TW201029984A - Diolefin compound, epoxy resin, curable resin composition and cured product - Google Patents

Abstract

A novel alicyclic epoxy resin having no ester bond in each molecule, and a precursor of the alicyclic epoxy resin. The precursor is a diolefin compound represented by formula (1) (wherein each of the plurality of R's independently represents a hydrogen atom or an alkyl group having 1-6 carbon atoms), and the epoxy resin is obtained by epoxidizing the diolefin compound.

Description

201029984 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a novel olefinic compound and an epoxy resin β in the form of a suitable electric and electronic material (4). [Prior Art] ❹ ❹ Epoxy resin is made of various hardeners. By hardening, it is used as a cured product excellent in mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., and is used in a wide range of fields such as an adhesive, a coating material, a laminate forming material, and a photoresist. . In recent years, ... a mobile phone with a camera, an ultra-thin liquid crystal or a plasma TV is attached to the field of semiconductor-related materials. Lightweight notebook computers and the like are focused on light, thin, short, and small electronic devices. Therefore, packaging materials such as epoxy resins are required to have very high characteristics. In particular, the structure of the front end seal is complicated, and if the liquid seal is not used, the seal is difficult. For example, the structural part of the Cavity_D〇Wn type such as the Enhaneed BGA (the bare BGA package) must be sealed, and the transfer molding (Transfer M〇lding) cannot be performed. Therefore, it is necessary to develop a high-performance liquid epoxy resin. In the case of composite materials, car bodies, and ship construction materials, RTM has been used for many years because of its simple manufacturing method. It is preferable that such a composition is a low-viscosity epoxy resin because it is easily impregnated with carbon fibers or the like. In addition, in the field of optoelectronics, especially in recent years, in order to smoothly transmit 'processing a large amount of information, the technology for generating optical signals by changing the signal transmission of electrical wiring has been gradually developed 3 201029984' In the field of optical components such as optical waveguides, blue light, and optical semiconductors, it is desired to develop a resin excellent in transparency. For these requirements, alicyclic epoxy compounds are attracting attention. The alicyclic epoxy compound is excellent in electrical insulating properties and transparency, and is used in various types such as transparent sealing materials, but such an alicyclic epoxy compound is used in this manner. Behind the advantages, there is a problem that the hardened material is hard and the rigidity is poor, and it is now reviewed to improve the shortcoming (Patent Document 丨). Further, most of the alicyclic epoxy resins which have been conventionally known to have a structure have a _ bond. When the molecule has a vinegar gene and is hydrolyzable at a high temperature, or when it is used for a strong acid, the physical properties of the cured product may be lowered... Although the molecule has an alicyclic skeleton but does not have a vinegar group. The epoxy compound is preferred. Such epoxy compounds are disclosed, for example, in Patent Documents 2 and 3. There are not many types of existing alicyclic epoxy compounds, and most of the raw materials before epoxidation are more expensive compounds. Moreover, even if the epoxide of the decadiene is relatively inexpensive, it has a low polarity and a sublimation property, and it has sublimation property, which is not only poor in work, but also has a high density of functional groups and hardening of toughness. Things. Patent Document 1: Japanese Public Opinions β β β β β β β β β 6 6 6 6 . . . . . nt nt nt nt nt nt nt nt nt nt nt 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 JP-A-2004-339417 SUMMARY OF THE INVENTION The object of the present invention is to provide a result of an effort to investigate the alicyclic epoxy resin of the 201029984 alicyclic epoxy resin without having an ester bond therein. The present situation, the present invention. That is, the present invention relates to: (1) a diene compound represented by the following formula (1):

0 (wherein a plurality of Han systems independently represent a hydrogen atom or an alkyl group); (2) an epoxy resin obtained by oxidizing the two persons described in the above (1); (3) The epoxy resin according to the above (2), which is obtained by oxidizing hydrogen peroxide or peroxy acid; (4) a curable resin composition containing the above (2) Or the epoxy resin and the hardening agent and/or the hardening catalyst described in (3). (5) A cured product obtained by curing the curable resin composition described in the above (4). The epoxy resin of the present invention does not have an ester bond in a molecular structure, and thus can provide a cured product excellent in mechanical properties. The curable resin composition of the present invention containing the epoxy resin of the present invention is extremely useful for a wide range of applications such as electrical and electronic material molding materials, injection molding materials, laminate materials, coating materials, adhesives, photoresists, and the like, especially because of low coloring property. Therefore, it is extremely useful for the optical material 201029984. [Embodiment] The diene compound of the present invention is obtained by reacting a cyclohexenealdehyde derivative with a trishydroxyalkylene derivative. The cyclohexenal derivative which can be used may, for example, be cyclohexenecarboxylic acid, methylcyclohexenecarboxaldehyde or ethylcyclohexenecarbaldehyde. Further, the trimethylolane derivative may be di-trimethylolpropane, di-trimethyloldecane, ditrishydroxymethylethane or di-trihydroxydecylbutane. The trishydroxyalkylene derivative is usually used in an amount of from 0.4 to 0.6 mol, preferably from 0 45 to 50 mol, per mol of the cyclohexene derivative. The diene compound of the present invention can be produced by a usual cyclic acetalization reaction. For example, a method in which a solvent such as toluene or xylene is used for azeotropic dehydration and a reaction is carried out in a reaction medium (U.S. Patent No. 2,945,8), and a phenol is gradually added after dissolving a polyhydric alcohol in concentrated hydrochloric acid. A method of carrying out a reaction (JP-A-48-96590), a method of using water in a reaction medium, (U.S. Patent No. 3,926, 〇), and an organic solvent in a reaction medium (Japanese Patent Laid-Open Publication No. Hei 7-215979) A method of using a solid acid catalyst (JP-A-2007-230992) or the like. In the present invention, any of the above methods may be used, and for example, a method in which a cyclohexenal derivative and a trimethylolane derivative are acetalized by a dehydration reaction under acidic conditions may be mentioned. This method is to add an acidic catalyst (such as an inorganic acid such as sulfuric acid or phosphoric acid: an organic acid such as toluenesulfonic acid, methanesulfonic acid or an ion exchange resin: heteropoly acid such as tungstic acid or molybdic acid, and an activity in a solvent such as toluene xylene; White clay, inorganic acid, vaporized tin, zinc-vaporized iron, other organic acid salts of acid 201029984, etc., are used for shrinkage. The reaction may also be carried out by azeotropic dehydration as needed. Further, the reaction can be carried out in a state in which the water becomes a two-layer system. The diene compound of the present invention synthesized in such a manner is a diuretic compound obtained by the above formula (1), and is generally in a liquid form.

The dilute of the present invention represented by the above formula (1) can be oxidized to form the epoxy tree & The method of oxidizing may be, for example, a method of performing oxygen by a peroxyacid such as peracetic acid or a method of oxidizing by a method of oxidizing hydrogen peroxide with air (oxygen), but is not limited thereto. Specific examples of the epoxidation by peroxyacid include the methods described in JP-A-2006-5218, and the like. In the epoxidation method of the hydrogen peroxide water, various methods can be applied, but in particular, Japanese Patent Laid-Open No. 591-8793, JP-A-621-2345 5G, Japanese Patent Laid-Open No. Hei-5-213919, and 曰The method disclosed in Japanese Laid-Open Patent Publication No. H-349579, Japanese Unexamined Utility Model Publication No. JP-A No. 2001-17864, and Japanese Patent Publication. 〇2 The following is a preferred method for obtaining the epoxy resin of the present invention. The reaction of the disaccharide compound and the polybasic acid salt of the present invention in an emulsified state of the organic agent, the buffer solution and the hydrogen peroxide water is as long as the polybasic acid used in the present invention has a polybasic acid structure. The material is not particularly limited, but preferably one is a polybasic acid containing tungsten or molybdenum and it is a tungsten-containing polydecanoic acid and a salt thereof, particularly preferably a tungstate.

Specific examples of the polybasic acid and its salts include: tungstic acid, 12·hesha acid A 201029984, hepatoic acid, 18-hesha acid, etc., such as salt, pin acid, π暇, 12-tungstenic acid, etc. An acid such as an acid or a molybdic acid acid such as phosphomolybdic acid, and the like. The relative masculine and soil-preserving winters (C〇Unter_Cati〇n) of these salts can be cited as four-level recordings, soil-like gold 4S ions, and metal ions. Alkaline earth metal ions such as money and magnesium ions are not limited to these. Specific examples of the ion, potassium ion, calcium ion, and ammonium ion include an alkali metal ion such as calcium ion, potassium or barium, and the like. The relative cation is sodium, and the amount of use is relative to the original isoric acid. The molar number of the crane atom is 1.0 to 20 millimoles, preferably millimole. Material 1 mole, converted to metal element (if, if it is molybdic acid, molybdenum atom molar 2.0~20 millimolar, more preferably 2.5~1〇 for 4 grade money salt) The ammonium salt having a carbon number of 10 or more, preferably 25 to 100, is preferably an aliphatic chain. The chain of the chain is preferably an aliphatic chain. The salt of the chain is exemplified by (12) ammonium. Salt), dilauryl dimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl group (mixture of a compound of a octyl group and a compound of a decyl group) ,··························································· And tris-hexadecylmethylammonium salt, dihardened tallow alkyl dimethyl ammonium salt, etc., but are not limited thereto. It is particularly preferable that the carbon number is 25 to 1 and the anion species of the salt is not particularly limited, and specific examples thereof include a derivative ion, a nitrate ion, a sulfate ion, and a hydrogen sulfate radical from 201029984. Acetate ion, carbonate ion, etc., but it is not limited to these. In the present invention, in particular, from the viewpoint of not containing dentate, a carboxylate ion, a sulfate ion, a hydrogen sulfate ion, an acetate ion, a carbonate ion or the like is preferably a carboxylate such as an acetate ion. Because there are fewer side reactions during epoxidation. When the carbon number exceeds 100, the hydrophobicity may become too strong, and the solubility in the aqueous layer of the 4-grade ammonium salt may be deteriorated. If the carbon number is less than 10, the hydrophilic enthalpy becomes strong, and similarly, the compatibility with the organic layer of the tetraammonium salt is deteriorated, which is not preferable. The amount of the graded salt used is preferably from 0.01 to 10 equivalents per equivalent of the valence (four) (preferably crane) used. More preferably, it is 0 05 to 6 〇 equivalent, and more preferably 0.05 to 4.5 times equivalent (where a particularly preferred range differs depending on the combination of the polybasic acid).

When G is, for example, a pseudo-acid, h2W〇4 2 is valence, and therefore it is preferably in the range of 〇.G2 〜2() molar relative to the humic acid i rabbit ear. Further, it is trivalent when it is acid, so it is preferably 〇3 to 2 〇 mol, and is * valence for (tetra) acid, so it is preferably 〇. 4 to 40 mil. When the amount of the secondary ammonium salt is less than the multiple of the valence of the polybasic acid, the soil oxidation reaction is difficult to carry out (the reaction proceeds rapidly depending on the case), and there is a problem that by-products are easily generated. When it is more than 1 〇 equivalent, not only the post-treatment becomes difficult, but also the effect of suppressing the reaction is caused, which is not preferable. Any of the buffers may be used, but it is preferred to use the acid salt in the reaction to dissolve the night. The pH thereof is preferably adjusted to be between pH 2 and 6, more preferably pH 3 to 5. 201029984 When less than PH2, the hydrolysis reaction of the epoxy group, and when it exceeds PH6, the reaction becomes extremely slow and should be easy to carry out. Too long a problem. The method of using the reaction time buffer may, for example, be a case of an acid- sulphate aqueous solution, or a scalar acid equivalent to a buffer of peroxidation #, or a squaric acid of dihydrogen sodium hydride. Use °, 1~10 (such as sodium hydroxide, potassium hydroxide, cesium to make a basic compound, etc.). H-adjusted I: This sodium bicarbonate, potassium carbonate force to make PH become the above pHn ^ two = ===添。!二=:Adjustment. The preferred squaric acid _ /0, more preferably 5~45% weight 〇 /0. 菫 菫 亩 ::: In this reaction, you can also use no buffer, do not adjust PH In the case of the U, the hydrate of the U is a dish. ; = 二二纳,三聚碟酸 is the non-secondary adjustment of the acid: straight == simple: the back refers to the direct addition is better. The amount of phosphoric acid used in this case is usually from 01 to 5 mol% equivalent = 4 mol% relative to hydrogen peroxide, more preferably 〇3 to 3 mol% equivalent. At this time, relative: hydrogenation 'right more than 5 mol% equivalent' must be adjusted pH, when not: 0.1 mol% equivalent, the following disadvantages occur: the hydrolysis of the resulting epoxide will become easier Carry out, or the reaction is slower, etc. This reaction uses hydrogen peroxide for epoxidation. The hydrogen peroxide used in the reaction is preferably a water mixture having a hydrogen peroxide concentration of 10 to 40% by weight because of its ease of use. When the concentration exceeds 40% by weight, the decomposing reaction of the epoxy resin generated in the operation becomes difficult. 201029984 is also easy to carry out, which is not preferable. This reaction uses an organic solvent. With respect to the amount of the organic solvent to be used, the weight ratio is 0.34 Å, preferably 〇3 to 5, more preferably 〇5 to 2.5, relative to the diene compound i which is the reaction substrate. When the weight ratio exceeds 10, the reaction becomes extremely slow and is not preferable. Specific examples of the organic solvent which can be used include an alkane such as hexane, cyclohexane or heptane, an aromatic olefin compound such as toluene or diphenylbenzene, decyl alcohol, ethanol, isopropanol, butanol or hexanol. And alcohols such as cyclohexanol. Further, as the case, ketones such as methyl ethyl ketone, decyl isobutyl ketone, cyclopentanone, and cyclohexanone, ethers such as diethyl ether, tetrahydrofuran, and dioxane may be used, and ethyl acetate or butyl acetate may be used. An ester compound such as methyl formate or a nitrile compound such as acetonitrile. The solvent of Optima is an aromatic olefin compound such as hexane, cyclohexan, Gengyuan, or the like, toluene or xylene. / For the specific reaction method, for example, when the reaction is carried out in batch mode, the dilute compound, hydrogen peroxide (aqueous solution), polybasic acid (catalyst), buffer, 4 ammonium salt and Organic solvent, in the second layer

y mixing. (4) Speed does not depend on ^. It may be a method of slowly adding after adding each component because (4) when hydrogen peroxide is added, it may be heated.

The reaction temperature is not particularly limited, and is preferably A and . The temple is 0~9〇°C, more preferably 0~75 C ’, especially 15C~60〇C. When the reaction temperature is too old, when drinking N, hydrolysis and inferiority are carried out, and when the reaction temperature is low, the shape should become extremely slow. Further, the reaction time may vary depending on the reaction temperature, the touch I, the yoke weight, etc., but from the viewpoint of industrial production, long-term reaction consumes a large amount of energy, which is not preferable. The preferred range is from 1 to 48 hours, more preferably from 〜3 to 36 hours, and even more preferably 11 201029984 is 4 to 24 hours. After the reaction is completed, excess hydrogen peroxide quenching treatment is performed. The quenching treatment is preferably carried out by using a basic compound for β, and a reducing agent and a basic compound are also preferred. A preferred treatment method is a method in which the residual hydrogen peroxide is quenched by using a reducing agent after the neutralization of the basic compound is adjusted to ρ Η 6 to 10. When the pH is not full, it is possible to generate a decomposition product when the excess hydrogen peroxide is reduced by heating. Examples of the reducing agent include sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, and vitamin C. In terms of the amount of the reducing agent used, the molar number of hydrogen peroxide relative to the excess amount is usually 0 01 to 2 Torr, more preferably 倍摩尔, and even more preferably 〇.05 to 3 times. Moor. The test compound may be a metal carbonate such as sodium hydroxide, potassium hydroxide, hydroxide, nitrogen oxide, metal hydroxide, carbonic acid steel or potassium carbonate, sodium phosphate, sodium hydrogen hydride, or ion exchange resin. Oxidation test +, in terms of the amount of use, when dissolved in water or organic solvents (eg ^, benzene, diphenylbenzene and other aromatic olefins, methyl isobutyl _, methyl ethyl ketone and other ketones, 袠 烧Glucan, octyl alcohol and other alcohols, methanol, ?, at, etc., in various solvents), such as alcohol, ethanol, isopropanol, etc., when used in excess of excess peroxide 'usually it is a Momo, preferably q is better than 〇. 〇5~3 for 苴 and is divided into pines, ear liquids... With water or the above organic solvents, add, or monomer The form is added. When the phase is not dissolved in water or an organic solvent (4), it is preferable to use a weight ratio of 201029984 times with respect to the amount of peroxidation gas remaining in the system. More preferably 10 to 500 times, and even more preferably 10 to 300 times. When a solid base which does not dissolve in an aqueous organic solvent is used, it may be treated after the aqueous layer and the organic layer described later are separated. After the quenching of the hydrogenated hydrogen (or before quenching), when the organic layer and the aqueous layer are not separated, or the organic solvent is not used, the organic solvent is added and operated, and the aqueous layer is extracted. The reaction product is taken out. The organic solvent used at this time has a weight ratio of 〇. 5 〜1 ’ 倍 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The organic layer separated by this operation may be washed and refined as needed, as needed. The obtained organic layer can be removed by using an ion exchange resin, a metal oxygen 4, an activated carbon, a composite metal salt, a clay mineral or the like as needed, and the water is washed and passed, and then the solvent is removed by (4) to obtain the desired ring shoulder. The purpose of the month. The epoxy resin of the present invention obtained by refining the human Hi-type by the column chromatography method or (4) may optionally be expressed as the main component of the formula (2).

(wherein there is a majority of alkyl groups)

R is a compound which independently represents a hydrogen atom or a carbon number of L 6 and is mixed with various structures represented by the formula (3): 13 201029984

P = H or CH3CO (wherein the combination of 'A to D' can be any combination). Further, a high molecular weight body obtained by polymerizing epoxy groups and other by-products are produced depending on the reaction conditions. The obtained epoxy resin can be used as, for example, various resin raw materials such as epoxy acrylate and a derivative thereof, a sulphur-based compound, and a cyclic carbonate compound. Hereinafter, the curable resin composition of the present invention containing the epoxy resin of the present invention will be described. The curable resin composition of the present invention contains the epoxy resin of the present invention as an essential component. In the curable resin composition of the present invention, two methods of thermal curing (curable resin composition A) using a hardener and cation hardening (curable resin composition B) using an acid as a curing catalyst can be applied. In the curable resin composition A and the curable group resin composition, the epoxy resin of the present invention may be used alone or in combination with other epoxy resins. When used in combination, the epoxy resin of the present invention accounts for 30% by weight or more, more preferably 40% by weight or more, based on the total epoxy resin. In particular, when the epoxy resin of the present invention is used as a modifier for the curable resin composition, it is added in an amount of from 1 to 30% by weight. 201029984 Other epoxy resins which can be used together with the epoxy resin of the present invention include: varnish type epoxy resin, bisphenol A type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin , phenol aralkyl type epoxy resin, and the like. Specific examples thereof include bisphenol A, bisphenol s, thiobiphenol (thi〇diphen〇1), bismuth, quinone, 4,4′-bisphenol, 2,2′-bisphenol , 3,3,5,5,·tetramethyl-[1,1'-bisphenol]-4,4,-diol, hydroquinone, resorcin, naphthalenediol, Tris-(4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, phenols (phenols, alkyl-substituted phenols, naphthols (naphth〇1), alkyl-substituted naphthols, dihydroxybenzenes, two Hydroxynaphthalene, etc. with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4' _bis ( Gas methyl)_1Γ _ biphenyl, 4,4' _ bis (methoxymethyl, -biphenyl, 14 bis (gas methyl) benzene, 14, bis (methoxy fluorenyl) benzene, etc. Polycondensate and such modified substances, functionalized bisphenols such as tetrabromobisphenol A, epoxy propyl ethers derived from alcohols, cycloaliphatic epoxy resins, epoxy propylamine epoxy resins, epoxy A propyl ester epoxy resin or a sesquioxane-based epoxy resin (in a chain, a ring, a ladder, or the like) A solid or liquid epoxy resin such as an epoxy resin having a glycidyl group and/or an epoxy-% hexane structure in a nonoxyne structure having a mixed structure of two or more types is not limited thereto. Two or more types may be used alone or in combination. In particular, when the curable resin composition of the present invention is used for optical applications, it is preferably used in combination with an epoxy resin having an alicyclic epoxy resin or a sesquioxane structure. In particular, in the case of an alicyclic epoxy resin, a compound having an epoxycyclohexene structure is preferred, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is preferred. 15 201029984 The epoxy resin may be exemplified by oxidation of a compound obtained by the following reaction: esterification of a cyclohexene carboxylic acid with an alcohol or acetalization of a cyclohexene methanol with a retinoic acid (Tetrahedron vol. 36 p. 2409 (1980), Tetrahedron Letter ρ·4475 (1980), etc., or Tishenko reaction of cyclohexenal (Japanese Unexamined Patent Publication No. 2003-170059, No. 2004-262871 Etc. The transesterification reaction of the cyclohexene carboxylic acid ester (the method described in JP-A-2002-52187). The alcohol is not particularly limited as long as it is a compound having an alcoholic thiol group, and examples thereof include: Ethylene glycol, propylene glycol, i 3 propylene glycol, • butanediol, 14 butanol, 1,5-pentanediol, iota, hexylene glycol, cyclohexane dimethanol, 2,4 diethyl pentane Glycol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricycl〇decane dimethan〇1, diols such as norbornenediol Triols such as dimethyl ether, dimethyl ketone, trimethoprim, trihydrocarbyl butyl, 2-hydroxymethyl-i, 4-butanediol, and tetraols such as pentaerythritol ditrimethylolpropane Wait. Further, the oxic acid may be oxalic acid, maleic acid 'fumaric acid, phthalic acid, isophthalic acid, adipic acid or cyclohexanedicarboxylic acid, but is not limited thereto. Further, an acetal compound obtained by reacting a cyclohexenal derivative with an acetal of an alcohol is exemplified. Specific examples of the 4 epoxy resin include: ERL_4221, UVR·6105 ' ERL_4299 (all trade names are made of dow chemical), and 2,21P, Yeppel, GT401, EHPE3150, EHPE 3150CE ( All the trade names are as follows (6) "匕学工业制制) and 二环戍二16 201029984 epoxides, but not limited to them (Reference: General Epoxy Basics P76-85). These may be used alone or in combination of two or more. Each of the curable resin compositions will be described below. Thermal curing by a curing agent (curable resin composition A) The curing agent contained in the curable resin composition A of the present invention may, for example, be an amine compound, an acid anhydride compound, a guanamine compound, a conjugate compound or a carboxy group. An acid compound or the like. Specific examples of the hardener which can be used include: ® diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diamine dipyridyl mill, isophorone diamine, dicyandione Polyamine resin synthesized from amine and linoleic acid and ethylene diamine, isophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride , methyltetrahydroisophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, butane tetracarboxylic anhydride, bicyclo [2, 2,1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3,4-tricarboxylic acid -3,4-anhydride, etc.; carboxylic acid resin, bisphenol A, bisphenol F, bisphenol s, bisphenol oxime obtained by addition reaction of various alcohols, carbitol modified polyfluorene oxide and the above anhydride , stilbene, 4,4,-bisphenol, 2,2'-bisphenol, 3,3,5,5,-tetramethyl-[1,1,·bisphenol]-4,4,- Glycol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane , phenols (phenols, alkyl-substituted phenols, naphthol, alkyl-substituted naphthols, dihydroxybenzenes, dihydroxynaphthalenes, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxyphenylhydrazine Aldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (gas 17 201029984 methyl)_1,1'-biphenyl, 4,4,-bis ( a polycondensate of methoxymethyl)-1,1,-biphenyl, 14,2-bis(methylmethyl)benzene, K.bis(methoxymethyl)benzene, and the like, and the modified substance, Self-chemical bisphenols such as bromobisphenol A, imidazole, boron trifluoride 1 amine complex, hydrazine derivative, condensate of phenol and phenol, etc., but are not limited thereto. These may be used alone or in combination of two or more. In the present invention, a compound having an acid needle structure and/or a carboxylic acid structure represented by the above acid anhydride or carboxylic acid resin is particularly preferred. The amount of the curing agent used in the curable resin composition A of the present invention is preferably from 7 to 12 equivalents based on the equivalent of the epoxy group of the total epoxy resin. When ◎ is less than 0.7 equivalents per equivalent of the epoxy group, or exceeds 1⁄2 equivalent, the hardening is incomplete and the good hardenability is not obtained. In the curable resin composition A of the present invention, a curing accelerator may be used in combination with a curing agent. Specific examples of the hardening accelerator which can be used include imidazoles such as methylimidazole, 2-ethylimidazole and 2-ethyl-4-mercaptoimidazole, and 2-(dimethylaminomethyl)-desir. 8-diaza-bicyclo(5,4,anthracene) eleven broken -7 and other third-order amines, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. In the case of using a hardening accelerator, it may be used in an amount of 0.1 to 5.0 parts by weight based on 1 part by weight of the total epoxy resin. The curable resin composition of the present invention may contain a filler-containing compound as a component imparting flame retardancy. The scaly compound may be a reactive type or an additive type. Specific examples of the filler-containing compound include trimethyl sulphate, triethyl silicate, tricresyl phosphate, trixylenyl phosphate, and stearylbenzene dibenzoate. Ester, tolyl-2,6-di-succinyl tris(diphenylene) ester, 1,3-phenylene di(dimonate di(diphenyl) 18 201029984 ester), 1,4-phenylene Phosphate such as bis(trimethylene benzene diphosphate), 4,4,-biphenyl (tris(xylylene) diphosphate); 9,1 〇 dihydro-9-oxa-10 - dish 菲 〇 〇 - oxide (9,10-dihydro-9-〇Xa_lo.phosphaphenanthrenelO-oxide), ❹ 10 (2,5_二经笨基)-1〇Η)-9-oxa- Phosphorus-containing compound such as 10-phosphorus-10 oxide; phosphorus-containing epoxy compound obtained by reacting epoxy resin with active hydrogen of the above-mentioned phosphine, red phosphorus, etc., preferably phosphate ester , a phosphine or a phosphorus-containing epoxy compound, particularly preferably 1,3-phenylene di(tris(monomethylbenzene) vinegar), 1,4_extended bis(tris(dimethyl)phosphate) ), 4,4, _biphenyl (tris(xylene) diphosphate) Or a phosphorus-containing epoxy compound. The content of the phosphorus-containing compound is preferably a phosphorus-containing compound/total epoxy resin = 〇丨 to 〇 6 (weight ratio). If the right side is less than 0.1, the flame retardancy is insufficient. If it exceeds 〇6, the hygroscopicity and dielectric properties of the cured product may be adversely affected. Further, the curable resin composition A of the present invention may optionally contain an antioxidant. The antioxidants which can be used include anticipating, sulfur-based, and dish-based antioxidants. The antioxidant may be used alone or in combination of two or more. The amount of the antioxidants to be used is usually 100 parts by weight, preferably 5 parts by weight, based on 100 parts by weight of the resin county in the curable resin composition of the present invention. The phosphorus-based resistance may, for example, be a plurality of antioxidants, a sulfur-based antioxidant, or the like. Examples of phenolic antioxidants include: 2 6 _ : tributyl phthalate, butylated bismuth phenol, hexamethylene phthalate octadecyl vinegar, and - second Butyl-4-pyridylphenyl)propionic acid isooctyl vinegar, 2,4.2. (n-octyl 201029984 thio)-6-(4-carbyl-3,5-di-t-butylaniline Mono-phenols such as 3,5,5-triazine, 2,4-di[(octylthio)methyl]-o-cresol; 2,2'-methylenebis(4-methyl- 6-t-butylbenzene), 2,2'-methylenebis(4-ethyl-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tributyl) Phenol), 44, _

Butylene bis(3-methyl-6-t-butylbenzene), triethylene glycol bis[3_(3_t-butyl-5-methyl-4-phenylphenyl)propionate] 1,6-hexanediol_bis[3_(3,5-di-t-butyl-4-phenylphenyl)propionic acid vinegar], N,N,·hexamethylene double (3 5_ Di(t-butyl-4-hydroxy-hydrocinnamate), 2,2·thiodivinylbis[3-(3,5-mono-t-butyl-4-phenylphenyl)propane Acid,],3,5-di-t-butyl-4,hydroxybenzylphosphonate-diethyl ester, ^^ bis-dimethyl butyl tert-butyl-4-hydroxymethylphenyl醯 醯 醯 丨 ethyl] 2 4 8 1 〇 tetraoxaspiro[5,5]undecane, bis(3 5_di-t-butyl-4-hydroxybenzyl sulfonate) calcium And other bisphenols; 1,1,3-tris(2-indolyl-4-hydroxy-5-t-butylphenyl)butane, 1,3'5-trimethyl-2,4,6- Tris(3,5-di-t-butyl-4-ylhydroxybenzyl) Ben, tetra-[methylene-3-(3',5,_di-t-butyl-4,-hydroxyphenyl) ) 丙 丙 酉曰 曱 曱 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、

睃]diol ester, tris-(3,5-di-tert-butyl-4-hydroxyl-based) iso-hydrogen hydrazide 1,3'5·di(3,5-di-third Base-4'-transbenzylidene)-s-triazine-2,4,6-(1Η'3Η,5Η)trione' adipose polymer type. Specific examples of the first-line antioxidant include, for example, 3,3, thiodipropionate, bismuth succinyl, 3, thiodipropionate, sucrose, 33, thiodipropionate Lipid esters, etc. Specific examples of the phosphorus-based antioxidants of triphenyl phosphite, phosphorous, and tris(nonylphenyl)phosphite include, for example, diphenylisodecyl acid ester and phenyl isodecyl phosphite 20 201029984 Xi Xi, Yi· Isodecyl pentaerythritol sub-acid S, bis(2,4-di-tert-butylphenyl) phosphite, cyclopentyne tetrakis(octadecyl) acetal (cyclicneopentanetetraylbis (octadecylphosphite) )), ring new bismuth tetrakis(2,4-di-t-butylphenyl) phosphite, cyclopentane tetrakis(2,4-di-t-butyl-4-methyl Alkyl phenyl linoleate, bis[2 _ tert-butyl·6·methyl-4-{2-(octadecyloxy)ethyl}phenyl]hydroarsenate Sulfate; 9,10-dihydro-9-oxa-10-phosphaphenanthracene oxide, 1〇_(35_di-t-butyl-4-hydroxyl- benzyl)-9, 10-Dihydro-9-oxa~ι〇_phosphaphenanthrene® oxide, 10-methoxyl-9,10·dihydro-9-oxa-l〇_phosphaphenanthrene _ Oxide, such as oxides, phenanthrene oxides, etc. These antioxidants may be used alone or in combination of two or more. In particular, in the present invention, a filled antioxidant is preferred. Further, the curable resin composition of the present invention may be added with a light stabilizer, a light stabilizer, or a hindered amine light stabilizer, especially HALS or the like. HALS is not particularly limited, and representative examples include dibutylamine, 13,5-triazine, N,N,_bis(2,2,6 6-tetramethyl-4-piperidinyl-16-hexa a cocondensate of decyldiamine with N-(2,2,6,6-tetramethyl-4-piperidinyl)butylamine, sulfonic acid monodecyl 1 (2-aminoethyl) _2,2,6,6-tetramethyl-derived co-condensate poly[{^1,1,3,3-®9-mercaptobutyl)amino-1,3,5-triazine-2, 4-diyl} {(2,2,6,6-tetramethyl-4-isopiperidinyl) fluorenylene}hexamethylene {(2,2,6,6-tetramethyl-4) Piperidinyl)histamine}], bis(1,2,2,6,6-pentamethyl-4 piperidinyl) [[3,5-bis(1 dimethylenediethyl)4. Phenyl]methyl]butylmalonate bismuth (2'2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(i,2,2,6,6- 21 201029984 Pentadecyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4(piperidinyl) sebacate, 2- (3,5-di-t-butyl-4-hydroxyl)diphenyl-2-bisbutylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidinyl) and the like. HALS can be used alone or in combination of two or more. Further, in the curable resin composition A of the present invention, a binder resin may be blended as needed. Examples of the binder resin include a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an Nbr-phenol resin, an epoxy-NBR resin, a polyamide resin, and a polyfluorene resin. Imine-based resin, polyfluorene-based resin, or the like, but is not limited thereto. The amount of the binder resin is preferably from 0 to 05 parts by weight, preferably from 0.05 to 20 parts by weight, based on 100 parts by weight of the resin component, depending on the range of flame retardancy and heat resistance of the cured product. Share. In the curable resin composition A of the present invention, an inorganic filler may be added as needed. Examples of the inorganic filler include cerium oxide, aluminum oxide, zircon, calcium silicate, calcium carbonate, cerium carbide, cerium nitride, boron nitride, cerium oxide, fosterite, and talc. Steatite), a powder such as spinel, titanium dioxide or talc, or a bead obtained by spheroidizing the same, but is not limited thereto. Especially when used for optical applications, it is preferred to use a nanometer size. These may be used alone or in combination of two or more. The content of the inorganic filler is from about 5% by weight to about 95% by weight based on the curable resin composition of the present invention. Further, the curable resin composition of the present invention may further contain a decane oxime agent, a stearic acid, a bismuth acid, a zinc stearate, a stearic acid or the like, a surfactant, a dye, a pigment, and the like. Various compounding agents such as ultraviolet absorbers and various thermosetting resins. 22 201029984 When the curable resin composition A of the present invention is used for an optical semiconductor sealing agent, a phosphor may be added as needed. The phosphor, for example, absorbs a portion of the blue light emitted by the blue LED element and emits a wavelength-converted yellow light' thus having the effect of forming white light. The fluorescent semiconductor is dispersed in the curable resin composition in advance to seal the photo-semiconductor. The Laoguang boat is not particularly limited, and conventionally used phosphors such as rare earth elements, thiogallate, orthosilicate, etc. can be used. More specifically, YAG fluorescence is used. Phosphors such as TAG, TAG phosphor, orthosilicate phosphor, thiogallate® phosphor, sulfide phosphor, etc., YA103 : Ce, Υ3Α15〇12 :

Ce, Y4Al2〇9: Ce, Y202S: Eu, Sr5(P04)3ci: Eu, (SrEu)〇. A1203 and the like. The particle size of the phosphor can be preferably from 1 to 250 // m, particularly preferably from 2 to 50 Am, using conventional particle size in the art. When the glare is used, the amount thereof is from 1 to 8 parts by weight, preferably from 5 to 60 parts by weight, per 100 parts by weight of the resin component. The curable resin composition A of the present invention is obtained by uniformly mixing the components. The curable resin composition A of the present invention can be easily formed into a cured product by the same method as in the related art. For example, the epoxy resin and the hardener of the present invention and the hardening accelerator, the hindrance compound, the binder resin, the inorganic filler, and the compounding agent which are added as needed may be sufficiently mixed using an extruder, a kneader, a roll, or the like. The curable resin composition is uniformly formed to obtain a curable resin composition, and the curable resin composition is molded by potting, melting (in the case of liquid without melting) injection molding or a transfer molding machine, and then 80 to 2 〇〇 ° C is heated for 2 to 10 hours to obtain a cured product of the present invention. Further, the curable resin composition A of the present invention is dissolved in toluene, dimethyl 23 201029984 benzophenone methyl ethyl ketone, methyl butyl butyl ketone, dimethyl ketoamine, dimethyl ethanoamine N-methyl η bilol A solvent such as ketone is used as a varnish for a curable resin composition, and then impregnated with a substrate such as glass fiber, carbon fiber, polycarbon fiber, polyacrylamide fiber oxidized fiber, paper, etc., and dried by heating to obtain a prepreg, which is pre-soaked. It is subjected to hot press forming, whereby it can be used as a cured product of the curable resin composition of the present invention. 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 of the present invention and the solvent. Further, the epoxy resin containing carbon fibers may be obtained by directly performing the liquid composition. Further, the curable resin composition A of the present invention can be used as a modifier of the film type composition. It can be used to improve the flexibility of the Bstage. The resin composition of the film type is applied to the release film in the form of the curable resin composition varnish of the present invention, and the solvent is removed in a heated state, followed by b-stage formation. A sheet-like adhesive form was obtained. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like. Next, the curable resin composition A of the present invention will be described as a sealing material for a photo-semiconductor or a die-filled material. When the curable resin composition A of the present invention is used as a sealing material or a viscous material of a light semi-conductive ray such as a high-brightness white LED, it is obtained by hardening a hardener containing the epoxy resin of the present invention. Additives such as a curing agent, a hardening accelerator, a decane coupling agent, an antioxidant, a light stabilizer, etc. are sufficiently mixed to prepare an epoxy resin composition' and used as a sealing material or for both a viscous material and a sealing material. . For the mixing method, the system 24 201029984 is mixed at room temperature or by heating using a kneading machine, a three-roll mill, a universal mixer, a planetary feeder, a homomixer, a homogenizer, and a bead mill f. High-brightness white LED calculation #Main-channel ray-semiconductor 7G parts are generally laminated on sapphire, sapphire, sapphire, sapphire, sapphire, Sic, Si, ZnO, etc. GaP, GaA, As, GaAsp, Ama, inp,

A semiconductor wafer such as A1N or InGaN is formed next to the lead frame heat sink and the package, and is also connected to a gold > 1 line which is used to pass current. In order to protect the semiconductor wafer from heat and moisture and to function as a lens, it is sealed with a sealing material such as epoxy wax. The curable resin composition A of the present invention can be used as the material (4) for this purpose. It is preferable from the viewpoint of engineering that the curable resin composition A of the present invention is used for both the viscous material and the sealing material. - In the method of using the curable resin composition A of the present invention to bond a semiconductor wafer to a substrate, the curable resin composition A of the present invention can be applied by dispensing H, dip, or screen printing. The semiconductor wafer is placed and heat-hardened, and the semiconductor wafer can be heated by a method such as hot air expansion type, infrared ray, or high frequency. The heating condition is preferably, for example, 8 Torr to 23 Torr, t, 1 minute to 24 hours, left 8 to reduce the internal stress generated during heat hardening, and may be pre-hardened, for example, 〇l2〇C, 30 minutes to 5 hours. Thereafter, the post-hardening is carried out under the conditions of 12 Torr to 18 Torr < t, 3 Torr to 10 hours. ^The sealing material is formed by injecting a sealing material into a mold frame into which the substrate of the semiconductor wafer is fixed in the above manner, and then injecting into the thermosetting to form a molding method, and injecting the bonding on the metal mold in advance 25 201029984 = The material 'a semiconductor wafer to be fixed on a substrate is impregnated thereto and subjected to hardening, and then a compression molding method such as demolding from a metal mold. The main inlet method can be exemplified by a dispenser, a transfer molding, and the like. For heating, a hot air circulation type, an infrared ray, a high frequency, or the like can be used. The heating condition is preferably, for example, 8 〇 to 23 〇〇 c, i minutes to 24 hours or so. In order to reduce the internal stress generated during heat curing, for example, it may be pre-cured at 80 ° C for 30 minutes to 5 hours, and then post-hardened under conditions of ΐ 2 〇 ΐ 8 〇 π for about 10 hours. © The cured product of the present invention obtained by curing the curable resin composition of the present invention can be used for various applications such as optical component materials. The term "optical material" generally means a material used for passing light such as visible light, infrared rays, ultraviolet rays, X-rays, and laser light through the material. More specifically, in addition to the LED sealing materials such as Lamp type and SMD type, the following may be mentioned. A material for a liquid crystal display device such as a substrate material such as a substrate material, a light guide plate, a polarizing plate, a phase difference plate, a viewing angle compensation film, an adhesive, or a polarizing element protective film in the field of a liquid crystal display. Moreover, it is expected to be a sealing material for a color pDp (plasma display) of a next-generation flat panel display, an antireflection film, an optical compensation film, a casing material, a protective film for a front glass, a substitute for a front glass, an adhesive, and use thereof. The mold material of the LED of the display device, the sealing material of the LED, the protective film of the front glass, the substitute material of the glass, the adhesive, and the substrate material in the plasma-addressed liquid crystal (pALC) display, the light guide plate, the cymbal, the polarized light Plate, phase difference plate, viewing angle compensation film, adhesive, polarizing element protective film, and protective film of front glass, front glass replacement material, adhesive, and field emission display in organic EL (electrical excitation 26 201029984 light-emitting element) display Various film substrates in the (FED), a protective film for the front glass, a front glass substitute material, and an adhesive. In the field of optical recording, there are: VD (Video Disc), CD/CD-ROM, CD-R/RW, DVD-R/DVD-RAM, MO/MD, PD (phase change disc), optical card (optical card) Disc substrate material, pick-up lens, protective film, sealing material, adhesive, and the like. In the field of optical machines, there are materials for lenses for still cameras, and scenery.

® finder prism, target prism, finder cover, and light-sensing section. In addition, the photographic lens and landscape device of the video camera. There are also projection lenses, protective films, sealing materials, and adhesives for projection televisions. A material for a lens of a light-sensing machine, a sealing material, an adhesive, a film, or the like. In the field of optical components, the fiber material around the optical switch of the optical communication system, the lens, the waveguide, the sealing material of the component, and the adhesive. Fiber optic material around the fiber optic connector, ferrule, sealing material, adhesive, etc. For light passive parts and optical circuit parts, there are lenses, waveguides, LED 密封 sealing materials, CCD sealing materials, and adhesives. Substrate materials, fiber materials, sealing materials for components, and adhesives around the optoelectronic integrated circuit (OEIC). In the field of optical fibers, there are lamps for decorative displays, light guides, industrial sensors, displays, signs, and the like, and communication infrastructure and digital optical fibers for connection in the home. A photoresist material for microlithography for LSI and super LSI materials. In the field of automobiles and conveyors, there are automotive reflectors, bearing guards 27 201029984 rings, gear parts, corrosion resistant coatings, switch parts, headlights, engine parts, package parts, various interior and exterior items, drive engines, brakes Oil tanks, anti-embroidered steel plates for automobiles, interior panels, interior materials, wire harnesses for protection _ bundles (Wire Harness), fuel hoses, automotive lamps, glass substitutes. Also, the train uses multiple layers of glass. And the toughness agent for the structural materials of the aircraft, the engine peripheral components, the wire harness for the protection-bundling (Wire Harness), and the corrosion-resistant coating. In the field of construction, there are materials for interior and processing, such as electric shields, sheets, glass interlayer films, glass substitutes, and solar cell peripheral materials. For agricultural use, there is a film for casing coating. Next-generation optoelectronic functional organic materials include organic EL element peripheral materials, organic light-refracting elements, optical amplification for optical-light conversion devices, optical computing elements, substrate materials around organic solar cells, fiber materials, and sealants for components. , adhesives, etc. Examples of the sealant include a potting, a dipping method, a transfer molding seal, an IC, an LSI COB, a c〇F, a capacitor, a transistor, a diode, a light-emitting diode, a 1C, an LSI, and the like. Perfusion sealing flip chip for TAB, etc. (4) p

(Chip), such as primers, BGA, csp, etc., for sealing in IC package type (reinforcing primer). Further, the curable resin composition A of the present invention can be used for a general use of a thermosetting resin such as an epoxy resin, specifically, an adhesive, a coating material, a coating agent, and a molding material (including a sheet and a film). In addition to the sealing material, the male material, the sealing material, the cyanic acid resin composition for the substrate, the curing agent for the photoresist, the acrylic vinegar resin, and the like, and the like, and the insulating material (including the printed circuit board and the electric wire coating). Addition to additives such as other resins. Examples of the following agents include: civil engineering, construction, automotive, and general affairs. 28 201029984 An adhesive for medical use and an adhesive for electronic materials. Among these, an adhesive for an electronic material may be an interlayer adhesive such as a build-up substrate or the like, an adhesive for a die bond, a semiconductor adhesive such as an under-fill, or a BGA. An adhesive for bonding, such as a primer for reinforcing, an anisotropic conductive film (ACF), or an anisotropic conductive paste (ACP). Examples of the sealant include a potting, a dipping method, a transfer molding seal, a 1C, an LSI COB, a COF, a TAB, etc. for a capacitor, a transistor, a diode, a light-emitting diode, a 1C, an LSI, or the like. Seals for use in the 1C package, such as priming, FHp 〇chip, and QC, bga, CSP, etc. (including reinforcing primer). Curable resin composition B (cation hardening by an 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, various conventional compound materials such as a diluent, a polymerizable monomer, a polymerizable oligomer, a t-starting adjuvant, and a photosensitizer may be contained. Further, various conventional additives such as an inorganic filler, a coloring pigment, an ultraviolet absorber, an antioxidant, and a stabilizer may be contained as needed. The acid hardening catalyst is preferably a cationic polymerization initiator, and a photocationic polymerization initiator is particularly preferred. The cationic polymerization initiator may be a rust salt such as an iodonium salt, a salt or a diazonium salt, and these may be used alone or in combination of two or more. Examples of active energy ray cationic polymerization initiators are: metal trifluoride (tetra) (U.S. Patent No. 3,375, 653), bis (all-combustion base) methane metal salt (U.S. Patent No. 3,586,616), aryl diazonium Salt compound (US 29 201029984 National Patent No. 3708296), aromatic rust salt of the via element (U.S. Patent No. 4058400), aromatic sulfonium salt of the Va element (U.S. Patent No. 4,609,905), and Ilia to Va elements Bis-carbonyl chelate (U.S. Patent No. 4,406,091), thiopyrylium salt (U.S. Patent No. 4,139,655), group VIb of MF6t ionomorphism (U.S. Patent No. 4,161,478; Phosphorus, antimony and arsenic), aryl sulfonium salts (U.S. Patent No. 4,231,951), aromatic iodonium salts and aromatic rust salts (U.S. Patent No. 4,256,828), and bis[4-(diphenylfluorenyl) Phenyl]sulfide-dihexafluorometal salt (Journal of Polymer Science, Polymer Chemi stry, Vol. 2, item 1789 (1984)). Further, it is also possible to use a mixed ligand metal salt of an iron compound and a sulphuric alcohol-ingering compound. Further, specific examples include "Ajaccio Optoma SP150", "Adoca Optoma SP170" (all manufactured by Asahi Kasei Kogyo Co., Ltd.), "UVE-1014" (manufactured by General Electric Co., Ltd.), "CD" -1012" (made by sartomer company), "RP-2074" (made by Rhodia Corporation), etc. The amount of the cationic polymerization initiator to be used is preferably 〇01 to 5 parts by weight, more preferably 〇H0 by weight, based on 100 parts by weight of the total epoxy resin component. Further, the photocationic polymerization initiator may be used in combination with two or more kinds of conventional polymerization initiator adjuvants and photosensitizers. Examples of the polymerization starting adjuvant include, for example, benzoin, benzil, benzoin methyl ether, benzoin isopropyl ether, phenelzine, 2,2-didecyloxy Acetophenone, 1,1-dioxaacetophenone, hydroxycyclohexyl phenyl ketone, 2-methyl-1(4-methylthiophenyl)-2-morpholinolpropanone, N, N-dimethylaminoacetophenone, 201029984 2: mercaptopurine, 2_ethylhydrazine, 2_t-butylhydrazine, anthraquinone, amyl-based 2-isolated sigh Dylone, 2,4-dimethylthiophenone, 2,4-diethyl thiodone, 2,4-diisopropyl thiodone, acetophenone dimethyl acetal, diphenyl hydrazine, A photoradical polymerization initiator such as 4-methyldiphenyl-, 4,4,-di-diphenyl ketone, H-di-diethylamine-based ketone or Michler's ketone. The amount of the polymerization starting adjuvant used in the photoradical polymerization initiator or the like is from 0.01 to 30 parts by weight, preferably from 0.1 to 10 parts by weight, per part by weight of the photo-radical polymerizable component. . Specific examples of the light sensitizer include onion, 2-isopropylthiophenone, 2,4-dimethylthiophenone, 2,4-diethylthione, and 2,4_diiso Propyl thiotonone, acridine orange, acridine yellow, phosphine R, benzoflavine, thioflavin T, N N dimethyl dimethyl benzoate, isoamyl N,N-dimethylaminobenzoate, triethanolamine, diethylamine, and the like. The amount of the photosensitizer used is 0.01 to 30 parts by weight, preferably 〇_1 to part by weight, based on 100 parts by weight of the total epoxy resin component. Further, in the curable resin composition B of the present invention, various compounding agents such as an inorganic filler, a dreaming agent, a coupling agent, a pigment, and a pigment, and various thermosetting resins may be added as needed. The specific examples are as described above. The curable resin composition B of the present invention is obtained by uniformly mixing the components. Further, it may be dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone or 7"-butyrolactone and homogenized, and then used by drying to remove the solvent. The solvent at this time is usually used in an amount of 10 to 70% by weight, preferably 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 hardened by the external irradiation of violet « * 31 201029984 , and the ultraviolet irradiation amount varies depending on the curable resin composition, and therefore depends on the respective hardening conditions. The irradiation amount which is hardened by the photocurable curable resin composition may be any curing condition which satisfies the cured product and has good strength. In the case of this hardening, since the light must penetrate the fine portion, the cyclic enamel resin of the present invention and the curable resin composition B are preferably higher in transparency. Further, the photocuring of the epoxy resin is difficult to completely cure only by light irradiation, and in applications requiring heat resistance, it is necessary to completely complete the reaction hardening by heating after light irradiation.加热 The heating after the above light irradiation is preferably in the range of the hardening temperature of the usual curable resin composition B. For example, the range of room temperature ～15 (rc, 3 〇 minutes to 7 days is appropriate. The temperature varies depending on the blending of the curable resin composition B, but in particular, the higher the temperature range, the more the hardening promotion after light irradiation It is effective, and it is effective in heat treatment for a short period of time. Further, the lower the temperature, the longer the heat treatment is required. The heat-hardening can also produce an effect such as aging treatment. Moreover, the curable resin composition The shape of the hardened material obtained by hardening B may be various shapes depending on the application, and is not particularly limited, and may be formed into a shape such as a film, a sheet, or a block. The method of forming depends on the applicable part and member. Further, examples of the method include a casting method, a casting method, a screen printing method, a spin coating method, a spray method, and a transfer method such as a transfer method, but they are not It is limited to these. The forming die can use a ground glass, a hard stainless steel grinding plate, a polycarbonate plate, a polyethylene terephthalate plate, a polymethyl methacrylate plate, etc. It is also a lifting mold for 32 201029984. It For the release property, a polyethylene terephthalate film, a polycarbonate film, a polyethylene film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyamide film, or the like can be used. For example, in the case of a cationically curable photoresist, first, a photocation of the present invention dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanyl or r-butyrolactone by a method such as screen printing or spin coating. The curable resin composition B is applied to a substrate such as a copper-clad laminate, a ceramic substrate or a glass substrate with a film thickness of 5 to 160 to form a coating film, and then the coating film is pre-dried at 6 〇 to 11 〇❹ C. Thereafter, the negative film of the desired pattern is irradiated with ultraviolet rays (for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a laser beam, etc.), followed by exposure and post-baking at 70 to 120 ° C. Thereafter The unexposed portion is dissolved and removed (developed) in a solvent such as polyethylene glycol monoethyl ether, and further, if necessary, further irradiated with ultraviolet rays and/or heated (for example, 100 to 200 c for 0.5 to 3 hours). Harden to harden In this way, a printed wiring board can be obtained. _ The cured product of the curable resin composition B of the present invention can be used for various applications such as optical component materials, etc. The term "optical material" generally means A material such as visible light, infrared ray, ultraviolet ray, or xenon ray laser that passes through the material. More specifically, in addition to a sealing material for LEDs such as a lamp type (Samp type) and an SMD type, the following may be mentioned. In the liquid crystal display field, a substrate material, a light guide plate, a prism sheet polarizing plate, a phase difference plate, a viewing angle compensation film, an adhesive, a polarizing element protective film, and the like are liquid crystal display device materials such as liquid crystal display devices. Next generation flat panel display color · ρΒρ (plasma display) sealing material 33 201029984 material, anti-reflection film, optical compensation film, outer casing material, front glass protective film, front glass replacement material, adhesive, and used in led The mold material of the LED of the display device, the sealing material of the LED, the protective film of the front glass, the substitute material of the front glass, the adhesive, and the plasma-addressed liquid crystal (PALC) The substrate material, the light guide plate, the cymbal sheet, the polarizing plate, the phase difference plate, the viewing angle compensation film, the adhesive, the polarizing element protective film, and the protective film of the glass in the organic EL (electroluminescence) display in the display The front glass replaces the material, the adhesive, and various film substrates in the field emission display (FED), the protective film of the front glass, the front glass substitute material, and the adhesive. The field of optical recording includes: VD (Video Disc), CD/CD-ROM, CD-R/RW, DVD-R/DVD-RAM, MO/MD, PD (phase change disc), optical card (〇ptical car ( i) Disc substrate material, pickup-up lens, protective film, sealing material, adhesive, etc. In the field of optical equipment, there are materials for lenses for still-life cameras, finder prisms, and targets. Target (target prism), finder cover, and light-receiving unit. Also, the photographic lens and landscape device of the video camera, as well as the projection lens, protective film, sealing material, and adhesive agent of the projection TV. The lens material, sealing material, adhesive, film, etc. of the machine. In the field of optical components, the fiber material around the optical switch of the optical communication system, the lens, the waveguide, the sealing material of the component, the adhesive, etc. Optical fiber materials, ferrules, sealing materials, adhesives, etc. Light passive parts and optical circuit parts include lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, etc. Optoelectronic integrated circuits (OEIC) Around Substrate materials, fiber materials, sealing materials for components, etc. In the field of optical fibers, there are illuminations for decorative displays, light guides, etc., sensors, displays, labels, etc. for industrial applications, and communication infrastructure. And optical fiber for connecting digital devices in the home, photoresist materials for microlithography for LSI and super LSI materials, and automotive lampshades for automotive and conveyors. Reflector), bearing retainer, gear part, resistance coating, switch part, headlight, engine parts, package parts, various internal and external items, drive engine, brake oil tank, automotive anti-embroidered steel plate, interior plate ( Interior panel), interior materials, protection _ wire harnesses (Wire Harness), fuel hoses, car lights, glass substitutes. Also, multi-layer glass for trains, and toughness agents for aircraft structural materials, engine periphery Components, protection - wire Harness, money-resistant coating. Built in the construction sector , processing materials, electric masks, sheets, glass interlayers, glass substitutes, solar cell peripheral materials. For agricultural use, there are films for shell coating. The next generation of photoelectric functional organic materials are organic EL components surrounding materials, organic The light-refracting element, the light ◎ amplifying element of the optical-light conversion device, the optical computing element, the substrate material around the organic solar cell, the fiber material, the sealing agent of the element, the adhesive, etc. The sealing agent may be a capacitor or a transistor. Infusion sealing flip-chip for use in infusion, immersion, transfer molding, 1C, LSI COB, c〇F, TAB, etc. for diodes, light-emitting diodes, 1C, LSI, etc. call

Seals for use in the package of IC packages such as Clnp), BGA, csp, etc. (reinforcing primer), etc. For other uses of the optical material, the curable resin composition B is used. General use, such as adhesives, coatings, coating agents, 35 201029984 molding materials (including sheets, films, FRP, etc.), insulating materials (including printed substrates, wire coatings, etc.), sealants, etc. Addition to additives such as resins. Examples of the binder include civil engineering, construction, general use for automobiles, and medical adhesives, and an adhesive for electronic materials. Among the above-mentioned adhesives for electronic materials, an interlayer adhesive such as a multilayer substrate such as a buiid-up substrate, an adhesive for a semiconductor such as a binder or an under-layer (under_fiu), and a primer for BGA reinforcement can be used. An adhesive such as an anisotropic conductive film (ACF) or an anisotropic conductive paste (ACP). EXAMPLES Next, the present invention will be more specifically described by way of Examples, and the following "parts" means parts by weight unless otherwise defined. Further, the present invention is not limited to the embodiments. In another example, the epoxy equivalent was measured using JIS K 7236, and the viscosity was measured at 25 ° C using an E-type viscometer. In the gas chromatography method (hereinafter referred to as "GC", the separation column uses HP5-MS (0.25 mm I.D.xl5m' film thickness 0 25 /zm), and the column heater temperature is set to the initial stage. The temperature is 〇(TC, which is raised at a rate of 15«>c per minute and is maintained at 30 (TC for 25 minutes. Helium is used as a carrier gas. Further, knee penetration chromatography (hereinafter referred to as "GPC") The measurement is as follows.

Shodex SYST EM-21 column (KF-803L, KF-802.5 (x2 root), (KF· 802), connected eluent using tetrahydrofuran, flow rate is [my minute column temperature is 40 °C] and the detection is UV (254 nni) was carried out, and the calibration curve was made of standard polystyrene made of Shodex. Example 1 150 parts of water, 3 -cyclohexyl hydrazone 201029984, 55.1 parts, di-trishydroxyl was added while filling with gas. 62 parts of propane-based propane and 73 parts of concentrated hydrochloric acid to a flask equipped with a stirrer, a reflux cooling tube and a stirring device, and reacted at 6 (rc for 1 hr. After the reaction was completed, 100 parts of water and 3% aqueous solution of sodium hydroquinone were added. The portion is further neutralized with dihydrogen hydride, and the methyl isobutyl ketone portion is added thereto, and after water washing three times with water, the solvent and the like are removed to obtain a formula (4). The diphosic compound (D_1) of the present invention is 1 part by weight.

The obtained compound was in the form of a liquid, and the purity obtained by GC was 94% Gpc, and the purity was confirmed to be 98%. The viscosity is 21 〇〇〇 mPa. s (25 ° C E-type viscometer). Example 2 15 parts of toluene, 5 parts of cyclohexene formaldehyde 55.1, and 1.6 parts of mono-dimethylolpropane were added while being filled with nitrogen, and ij parts of a benzene sulfonate were supplied to a mixer. The reflux cooling tube, the mixing device, the Dean_surkf flask, and the refluxing condition - while removing water - were reacted for hours. After the reaction was completed, 3 parts of sodium dipolyphosphate was added, followed by 1 Torr. After 匚 stirring for W minutes, it was carried out; it was treated with the addition of 2 parts of toluene and 1 gram of weight (tetra) of dihydrogen hydride solution, and it was washed with water and washed three times with 100 parts of water. After the addition of the methyl group W#', the water is washed three times with water (10 parts), and then the tooth, the preparation, and the like are added to obtain 8 parts of the diene compound (D-2) of the present invention represented by the above formula (4). The purity obtained by GC was 98% purity. The viscosity was such that the shape of the obtained compound was liquid. The analytical analysis obtained by GPC was confirmed to be 37 93% 201029984 22000 mPa · s (25 〇C E type viscosity meter). Example 3 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, 0.78 of disodium hydrogen phosphate, and 2.7 parts of dihardified tallow alkyl dimethylacetate (50% by weight of hexane solution by LION AKZO) were added while nitrogen gas was applied. After a flask equipped with a stirrer, a reflux cooling tube, and a stirring device to form a tungstic acid catalyst, 120 parts of toluene and the compound (D-2) of the formula (4) obtained in Example 2 were added, and then borrowed. The liquid is in an emulsified state by stirring again. The solution was heated to 50 ° C, and 55 parts of 35% hydrogen peroxide water was added thereto while stirring vigorously, and the mixture was stirred at 50 ° C for 30 hours. The progress of the reaction was confirmed by GC, and as a result, the conversion ratio of the substrate after completion of the reaction was > 99, and the peak of the raw material disappeared. After neutralizing with a 1% aqueous sodium hydroxide solution, 25 parts of a 20% aqueous sodium thiosulfate solution was added and stirred for 30 minutes, and then allowed to stand. The organic layer separated into two layers was taken out, and 20 parts of crushed gum (WAKO-GEL C-300), 10 parts of activated carbon (CAP SUPER by NORIT), and 20 parts of bentonite (hojun yuejjj) were added thereto. After stirring at room temperature for 1 hour, filtration was carried out. The obtained liquid was washed with water three times with 100 parts of water, and the organic layer obtained was distilled off to obtain an organic solvent, whereby 99 parts of the epoxy resin of the present invention containing the compound represented by the following formula (5) as a main component was obtained.

As a result of measurement by GPC, it was confirmed that the compound (EP-1) containing the skeleton of the formula (5) was 85%. Further, the viscosity is 230 mPa.s (25 °C E-type viscometer), and the epoxy 38 201029984 equivalent is 264 g/e.q. Next, 20 parts of the obtained epoxy resin (EP-1), 40 parts of silicone (WAKO-GEL C-300), and 100 parts of toluene were added, and after sufficiently stirring, the solvent was distilled off by a rotary evaporator. The obtained epoxy group-containing phthalocyanine was packed on a ruthenium tube column which was previously laminated in 200 parts, and the developing solvent was used as a hexane: ethyl acetate = 9 : 1 to hexane: ethyl acetate 1: 9 In such a manner of slowly increasing the polarity, the compound of the above formula (5) is separated by a silica gel column chromatography, and the obtained fraction is recovered by a solvent using a rotary evaporator, whereby a colorless compound of the above formula (5) is obtained. (EP-2). The epoxy equivalent is 244 g/eq, and the viscosity is 140 Pa·s (the purity of the 25° CE type viscometer and GPC is about 95%. 〇 The epoxy resin (Epj, EP-2) of the present invention obtained in Example 3' Use of mercapto hexahydrophthalic anhydride (Nippon Chemical and Chemical Co., Ltd., Ricahside MH700G, hereinafter referred to as H1) as a hardener, using Hexadecyl Tridecyl Ammonium Hydroxide (Tokyo Chemical Industry Co., Ltd. a 25% sterol solution, referred to as C1) ❾ as a hardening accelerator, and blended in a mixing ratio (parts by weight) shown in Table 1 below, followed by defoaming for 20 minutes to obtain the curability of the present invention. Resin composition. (Heat resistance test: DMA) After the vacuum defoaming of the curable resin composition obtained in Example 3 was carried out for 2 knives, a 7 mm wide, 5 cm long, and 8 (10) thick melon was slowly injected. The test piece was a metal mold, and then the polyimide film was covered from above. The main type was cured under the following conditions to obtain a test piece for dynamic viscoelasticity. The dynamic viscoelasticity test was carried out under the conditions shown in the test pieces. 39 201029984 Hardening condition 120°C xl hour + 150°C x3 hour test Conditional dynamic viscoelasticity measuring device: Manufactured by TA-instruments, DMA-2980 Measuring temperature range: -30 ° C to 280 ° C Heating rate: 2 ° C / min Test piece size: using a product obtained by cutting out 5 mm x 50 mm (thickness about 800 // m). Analytical conditions

Tg: The peak point of Tan-5 at the time of DMA measurement was taken as Tg. (Thermo-mechanical property test: TMA) The curable resin composition obtained in Example 3 was subjected to vacuum defoaming for 20 minutes, and then injection molded with a 0 5 mni tube made of Teflon (registered trademark) to make the injection type. The test piece was obtained by hardening under the above conditions. Using this test piece, the heat resistance test was carried out under the conditions shown below. Measurement conditions Dynamic viscoelasticity tester: Vacuum technology (stock) system TM-7000 Measurement temperature range: 4 (TC~250 °C Heating rate: 2 °C / min Test piece size: using cut out 0 5 mm 10 mm 201029984 Table 1 Example 4 Example 5 Composition Epoxy Resin EP-1 5.28 EP-2 4.88 Hardener H1 3.36 3.36 Hardening Catalyst C1 0.02 0.02 Heat Resistance Test Results DMA Tan (5 (°C) 210 217 Thermomechanical Characteristic test results TMATg (°C) 181 186 Examples 6, 7 and Comparative Examples 1, 2 0 The epoxy resin (EP-1) of the present invention obtained in Example 3, as a comparative example (3, 4- Epoxycyclohexylmethyl-(3,4-epoxy)cyclohexylformate (ERL-4221 epoxy equivalent 140g/eq·hereinafter referred to as EP-3) manufactured by Dow Chemical Co., Ltd., using H1, cyclohexane- 1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn, manufactured by Mitsubishi Gas Chemical Co., Ltd., hereinafter referred to as H2) was used as a curing agent, and C1 was used as a curing accelerator, and is shown in Table 2 below. The blending ratio (parts by weight) was blended, and defoaming was carried out for 20 minutes to obtain a curable composition of the present invention. The resin composition was subjected to an LED test in the following manner. The hardening conditions were pre-hardening at 120 ° C for 1 hour, and then 150 ° C for 3 hours. (LED test) Hardening of Examples 6, 7, and Comparative Examples 1, 2 The resin composition was subjected to vacuum defoaming for 20 minutes, and then filled into a syringe and injected into a 5 mm square surface-mount type LED having a light-emitting element having an emission wavelength of 465 nm, using a precision discharge device. Hardening conditions are hardened to obtain test LEDs. 201029984 (LED lighting test) The lighting test is a lighting test for a substrate with a test LED for a predetermined current, that is, twice the current of 30 mA. The measurement conditions are as follows. The measurement item is measured by using an integrating sphere to measure the illuminance after lighting for 200 hours, and the illuminance retention rate of the test LED is calculated. The detailed conditions of the illumination are: 465 nm. Driving method: constant current mode, 60 mA (determined current of the light-emitting element) 30 mA) Drive environment: 85 ° C, 85% Evaluation: illuminance after 200 hours and its illuminance retention rate Table 2 Example 6 Comparative Example 1 Example 7 Comparative Example 2 Composition Epoxy resin EP-1 5.28 5.28 EP-3 2.80 2.80 Hardener H1 3.36 3.36 1.25 1.25 H2 1.25 1.25 Hardening catalyst C1 0.02 0.02 Illumination after 200 hours of LED lighting test (mW) 6217 4570 6717 6707 Illuminance retention rate (% 86 78 82 76 From the above results, it can be understood that the epoxy resin of the present invention does not have an ester bond in its resin skeleton, and the LED light test result is clear that it can provide light and humidity which can also withstand LED, A cured product with excellent thermal properties and electrical properties. The present invention will be described in detail with reference to the specific embodiments thereof. It is to be understood that various modifications and changes can be made without departing from the spirit and scope of the invention. Further, the present application is based on a patent application filed on Oct. 6, 2008 (Japanese Patent Application No. 2008-259469), which is incorporated herein by reference. Further, all of the reference portions cited herein are used in the present invention. [Simple description of the diagram] ® None [Key component symbol description] None 43

Claims (1)

201029984 VII. Patent application scope: 1. A diene compound represented by the following formula (1): (wherein a plurality of alkyl groups of R 6 to 6 are present). Each of the hydrogen atoms or the carbon number is independently an epoxy resin, which is obtained by oxidizing the compound of the object of the invention. The diene of the target range 1 = the epoxy resin of the second application of the patent range, which is obtained by oxidation of hydrogen or peroxyacid. Oxidation 4. The hardenable resin composition contains the epoxy resin and hardener and/or hardening catalyst of the patent application or item 3.匕5.- Kind of hardened material, which is obtained by hardening the sclerosing tree of the patent application scope*. None 44