > 99%, and the peak of the raw material disappeared. Then, after neutralizing with a 1% aqueous sodium hydroxide solution, 25 parts of a 2% by weight aqueous sodium thiosulfate solution was added and stirred for 3 G minutes, and the money was allowed to stand. The organic layer separated into two layers was taken out, and 10 parts of celite (1^.〆c_) was added thereto, activated carbon (CAP SUPER manufactured by IT IT) 2G parts, bentonite (BengelSH manufactured by H〇Jun) 2 〇#, filtered at room temperature for a few hours. Then, the water (10) is washed three times with the obtained money, and the organic solvent is distilled off, thereby obtaining the following formula (6).

The epoxy resin (Ερ·丨) of the present invention is 99 parts. It was confirmed by GPC's measurement that it contained 9S% of the compound of the skeleton of the formula (6) 49 201038549. Further, in the Gc measurement, the purity was 93%. In addition, its viscosity is 13500 mpa.s (3 〇. underarm, E-type viscometer), and the epoxy equivalent is 248 g/eq. Example 3 With respect to 5 parts of the obtained epoxy resin (EP_丨), a silicone resin (manufactured by Wakogel C-300' and Wako Pure Chemical Industries, Ltd.) 5 parts, ethyl acetate: hexane-14 polymerization solvent was used. And purified by column chromatography. The epoxy resin (Ep_2) obtained was 丨3 parts, and the purity of the obtained epoxy resin was confirmed to be a compound containing the skeleton of the formula (6) in %% or more from the measurement results of GPC. Further, in the GC measurement, the purity was about 99%. In addition, its viscosity is 11 〇〇〇 mPa. s (3 〇. underarm, E-type viscometer), and the epoxy equivalent is 236 g/eq. Examples 4, 5, and 6 For the epoxy resin (Ep_b EP_2) of the present invention obtained in Examples 1 and 2, methyl hexahydrophthalic anhydride (Nippon Chemical and Chemical Co., Ltd.) was used as a hardener. ) Manufactured, RikacidMH7〇〇G, hereinafter referred to as H1), bicyclo[2,2,1]g-burn _2,3-dicarboxylic anhydride (manufactured by New Japan Physical and Chemical Co., Ltd., (10) Heart HNA^100, hereinafter referred to as H2), cetyltrimethylhydroxide as a hardening accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., 25% methanol solution, referred to as C1), and the mixing ratio (parts by weight) shown in Table 1 below After the mixing, defoaming was carried out for 20 minutes, whereby the curable composition of the present invention was obtained. Using the obtained curable resin composition, heat resistance was examined in the following manner. The results are shown in the table. Further, the curing conditions were carried out in 50 201038549, 120 ° C, and 3 hours pre-hardening, and then 15 (Γ (: χΐ hour hardening. (heat resistance characteristic test)) The hardening resin compositions obtained in Examples 4 to 6 were carried out. After vacuum defoaming for 2 minutes, it was gently cast into a metal mold for a test piece having a width of 7 mm, a length of 5 cm, and a thickness of about 800, and then capped from above using a polyimide film. The condition of the cast material was hardened to obtain a dynamic viscoelasticity I. The film was subjected to the dynamic viscoelasticity test using the test pieces under the conditions shown below. 〇 Measurement conditions 800 Dynamic viscoelasticity Measurer: manufactured by TA-instruments, measuring temperature range: _3 〇. 〇~28 (TC heating rate: It/min sizing size: using test piece β m cut into 5 mm x 50 mm) DMA-2980 (thickness approx. For analysis of conditions

Tg: Tan 5 in the dynamic viscoelastic (DMA) measurement is taken as Tg. 25 ° C elastic modulus: Determination of 25. (:The modulus of elasticity of time. 51 201038549 [Table 1]

Item Example 4 Example 5 Example 6 Composition EP-1 4.96 EP-2 4.72 4.72 Hardener (H1) 3.36 3.36 Hardener (H2) 3.56 Hardening Catalyst (C1) 0.04 0.04 0.04 Heat Resistance DMA(tan0) 185〇 C 189〇C 156〇C Examples 7, 8 and Comparative Example 1 The epoxy resins (Epj, EP-2) of the present invention obtained in Examples 2 and 3, and 3, 4 epoxy as a comparative example Cyclohexyldecyl-3,4-epoxycyclohexylcarboxylate (ERL-4221 manufactured by Dow Chemical Co., Ltd., epoxy equivalent: 140 g/eq., hereinafter referred to as Ep_3), used as a hardener and as The curing accelerator was mixed with the compounding ratio (parts by weight) shown in the following Table 2, and then defoamed for 2 minutes to obtain the curable composition of the present invention and comparative use. Using the obtained curable resin composition, a heat durability transmittance test and an LED test were carried out in the following manner, and the results are shown in Table 2. Further, the 'hardening condition was performed by pre-curing i 2 〇 ° C for 2 hours and then hardening at 140 〇 C X for 2 hours. (Thermal Durability Transmittance Test) After the vacuum curable resin composition obtained was subjected to vacuum defoaming for 2 minutes, it was gently cast to a size of 30 mm x 20 mm x 1 mm to a heat-resistant tape. On a glass substrate with a barrier. According to the hardening of the regulations 52 201038549 « The conditions of the washing 1st hardened to obtain a transmittance test piece having a thickness of 1 mm. Using these test pieces 'measured at 150 by a spectrophotometer. (The transmittance was measured in an oven for 96 hours before and after (measuring wavelength: 375 nm), and the rate of change was calculated. (LED test) After the vacuum curable resin composition obtained was subjected to vacuum defoaming for 20 minutes, Filled into a syringe and washed and cast into a surface mount type LED package with a center light beam of 465 nm and an outer diameter of 5 mm square using a precision ejection device (inner diameter 4.4 mm, outer wall height) It is 1.25 mm). It is then hardened by the specified hardening conditions to obtain the test LED. (1) LED lighting test The lighting test is performed at a predetermined current of 30 mA. The detailed conditions are as follows As a measurement item, the illuminance of the LED for the test LED was measured using an integrating sphere to measure the illuminance of the LED for the test. ^ Lighting detailed conditions Illumination wavelength: 465 nm Driving method: Constant current mode, 30 mA ( The current rating of the light-emitting element is 30 mA.) Driving environment: 85 ° C, 85% Evaluation: The case where the illuminance reduction degree is less than 5% is judged as 〇, and the case where 5% or more and less than 10% is determined as △, More than 10% 53. 2010-0549 (2) LED thermal cycle test The thermal cycle test is set to 2 eight chains in the cold rolling time, I will be required to raise and lower the temperature for the cuckoo clock and repeat -4 (TCxl5 minutes ~ 12 (rcxl5' was then visually observed for 1 (9) times, and after the test, cracks and peeling were caused by the test. The evaluation was judged as X by the occurrence of cracks and peeling, and the case where no cracks and peeling occurred was judged as 〇. [Table 2]

Hardened physical property heat durability transmittance test LED lighting test LED thermal cycle test

500 times 85.9% 88.1% 84.0% 〇〇〇X 〇X Example 9 Comparative Example 2 The epoxy resin (EP-1) of the present invention obtained in Examples 2 and 3 and the epoxy resin as a comparative example Resin (eP_3), bis(3,4-epoxycyclohexylfluorenyl (tetra) adipic acid (ERL-4229 manufactured by D〇w Chemical Co., Ltd., epoxy equivalent of i96 g/eq·, hereinafter referred to as EP-4), The quaternary quaternary salt (the ΡΧ-4ΜΡ manufactured by Nippon Chemical Industry Co., Ltd., hereinafter referred to as C2) which is used as a hardening agent, and the compounding ratio (parts by weight) shown in the following Table 3 are used. The foaming was performed for a minute to obtain a curable resin composition for use in the present invention and for comparison. 54. Using the obtained curable resin composition, the LED lighting test was carried out in the manner as shown. The results are shown in Table 3. Further, the hardening conditions were carried out by pre-hardening at 110 ° C for 3 hours, and then 13 (TC >< 5 hours of hardening. (LED lighting test A) The vacuum curing of the obtained curable resin composition was carried out for 20 minutes. After the bubble, fill it into the syringe and wash it with a precision spray device. It is mounted on a surface mount LED package (with an inner diameter of 4.4 mm and an outer wall height of i 25 mm) with a center light-emitting wave of 465 rnn and an outer diameter of $ mm square. Thereafter, the specified hardening conditions are used. The test LED is obtained by hardening it. The lighting test is performed at twice the predetermined current, that is, 60 mA. The detailed conditions are as follows. As the measurement item, the illumination is measured using an integrating sphere for 2 hours before and after lighting. Calculate the illuminance retention rate of the test LED. Detailed lighting conditions: 465 nm LED component: Drive mode: Constant current mode, 60 mA (30 mA for the illuminating component) Drive environment: 85. (:, 85% (LED lighting test B) In addition, in the same environment as the above LED lighting test (ie, 85 <>c, 85% of the conditions), the test LED is not lit and stored, and the integrating sphere is used for measurement. The illumination of the test coffee was maintained at a rate of 55 201038549 degrees. [Table 3] Item Example 9 Comparative Example 2 Comparative Example 3 Composition EP-1 4.96 EP-3 2.80 EP-4 3.48 Hardener (H1) 3.36 3.36 3.36 Hard Catalytic (C2) 0.02 0.02 0.02 LED lighting test A (illuminance retention) 72% 54% 53% LED lighting test B (illuminance retention) 98% 92% 87% Synthesis Example 1 with mixer, reflux cooling In the flask of the tube and the stirring device, 12 parts of dicyclopentadienyldithiol and fluorenylhexahydrophthalic acid anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd., Rikacid MH, hereinafter referred to as an acid anhydride) were added while performing nitrogen purge. H-3) 73 parts, 1,2,4-cyclohexanetricarboxylic acid-1,2-dianhydride (Mitsubishi Gas Chemical, H-TMAn, hereinafter referred to as H-4), heated and stirred at 40 ° C After 1 hour, heating and stirring at 60 ° C for 1 hour (by GPC, it was confirmed that dicyclopentadiene dimethanol became 0.5% or less), thereby obtaining a hardener composition as a mixture of polyphenolic acid and an acid anhydride (HA- 1) 1 copy. The functional group equivalent of the obtained compound was 171 g/eq. (The carboxylic acid and the acid anhydride were each considered as a functional group). Synthesis Example 2 In a flask equipped with a mixer, a reflux cooling tube, and a mixing device, 2,4-diethylpentanediol (Kyowa Hakko Chemical Co., Ltd.) was added while nitrogen gas was purged. Kyowadiol PD-9) 10 parts, anhydride (H-3) 73 parts 'heated and stirred at 40 ° C for 1 hour, followed by 6 Torr. (: heating and stirring for 1 hour (confirmation of disappearance of dicyclopentadiene dimethanol by GPC), thereby obtaining 60 parts of a hardener composition (HA-2) as a mixture of a polycarboxylic acid and an acid anhydride. The functional group equivalent weight is 17 〇g/eq_ °. Examples 10 and 11 The epoxy resin (ej>_丨) of the present invention obtained in Example 2, and hydrazine as the hardener composition are synthesized in Examples 1 and 2. The hardener composition (HA -1 ), (HA-2 ), respectively obtained as an additive, zinc phthalate complex (

XC-9206 manufactured by Industries, hereinafter referred to as ΑΕΜ), hindered amine compound (LA-52 manufactured by Adeka, hereinafter referred to as AD_2), and blended with the compounding ratio (parts by weight) shown in Table 4 below to obtain the hardening of the present invention. Sexual composition. (Thermal Durability Transmittance Test) Q After the vacuum curable resin composition obtained was subjected to vacuum defoaming for 20 minutes, it was gently cast to a thickness of 3 mm x 20 mm x 1 mm to be made of heat-resistant tape. On the glass substrate of the barrier. The washed product was subjected to 1 HTCX for 2 hours of pre-hardening, and then subjected to 15 (n: χ 3 hours hardening to obtain a test piece for transmittance of 1 mm in thickness. Using the obtained test piece, it was measured by a spectrophotometer for 15 generations. (4) The transmittance before and after the % hour (measurement wavelength: 400 nm) was placed, and the rate of change was calculated. 57 201038549 [Table 4] Example of the project] Π Ί - Epoxy resin (ΕΡ-1) 4.96 __Implementation Example 11 Hardener (ΗΑ-1) 3 4?, 4.96 Composition Hardener (ΗΑ-2) Additive (AD-1) 0.05 Additive (AD-2) 0 01 0.05 _ 0.01 Transmittance (initial) Retention after heat resistance test Rate 89% 90% 87% From the above results, it is understood that the present invention has the properties and toughness (according to the heat-resistant cycle test) resin composition. The soil oxygen resin can form an optically excellent hardenability of the present invention. It will be apparent to those skilled in the art that the present invention may be modified and modified without departing from the spirit and scope of the present invention. The present application is based on the patent application of March 2009. Patent wish 2〇〇9_〇67197) cites all of its contents. In addition, it is incorporated in the body cited here. The application for the application on the 19th is also referred to as a reference by a reference [simplified description] Main component symbol description] Benefit 58

Claims (1)

201038549 VII. Patent application scope: 1' kind of diene compound, which is characterized by: It is represented by the following formula (1) 〇 0 R (wherein, the number of carbons or carbons is 1 (1), and the R groups existing in the plural are independently present, indicating a burnt group of 6; in addition, p represents hydrogen as a radical or direct bond having a carbon number of 1 to 6. Knot). 2 · A kind of epoxy resin' is characterized by: β^ #一烯烯#人1 You are the first item of the patent research (the one compound is obtained by oxidation. Or it is peracid and epoxidized. (4) Richeng Oxidation Oxygen 4·-Epoxy Resin Composition' is characterized by the inclusion of an epoxy resin and a hardener and/or a hardening catalyst according to any one of items 2 and 3. — Scotch hardened material, characterized in that the epoxy resin composition of the fourth application patent scope is hardened. VIII. Schema: No 59