TW201247746A - Epoxy silicone resin and hardening resin composition using same - Google Patents

Abstract

Provided are: a thermosetting resin composition a hardened material of which has high hardness, which has excellent heat resistant colorability, ultraviolet resistant colorability, strength and flexibility, which causes less damage to a package under a heat cycle, and which is suitable in the field of electronic materials or for optical semiconductor encapsulation; and an epoxy silicone resin suitable therefor. This epoxy silicone resin is represented by general formula (1) and has an epoxy equivalent of 170-2000 g/eq. This thermosetting resin composition comprises this epoxy silicone resin (A) as an epoxy resin component, a hardener (B) and a hardening accelerator (C). (In the formula, R1 represents a hydrocarbon group, m represents a number of 01 is a diglycidyl isocyanuryl-propyl group represented by formula (2), and Z is a divalent organic residue in which both termini are carbon atoms and which contains an Si atom inside.)

Description

201247746 VI. Description of the Invention [Technical Field] The present invention relates to an epoxy epoxy resin having a linear or cyclic decane bond, and optical properties, hardness, bending properties, heat resistance thereof as essential components thereof A thermosetting resin composition excellent in coloring property and light resistance coloring property, in particular, a thermosetting resin composition suitable for the field of electronic materials or optical semiconductor materials. [Prior Art] Epoxy resin is excellent in electrical properties, adhesion, heat resistance, etc., and is mainly used in many applications in the field of coatings, soil and electrical fields. In particular, aromatic epoxy resins such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, phenol novolak epoxy resin, and cresol novolak epoxy resin are water resistant, Since it is excellent in adhesiveness, mechanical properties, heat resistance, electrical insulation, economy, and the like, it can be widely used in combination with various curing agents. However, since these resins contain an aromatic ring, they are susceptible to deterioration by ultraviolet rays and the like, and are limited in use in the field of seeking weather resistance and light resistance. Since the epoxy resin composition has high hardness due to the cured product, it is excellent in handleability, and it is often used for low-output applications because it can obtain necessary durability for low-output white LED package applications. However, in high-output LEDs, it is susceptible to discoloration due to an increase in the amount of luminescence or heat generation, and it is difficult to obtain a sufficient life. In order to prevent discoloration caused by an increase in calorific value, an epoxy resin exhibiting a high glass transition temperature may be used, but such an epoxy resin-5-201247746 is highly elastic, and bending properties such as strength and deformability are lower than normal. The epoxy resin 1 also has a problem that the sealing material is easily cracked or the like in an environment that can cause cutting processing such as cutting or rapid temperature change. In addition, with the short-wavelength of the LED light-emitting wavelength in recent years, if it is used continuously, there is also a problem that the library is discolored and the light-emitting output is easily lowered. Therefore, in the package material, improvement in heat resistance coloring property and light resistance is further sought, and mechanical strength is obtained. In recent years, the development of LED packaging materials using a silicone resin having excellent heat resistance and light yellowing resistance as a substrate has been underway, and a resin composition obtained by an addition reaction of anthrahydroquinone with an alkenyl group or a curing agent is used. A resin composition obtained by hardening an epoxy group of an epoxy resin has been reported. However, the epoxy resin or the epoxy resin having a ruthenium skeleton in the main chain has many high flexibility derived from the oxime skeleton, but has disadvantages in that the hardness of the cured product is low, the surface is liable to be sticky, or the strength is low. . Therefore, it is easy to cause deterioration in transparency such as adhesion of dust, difficulty in handling property at the time of LED production, and limitation in production method, composition, design, and use. Further, a resin containing a phenyl group having a high hardness of a ruthenium skeleton. The operability is improved, but there are problems in strength and deformation, and there are disadvantages such as sudden cracking of the temperature due to sudden temperature change when the lamp is turned off. A resin having a low epoxy group equivalent of an epoxycyclohexyl group can improve the workability such as surface hardness, but it does not have the heat-resistant coloring property which is detrimental to the advantages of hydrogen peroxide, and is not able to withstand the requirements as an LED package material, and seeks further improve. Further, the resin composition composed of the organic olefin compound and the organopolysiloxane having a hydrogen group can be improved in terms of strength and yellowing. Moreover, the LED factor of 201247746, which is mounted on the backlight of a mobile phone or a monitor, is many. Therefore, it is necessary to pass the reflow process of the soldering package once on the circuit board. The lead-free solder package LED package that is exposed to the environment is exposed to a reflow oven at about 260 ° C. Therefore, the color change of the package, the crack, and the adhesion of the package and the bonding site are not affected by the sharp temperature change. In the event of damage to the line breakage caused by the expansion of the package material, the improvement in yield and productivity is sought. In this way, even if the epoxy resin having excellent weather resistance is used as the substrate, it is impossible to obtain the physical properties required for the LED package, and it is required to have sufficient hardness, strength, and deformability, and it is excellent in heat-resistant coloring and UV-resistant coloring. A material having the same mass productivity and workability as an epoxy resin. In Patent Document 1, a polyorganosiloxane having an anthracene hydrogen group and a polyorganosiloxane having an alkenyl group have been disclosed. The resin composition obtained by the addition reaction. Patent Document 2 discloses a phenyl group-containing curable polyorganosiloxane composition, an optical semiconductor device encapsulant using the same, and an optical semiconductor device. Patent Document 3 discloses an epoxy oxirane resin having a linear chain having an epoxycyclohexyl group in the side chain and a cyclic decane structure. In Patent Documents 4 and 5, a polyorganosiloxane resin having a diglycidyltrimeric isocyanate group at least at both ends of a main chain and a composition containing the same are disclosed. Patent Document 6 discloses a composition comprising: an organic ruthenium compound having two anthracene hydrogen groups, and a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule. An addition reaction product having at least two addition reaction carbon-carbon double bonds in one molecule and a composition of a compound having a Si—H group in one molecule. However, this is equivalent to the thermosetting resin composition described in Patent Document No. 201247746, and it is difficult to sufficiently have the above characteristics. [Patent Document 1] JP-A-2010-248413 [Patent Document 2] JP-A-2010-84184 [Patent Document 3] International Publication w 0 2 0 0 8 - 1 3 3 I 6 8 [Patent Document 5] Japanese Laid-Open Patent Publication No. JP-A-2009-203258 (Patent Document No. JP-A-2009-069210) The present invention provides a thermosetting resin composition which is high in hardness, heat-resistant coloring property, UV-resistant coloring property, strength, and deformability, and has a small damage even in a reflow or thermal cycle. Electronic materials or optical semiconductor packaging. Another object is to provide an epoxy oxime resin suitable as a material of the above thermosetting resin composition. The present invention relates to an epoxy epoxy resin which is represented by the formula (1) and has an epoxy equivalent of from 1 to 80 g/eq;

-8 - 201247746

(wherein R! represents a hydrocarbon group having a carbon number of 1 to 10, which may be the same or different, m represents 0 < mS100, η represents the number of OSnS100, and Ει represents a diglycidyl group represented by the formula (2) Trimeric isocyanato-propyl; Z represents a divalent organic residue containing a carbon atom at both ends and containing a Si atom in the interior.) Z in the formula (1) is a formula (3) or a pass. A divalent organic residue represented by the formula (4). [Chemical 2]

(wherein R2 represents a hydrocarbon group having 1 to 1 carbon atoms, which may be the same or different, and 1 is a number of 0S1S100.) -9 - 201247746 [Chemical 3] R3 λ I Ό- • (CH2)2 丨/ , Si — Si

RaUR3l o ,si- R3 ii-R3 .〇/ \(ch2)2- (4) (wherein R3 represents a hydrocarbon group having 1 to 1 carbon atoms, which may be the same or different, and j and k respectively represent 〇 An integer of ~4, 1 S j+kS 4 .) A method for producing an epoxy-oxygen resin represented by the formula (1) of the present invention, which comprises at both ends represented by the formula (5): The polyorganic cerebral oxygen chamber of SiH reacts a polyorganic shale with a vinyl group at both ends represented by the general formula (6) or the general formula (7) in a theoretical amount, and then the remaining SiH group The terminal blocking reaction was carried out using monoallyl diglycidyl trimeric isocyanate. 【化4】

[wherein the 1^ and η systems have the same meaning as the general formula (1)) -10- (5) 201247746 [Chemical 5]

k> (wherein, R2 represents a hydrocarbon group having a carbon number of 1 to 1 ,, which may be the same or different. 1 is not 0 0 1 ^ 100) [Chem. 6]

(wherein R3 represents a hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different, and j and k respectively represent an integer of 〇~4, i$j+kS4.) Further, the present invention relates to a thermosetting resin. The composition is characterized in that the thermosetting resin composition containing an epoxy resin, a curing agent (B), and a curing accelerator (C) as essential components contains the above-mentioned epoxy oxime tree (A) as Epoxy resin composition. The curing agent (B) may, for example, be an acid anhydride, an amine compound which is liquid at room temperature or an amine resin which is liquid at room temperature. The hardening accelerator (C) may, for example, be a grade 4 ammonium salt or a grade 4 scale salt. Further, the epoxy resin component may, for example, contain 100 parts by weight of epoxy resin (D) at room temperature in an amount of 5 to 15 parts by weight based on 100 parts by weight of the epoxy epoxy resin (A), and epoxy resin. The equivalent is iso ~looo g/eq. The thermosetting resin composition can be used as a resin composition for an optical component, a resin composition for an electronic component, a resin composition for an optical semiconductor component, or a liquid encapsulating resin composition for a semiconductor. Further, the led device of the present invention is characterized in that it is packaged using the above-described thermosetting resin composition. [Formation for Carrying Out the Invention] Hereinafter, embodiments of the present invention will be described in detail. The epoxy oxirane resin of the present invention is represented by the above formula (1) and has an epoxy equivalent of from 1 to 70 g/eq. In the formula (1), 11! represents a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a hexyl group, a phenyl group or a naphthyl group, but is not limited thereto, and may be the same or different. The preferred Ri and the thermosetting resin composition are methyl groups from the viewpoints of physical properties such as heat resistance and light color resistance when the cured product obtained by heat treatment is used. In the formula (1), m is 0 < mS100, and η is OSnS100, and it is necessary to contain a Z component. Preferably, the number of m and n is from the viewpoint of heat-resistant colorability, light-resistant coloring property, and mechanical property when it is a cured product, and is preferably 〇<m $ 3 0, 0 $n$30, 0 < m + n$50» 0<m$8, 〇^ η ^ 8 ' 0<m + n $20, most preferably m is 0.3~2, η is 1~10, m + n is 1.5~10, especially 0.2<mS2, 0$n $8, 0.5 < m + nS10. Here, m and η are average -12- 201247746 値 (number average). In the general formula (1), the "Z" is a divalent organic residue having a carbon atom disposed at both ends and containing a Si atom. Such a structure is, for example, a structure represented by the general formula (8), (9), (10), (11) or (!2). 【化7】

(In the formula, R4, r6, and r9 represent a divalent hydrocarbon group having 1 to 1 carbon atoms, and may have an aromatic ring therein. R5, R8, and Ru each independently represent a valence of 1 to 1 carbon. a hydrocarbon group. r7 represents a phenyl or a naphthyl group. Rio represents a divalent hydrocarbon group having a carbon number of 1 to 2 fluorene, and may have an aromatic ring or an etheric oxygen atom therein, and A single line representing the 'end of the chemical formula' indicates a single bond. -13- 201247746 [化8]

(wherein R2 and 1 are the same as those in the formula (3), and R3, j, and lc are the same as those described in the formula (4), and R12 and r13 are zenically representing a carbon number of 1 to 1 〇 The divalent hydrocarbon group. Among these, the preferred structure is easy to obtain, the easiness of production of the epoxy-based epoxy resin of the present invention, heat-resistant colorability as a cured product, light-resistant coloring property, and mechanical property. From the viewpoint of the structure represented by the general formula (11) or the general formula (12), it is preferable that r2 in the general formula (11) is methyl ' 〇 $1 each 2 〇, R 3 in the general formula (12) Is methyl, k=l, j = l. Among them, the structure represented by the formula (3) or the formula (4) is preferred. In the general formulae (3) and (4), R2 and R3 independently represent a hydrocarbon group having a carbon number of 1 to 10, but a preferred smoke group is the same as described for R i . In the general formulae (3) and (11), when the number of repeats has an integer, the average enthalpy (number average) is a number in the above range. The epoxy oxirane resin of the present invention is a polyorganosiloxane containing SiH at the end of the formula (5), which is obtained by the formula (6) or the formula (?), • 14 - 201247746 The polyorganosiloxane containing a vinyl group at both ends reacts at a theoretical amount. Then, the remaining SiH group is subjected to a terminal blocking reaction using monoallyl diglycidyl trimer isocyanate, which can be advantageously produced. In the method for producing an epoxy-oxygen resin of the present invention, a polyorganosiloxane containing SiH at both ends represented by the formula (5) is used as a raw material, and the amount of the unreacted SiH group remaining is used to obtain a formula (6). Or a polyorganosiloxane containing a vinyl group at both terminals represented by the formula (7) by a hydrogenation reaction, and then, by using a monoallyl diglycidyl trimeric isocyanate, the unreacted SiH group is used. The end capping reaction was carried out. The ratio of the unreacted SiH group is related to the E content of the epoxy-based epoxy resin represented by the formula (1), and as a result, it is related to the epoxy equivalent. Therefore, in order to satisfy the above range of the epoxy equivalent, the unreacted SiH group may be left unrestricted, but it is preferable to leave 20 to 80% of the SiH group. In this reaction, it is particularly preferred that the polyorganosiloxane containing SiH at both ends is first introduced into the reaction system, and then the unreacted SiH residual ethylene-containing polyorganosiloxane is successively added to confirm the reaction (hydrazine hydrogenation). After the end of the reaction, the terminal blocking reaction was carried out using monoallyl diglycidyl trimer isocyanate. Further, two or more kinds of polyorganosiloxanes represented by the formula (6) or the formula (7) may be used. Other than the above, for example, a polyorganosiloxane containing SiH at both ends, a polyorganosiloxane having a vinyl group at both terminals, and a monoallyl diglycidyl trimeric isocyanate are once introduced into the reaction system to carry out hydrazine. Hydrogenation, or mixing a polyorganosiloxane containing a vinyl group at both ends with a monoallyl diglycidyl trimeric isocyanate and putting it into a reaction system, followed by a polyorgano-oxygen group containing SiH at the end of two-15-201247746 When the alkane is subjected to a hydrazine hydrogenation reaction, the reaction rate of the hydrazine hydrogenation reaction is faster than that of the monoallyl diglycidyl trimeric isocyanate and the vinyl group-containing polyorganooxy oxane at both ends, so that it is easily selected in the reaction system. A rhodium oxide resin having no epoxy group is produced. Therefore, the obtained epoxy-oxygen resin causes phase separation, white turbidity, loss of transparency, and even if white turbidity does not occur, the effect of the present invention cannot be obtained in terms of physical properties of the cured product, which is not preferable. The hydrazine hydrogenation reaction (addition reaction) is well known in the presence of a noble metal strontium. As long as the catalyst is a well-known one, various noble metals or complex compounds thereof can be used. The noble metal catalyst may, for example, be platinum, rhodium, palladium, iridium or iridium. However, the present invention is not limited thereto, and two or more kinds may be used depending on the cold. Further, it is also possible to use such a metal to be immobilized on a fine particle-shaped carrier material such as carbon, activated carbon, alumina, cerium oxide or the like. The complex compound of the noble metal may, for example, be a uranium halide compound (PtCl4 'H2PtCl6 · 6H2O 'Na2PtCl6 · 4Η2, 0, etc.), a platinum-olefin complex, a platinum-alcohol complex, a platinum-alcohol complex , platinum-ether complex, platinum-carbonyl complex, ketone-keto complex, platinum-1,3-divinyl-1,1,3,3-tetramethyldioxane, etc. Platinum-vinyl alkane complex, bis(r-methylpyridine)-platinum dichloride, trimethylene dipyridine-platinum dichloride, dicyclopentadiene-platinum dichloride, cyclooctane Alkene-platinum dichloride, cyclopentadiene-uranium dichloride, bis(alkynyl)bis(triphenylphosphine)platinum complex, bis(alkynyl)bis(cyclooctadiene)platinum complex Further, ruthenium chloride, ruthenium (triphenylphosphine) ruthenium chloride, ruthenium ammonium-ruthenium chloride complex, and the like are not particularly limited, and two or more kinds may be used as needed. -16- 201247746 The above-mentioned noble metal catalyst may be used alone or in a solvent, and the ratio may be used in the reaction system after that, and is not particularly limited, but is 0.1 ppm to 1000 ppm relative to the general counterweight. range. The hydrazine hydrogen addition reaction system may be diluted with an organic solvent even if it has no solvent, and is not particularly limited as long as it is a compound which is well-affected. Halomethyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ring, benzene, toluene, o-xylene, m-xylene, dichlorobenzene such as chloroform, carbon tetrachloride or 1,2-dichloroethane Ethers such as aromatics and diethylene glycol dimethyl ether, and ethyl acetate and n-butyl acetate may be selected from two or more organic solvents to form a mixture of temperature conditions in the hydrogen addition reaction. Generally, it is 0 ° C ~ 200 ° C, preferably 30 ° C ~ 1 80 ° C » It takes time to carry out, it is not economical. When the addition reaction of the epoxide group and the hydrazine group is carried out at 20 (TC), the function of the sclerosing resin composition in the synthesis reaction of the epoxy oxirane resin appears, and the monoene trimeric isocyanate The curable resin composition can be formed by using a compound of a vinyl group and an epoxy group in one molecule to form a curable resin composition. One or more compounds of a vinyl group and an epoxy group are dissolved and dissolved in advance. The noble metal catalyst reacts at a concentration of 1 ppm to 10,000 ppm of the raw materials to be used, but does not cause an aliphatic ketone p-xylene such as dichloromethane, a sulfonated hydrocarbon, acetone, ketone or the like. An ester such as chlorobenzene, ether or triethylene glycol dimethyl. The solvent is used. There is no particular limitation, but one: 〇°c or less is carried out in the reaction or more, and it is difficult to control the reaction. The propyl diglycidyl group of the present invention contains at least one catalyzed reaction, and at least one of the obtained molecules is contained, for example, allyl -17-201247746 glacial glyceryl ether, glycidyl methacrylate, 4-ethylene The cyclohexene oxide, the citric acid oxide, the monovinyl diepoxide ring, and the like are not limited thereto, and two or more kinds may be used. The amount used is not particularly limited. The viewpoint of the function of the curable resin composition of the invention is preferably 5 Om〇% or less of monoallyl diglycidyl trimer isocyanate. The epoxy epoxy resin of the present invention has an epoxy equivalent of 170 to 2000 g. /eq, preferably 200 to 1 000 g/eq, and most preferably 230 to 700 g/eq. In this range, a cured product excellent in transparency, heat-resistant coloring property, glass transition point temperature, and bending deformability can be obtained. When the epoxy equivalent is outside this range, the cured product becomes brittle, or the surface hardness becomes low, or the adhesion is caused, and the heat resistance of the fish is deteriorated, which is not preferable. Next, the composition of the thermosetting resin according to the present invention will be described. The thermosetting resin composition contains an epoxy resin, a curing agent (B), and a curing accelerator (C) as essential components, and contains the epoxy epoxy resin of the present invention as an epoxy resin component. In the resin composition, the epoxy oxime of the present invention is referred to. The oxy-resin is an epoxy oxime resin (A). The curing agent (B) contained in the thermosetting resin composition of the present invention is preferably a known curing agent for an epoxy resin. Various compounds, such as organic amine compounds such as polyallylamine, polyamidamine, dicyandiamide and derivatives thereof, 2-methylimidazole, 2-ethyl-4-methylimidazole, etc. Imidazole and its derivatives, bisphenol A, bisphenol F, brominated bisphenol A, naphthalenediol, 4,4'-bisphenol and other divalent phenol compounds, phenol or naphthols and formaldehyde or xylene Awakening varnish obtained by condensation reaction of alcohols -18-201247746 Polycarboxylic acid, succinic anhydride, maleic anhydride, phthalic anhydride, six obtained by reaction of resin or aralkyl phenol resin, acid anhydride compound and polyvalent organic alcohol Hydrogen anhydride, methylated hexahydrophthalic anhydride, nadic acid anhydride, hydrogenated nadic anhydride, trimellitic anhydride, pyromellitic anhydride or the like, bisamine compound such as adipate bisamine An organic cationic molecule having a sulfonic acid cation, an iodine cation, and a tetrafluoroboron anion A cationic curing agent composed of an onium salt compound such as an anion species such as a hexafluorophosphorus anion, a hexafluoroarsenic anion or a hexafluoroanthracene anion may be used in an amount of two or more kinds as needed. A preferred curing agent-based acid anhydride for obtaining transparency, heat-resistant coloring property, and light-resistant coloring property of the present invention, a compound having an amine group which is liquid at room temperature, or a phenol resin. In particular, the acid anhydride is more preferably hexahydrophthalic anhydride, methylated hexahydrophthalic anhydride or hydrogenated nadic acid anhydride. The hardening accelerator (C) is a known hardening accelerator for an epoxy resin, and various compounds can be used as long as it is known. For example, an organic metal salt such as a tertiary amine or a salt thereof, an imidazole or a salt thereof, an organic phosphorus compound or a salt thereof, such as zinc octoate or tin octylate, may be used, and two or more types may be used as needed. Particularly preferred hardening accelerators for obtaining the effects of the present invention are the fourth-order ammonium salts, the organophosphorus compounds, and the fourth-order scale salts. More preferably, the catalyst is a class 4 scale salt. The thermosetting resin composition of the present invention has the above-mentioned components (A), (B) and (C) as essential components, but it is intended to be a preferred form of the skilled person in the adjustment of the viscosity 'hardening rate, etc. (D) The component may be an epoxy resin or an epoxy compound which has two or more epoxy groups in one molecule other than the component (A) and is liquid at room temperature. At this time, the mixture of (A) and (D) and the epoxy-19-201247746 equivalent are in the range of 180 to 1 000 g/eq, and the effects of the present invention can be obtained. (A) The ratio of use of the component to the component (D) is in the range of 100 parts by weight of the epoxy resin (A), preferably 50 parts by weight of the epoxy resin (D) at room temperature. . The component (D) may be any one of the compounds as long as it is liquid or separately in a chamber. For example, an aromatic ring of an epoxy resin derived from a monocyclic divalent phenol such as m-xylenol, hydroquinone or 2,5-di-tert-butylhydroquinone may be used. An epoxy resin derived from a naphthalene glycol such as diol, 1,4-naphthalenediol, 1,5-naphthalenediol or 1,6-naphthalenediol '2,7-naphthalenediol, and Aromatic ring via nuclear hydrogenation, 4,4'-isopropylidenediphenol, 4,4'-isopropylidene bis(2-methylphenol), 4,4'-isoindolyl bis (2, 6-dimethylphenol), 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxy-3,3'-dimethyldiphenylmethane, 4,4'-dihydroxy-3 , 3',5,5'-tetramethyldiphenylmethane, 4,4'. second butylene bisphenol, 4,4'-isopropylene bis (2-tert-butyl phenol), 4 An epoxy resin derived from a bisphenol such as 4'-cyclohexylidenediol or 4,4'-butylidenebis(6-tert-butyl-2-methyl)phenol, and an aromatic ring thereof Nuclear hydrogenated epoxy resin. Further, for example, an alicyclic epoxy resin represented by the general formulae (13) to (17) is also preferable.

-20- 201247746

(In the formula, i and h each independently represent an integer of 1 to 2 Å) Further, for example, an epoxy oxirane resin represented by the formula (18) can be mentioned. (R14Si〇3/2) e (R15R16SiO) f (Me3Si01/2) g (18) (In the formula, Ri4 to R16 are each a hydrocarbon group or an aromatic group having an epoxy group having 1 to 20 carbon atoms. Further, it may have 1 to 3 etheric oxygen atoms in the interior. However, one or more of Ri4 to R16 must contain an epoxy group. Further, R15 and Ri6 may have an epoxy group at the same time. + f+g=l, OS e<l, 0<f<l, 0<g<0.75). When the curable resin composition of the present invention is used as an LED package, it is preferable to blend an antioxidant to prevent oxidative degradation during heating, and to form a cured product having little coloration. As long as the antioxidant is a well-known person, various compounds can be applied. For example, 2,6-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-t-butyl-p-ethyl cresol, stearyl-wan-(3,5-di Monophenols such as tributyl-4-4-hydroxyphenyl)propionate, 2,2-methylenebis(4-methyl-6-tert-butylphenol), 2,2-methylene Bisphenol (4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), bisphenols, M, 3_ 2-Methyl-4-hydroxy-21 - 201247746 base _5_t-butylphenyl)butane ' 1,3,5-trimethyl. 2,4,6-gin(3,5-di-t-butyl-4-ylhydroxybenzyl)benzene, hydrazine [methylene-M3,5-di-t-butyl-4-hydroxyphenyl)-propyl Acid esters such as methane, etc., 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, 1〇-(3,5-di-tert-butyl-4-hydroxyl Benzyl)-9,10·dihydro-9-oxo-10-phosphonium-10-oxo t, 10-deoxy-9,10-dihydro-9-oxo-10-phosphaphene-10- Oxygen phosphorus phenanthrene oxides such as oxides, dilauryl 3,3,-dilauryl 3,3,-thiodipropionate, dimyristyl 3,3'-dilauryl 3,3'- An ester-containing thioether compound such as thiodipropionate, stearyl 3,3'-dilauryl 3,3'-thiodipropionate or pentaerythritol ruthenium (3-lauroside thiopropionate) Antioxidants. These antioxidants can be used in combination of two or more kinds as needed. Further, other thermosetting resins may be blended in the thermosetting resin composition of the present invention. Examples of such a thermosetting resin include an unsaturated polyester resin, a thermosetting acrylic resin, a thermosetting amine resin, a thermosetting behavin resin, a thermosetting urea resin, and a thermosetting ureic acid. The ester resin, the thermosetting oxetane resin, the thermally degradable epoxy group/oxetane composite resin, and the like are not limited thereto. The curable resin composition of the present invention contains the components (A) to (C) as essential components, but may be a resin component (components such as a monomer, a hardener, and a hardener which are hardened to form a part of the resin other than the resin) 60% by weight or more of the accelerator, but not containing a solvent or a chelating agent, preferably 80% by weight or more, more preferably 90% by weight or more, of the components (A) to (B). The blending ratio of the component (A), the component (B) and the component (C) can be determined as follows. When the component (B) is not a cationic curing agent, it is preferably an epoxy group of the total oxime component. -22-201247746 The functional group in the curing agent of the component (B) has an equivalent ratio of 0.8 to 1.5. After the external hardening in this range, the unreacted epoxy group or the functional group in the hardener remains, and the function such as hardness or heat resistance when the cured product is formed is lowered, which is not preferable. Further, the blending ratio of the component (C) of the hardening accelerator is preferably in the range of from 0.1 to 5 wt% based on the total of the epoxy group and the component (B) of the all-epoxy component. When the amount is less than 0.1% by weight, the gelation time becomes slow, and the rigidity at the time of hardening is lowered to cause a decrease in workability. On the other hand, if it exceeds 5.0 wt%, it hardens during the molding and is liable to be unfilled. When the component (B) is a cationic curing agent, it is preferably 0.1 part by weight to 5 parts by weight based on 1 part by weight of the total epoxy component. When the amount is less than 0.01 part by weight, the curing failure tends to occur. On the other hand, if it exceeds 5 parts by weight, the transparency and heat-resistant coloring property are not preferable. When the thermosetting resin of the present invention is used as an electronic component, the use and the manufacturing procedure are not particularly limited. For example, in the case of a semiconductor encapsulating material, a chelating agent such as cerium oxide is mixed in a thermosetting resin composition of the present invention, and kneaded by a kneader or a hot 3-roller, and then pelletized and fed into a mold for packaging. The mold cavity makes the heat hardening transfer mold mode. Further, it is mixed with a curing agent which is liquid at room temperature, and if necessary, a chelating agent such as cerium oxide or alumina 'titanium oxide is used to form a desired viscosity, and then a resin can be injected at a specific position. Glue way. In addition, the circuit board may be obtained by, for example, impregnating a substrate of a glass cloth or the like with a thermosetting resin composition of the present invention, bonding the copper foil by press molding, or coating the copper foil by a casting method or the like. A method of bonding a thermosetting resin composition to a desired substrate. -23- 201247746 In addition, when the bottom is used as a joint between the package and the protective substrate and the semiconductor, it is hydrated with a hardener at room temperature, and if necessary, cerium oxide, aluminum oxide, or oxidation is used. After forming a desired viscosity by using a filler such as titanium or rubber particles, the resin can be dispensed at a specific position. In addition, the use of the optical component is, for example, an optical lens, a package for an optical semiconductor, a white molding material for an optical semiconductor, a light semi-adhesive, and the like, and the use thereof is not limited thereto, and is a known use and manufacturing. The program is ready to apply. For example, the optical lens material can be produced by a known process such as dispensing, transfer molding, or injection molding. The package material for an optical semiconductor device (LED device) is a method in which a light semiconductor device is connected to an external electrode by a gold wire or the like, and then a known technique such as a transfer molding method or a dispensing method is used. In this case, the thermosetting resin composition of the present invention can be used for the purpose of converting light emitted from the optical semiconductor element, and various known fluorescent powders can also be used. Further, in order to exhibit moderate shakeability, a known additive such as cerium oxide or an aerosol or a known additive such as a decane coupling or a surfactant may be added. The white molding material for optical semiconductors can be applied to the thermosetting resin composition of the present invention, and a crucible such as cerium oxide, titanium oxide or aluminum oxide is mixed, and kneaded by a kneader or a hot 3-roller to carry out tableting. The mold is fed into the mold cavity of the mold, and the mold is transferred by heat hardening. The adhesive for an optical semiconductor device can be applied to the thermosetting resin composition of the present invention, and if necessary, a kneading agent such as ceria, titanium oxide, aluminum oxide or -24 - 201247746 silver powder can be used as a kneading agent such as a roll. The substrate is coated on the substrate by a method, or a known film material is used, and the method is such that the film is bonded to the substrate, and the optical semiconductor element is mounted. The thermosetting resin composition of the present invention is obtained by using a film such as a spin coater or a bar coater on a substrate such as a fluororesin film or a polyimide, and then thermally curing the substrate to obtain a film. The thermosetting resin and the thermosetting obtained by the above method can be applied to an electronic component or an optical component, and can be applied to a flexible printed circuit board, an anisotropic conductive thin film, a die-bonded film, or the like. Uses for protective films for electronic components such as interlayer insulating materials, films for optical waveguides, and optical semiconductor films. [Embodiment] [Embodiment] Next, the present invention will be specifically described based on examples, but the present invention is not limited to the embodiments described below. Example 1 In the general formula (5), 1 is a methyl group, and the average 値 of η is 4, 516 parts by weight (SiH basis amount) of a polyorganoleium having an SiH group, 582 parts by weight of dioxane, and carbon support. The alloy (white gold is placed in a weight, and is filled with a stirring motor, a reflow cooling tube, a nitrogen dispenser, etc. to form a thin heat-hardening, and the PET is thin and coated. The film is used for various films, covering, and transparent. Optical parts The present invention was heated at a temperature of 1 Q0 ° C while stirring at a temperature of 2 -25 - 201247746 liters of a separate flask of 2.4 匮3 %) 1.8. Then, in the formula (6), 67 parts by weight of an organic oxirane having a vinyl group at a terminal of R2 and a ratio of 1 to 0 (0.7 equivalent of a vinyl group) was put into the reaction system for 1 hour. By gel permeation chromatography (GPC), it was confirmed that 472 parts by weight of N-allyl diglycidyl trimeric isocyanate (vinyl equivalent of 1.7 equivalents) after the disappearance of the organic oxirane having a vinyl group at both terminals disappeared. The solution dissolved in 472 parts by weight of dioxane was put into operation for 1 hour. After the completion of the reaction, the internal temperature was raised to Π, and the reaction was carried out while refluxing the dioxane. The reaction solution was added dropwise to a 0.1 equivalent potassium hydroxide/methanol solution, and hydrogen evolution was not observed. The reaction was terminated, and the residual platinum catalyst was filtered using Celite. The solvent of the filtrate is removed by using an evaporator to obtain a methyl group in the general formula (1), an average enthalpy of m is 0.4, an average enthalpy of η is 4, and 112 is a methyl group in the general formula (3). , 1 = 0 epoxy epoxy resin (ES 1) 10 〇 5 parts by weight. The epoxy equivalent of this resin is 312 g / eq, the viscosity at room temperature is 5 · 6 P a · s 〇 Example 2 In the general formula (5), R is a methyl group, and the average 値 of η is 4, 86 parts by weight of polyorganosiloxane having a SiH group at both ends (0.4 equivalent of the ii group), and 190 parts by weight of dioxane. 0.32 parts by weight of platinum (platinum. 3%) was placed in a 1 liter separation flask equipped with a stirring motor, a reflux cooling tube, and a nitrogen line, and the temperature was raised to 100 ° C while stirring. Then, in the general formula (6), R2 is a methyl group, and an average enthalpy of 1 is 4, and 51 parts by weight of an organic siloxane having a vinyl group at the end (vinyl equivalent of 0.2 equivalent) is spent 1 hour -26-201247746 In the reaction system. After confirming the increase in molecular weight by the gel permeation chromatography (GPC) method, 56 parts by weight of N-allyl-Ν', N"-diglycidyl isocyanurate (vinyl equivalent of 0.2 equivalent) was obtained. The solution dissolved in 56 parts by weight of dioxins was put into operation for 1 hour. After the completion of the reaction, the internal temperature was raised to no ° c, and the reaction was carried out while refluxing the dioxane. /Methanol solution was dropped into the reaction solution to confirm the disappearance of hydrogen gas, and the remaining platinum catalyst was filtered using Celite. The solvent of the filtrate was distilled off using an evaporator to obtain R in the formula (1), which was methyl or m. The average enthalpy of 1, the average 値 of η is 4 and Z is 167 parts by weight of the epoxy oxirane resin (ES 2) in which R 2 is a methyl group and 1 = 4 in the formula (3). The epoxy equivalent of the resin is 451. g/eq, viscosity at room temperature is 2.0 Pa·s. Example 3 In the general formula (5), 1 is a methyl group, and n has an average enthalpy of 8 and a polyorganosiloxane 726 having a SiH group at both ends. Parts by weight (2.0 equivalents for SiH group), 1 16 60 parts by weight of dioxane, uranium supported by carbon (3% of platinum support), 1.9 6 parts by weight, charged with stirring In a 3-liter separable flask of a reflux, a cooling tube, and a nitrogen line, the temperature was raised to 100 ° C while stirring. Then, in the formula (6), the ruler 2 was a methyl group, and the ring was a vinyl group at both ends. 93 parts by weight of the organic oxirane (vinyl oxime equivalent) was put into the reaction system for an hour; the gel permeation chromatography (GPC) method was used to confirm that the increase in molecular weight was stopped, and the N-ene was made. 281 parts by weight of propyl-N',N',-diglycidyl isocyanurate (vinyl is ι·〇 equivalent) dissolved in 281 parts by weight of dioxane, and the solution was taken for 1 hour. The temperature was raised to -27-201247746 1 1 0 °c, while the dioxane was refluxed, and the reaction was carried out. The reaction solution was added dropwise to the potassium hydroxide/methanol solution to confirm the loss of hydrogen, and the remaining lead was filtered using C elite. The solvent is distilled off using a solvent of the evaporating liquid to obtain R in the general formula (1), which is formazan, and the average enthalpy of η is 8, and Z is in the formula (3), and RZ is an epoxy oxirane resin. (ES 3) 1 〇 23 parts by weight. The resin has a viscosity of 538 g/eq at room temperature of 1.1 pa. s» Example 4 will be in the formula (5) The average of the core is methyl and n is 430 parts by weight (SiH amount) of polyorganosiloxane having SiH group, 949 parts by weight of dioxane, and platinum supported on platinum (the amount of platinum supported is loaded with stirring) In a motor, a reflux cooling tube, and a nitrogen separation flask, the temperature was raised to 100 ° C while stirring. In the formula (7), R 3 is a methyl group, and j = k = 1 has an ethyl siloxane of 160 parts by weight at both ends ( The vinyl group is 1.0 equivalent in the reaction system. After stopping the increase in the amount of gel permeation chromatography (GPC), the N-allyl-N',N"-bi-dihydrate isocyanate is made. 2S1 parts by weight (vinyl is 1.0 羹) dissolved 281 parts by weight of the solution was taken for 1 hour. After the completion of the reaction, the temperature was raised to 11 ° C, and the reaction liquid was added dropwise to the counter-equivalent potassium hydroxide/methanol solution while refluxing the dioxane, and the residual platinum catalyst was filtered using Celite. The solvent of the filtrate is distilled off to obtain an average sulfhydryl group in which the R i is a 0.1 equivalent gas in the general formula (1), and the epoxy equivalent of 1 = 0 is 4 The terminal group was 2.0 when 3%) 1.5 liters of 3 liters of the heavy line, and then the ring of the alkenyl group was charged for 1 hour, and it was confirmed that the molecular glyceryl group was trimerized in dioxane to raise the internal temperature. In the case of 0.1, the hydrogen is produced by the evaporator and the base is m, and the level of m is -28-201247746. The average enthalpy is 1, the average 値 of η is 4 and Z is in the formula (4), R3 is methyl, j=k=l Epoxy oxirane resin (ES4) 791 parts by weight. The resin had an epoxy equivalent of 429 g/eq and a viscosity of 8.1 Pa·s at room temperature. Synthesis Example 1 26.4 parts by weight of an organohydrogen siloxane represented by the formula (19) (2.0 equivalents of SiH group), 78 parts by weight of dioxane, and carbon-supported uranium (platinum loading: 3%) 0·14 by weight The mixture was placed in a 500 ml separation flask equipped with a stirring motor, a reflux cooling tube, and a nitrogen line, and the temperature was raised to 100 ° C while stirring. Then, 56.2 parts by weight of N-allyl-N',N"-diglycidyl trimer isocyanate (vinyl group was 2.0 equivalent) was dissolved in 56 parts by weight of dioxane, and the solution was put in for 1 hour. After the completion, the internal temperature was raised to ii 〇 ° C ' while dioxane was refluxed, and the reaction was carried out. The reaction liquid was added dropwise to 1 equivalent of potassium hydroxide/methanol solution to confirm the disappearance of hydrogen generation, and Celite was used. Platinum catalyst remaining in Shanghai. Emulsifying the solvent of the filtrate using an evaporator to obtain an epoxy resin (ES 5) 74 containing an epoxy group-containing trimeric isocyanate ring at both ends and side chains. Parts by weight. The resin has an epoxy equivalent of 203 g/eq and does not exhibit a fluid semi-solid shape at room temperature. -29- 201247746

Examples 5 to 8 Using methylated hexahydrophthalic anhydride (ΜΗ: anhydride equivalent: 168 g/eq) 'The epoxy epoxy resin (A) (ES 1 to 4) obtained in Examples 1 to 4 was added to make a ring. The ratio of the oxygen equivalent to the anhydride equivalent is 1:1, and the mixture is sufficiently mixed, and further 'into the tetra-n-butyl quinone diethylphosphine disulfate all _ 0.5% by weight as a hardening accelerator, and mixed, and vacuum degassed in a mold. Thereafter, the film was cured at 1 20 ° C for 4 hours, and further cured at 1 60 ° C for 12 hours to prepare a resin plate having a thickness of 1 mm and 4 mm. Example 9 Preparation of 70 parts by weight of the oxime oxirane resin (ES 2) obtained in Example 2 as the component (A), further blending 3,4-epoxycyclohexenylmethyl-3' 4'-epoxycyclohexene carboxylate (EpC; epoxy equivalent 130 g/eq) 30 parts by weight of a resin liquid as the component (D). This resin liquid and MH' are added in such a manner that the ratio of the epoxy equivalent to the acid anhydride equivalent becomes i:i, and the mixture is sufficiently mixed, and further, tetra-n-butyl fluorene, hydrazine, _diethylphosphine-30-201247746 is charged. 0.5% by weight of the entire disulfate was used as a curing accelerator, mixed, vacuum-deaerated, and cured in a mold at 120 ° C for 4 hours, and further cured at 160 ° C for 12 hours to prepare a resin sheet having a thickness of 1 mm and 4 mm. Example 1 〇 Preparation A 70 parts by weight of the epoxy oxirane resin (ES 4) obtained in Example 4 was used as the component (A) to further blend 3,4-epoxycyclohexenylmethyl-3 ',4'-Epoxycyclohexenecarboxylate 30 parts by weight of a resin liquid as the component (D). The resin liquid and MH were added so that the ratio of the epoxy equivalent to the acid anhydride equivalent was 1:1, and the mixture was sufficiently mixed, and further, 0.5% by weight of tetra-n-butylselen diethylphosphine disulfate was added as a hardening. The accelerator was mixed, vacuum-degassed, and hardened in a mold at 120 ° C for 4 hours, and further cured at 160 ° C for 12 hours to prepare a resin plate having a thickness of 1 mm and 4 mm. Example 1 1 to 1 4 was added to the examples 1 to 4 by using diethyltoluenediamine (DETDA: active hydrogen equivalent: 45 g/eq) so that the ratio of the epoxy equivalent to the active hydrogen equivalent was 1:1. The obtained epoxy oxirane resin (A) (ES 1 to 4) was thoroughly mixed, and further, 0.5% by weight of the entire 2-ethyl-4-methylimidazole was added as a hardening accelerator, and vacuum degassed in a mold. It was hardened at 1 to 20 ° C for 4 hours, and further hardened at 160 ° C for 12 hours to prepare a resin plate having a thickness of 1 mm and 4 mm. -31 - 201247746 Comparative Example 1 Without using the component (A), 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (EpC) 26 weight A resin plate having a thickness of 1 mm and 4 mm was produced in the same manner as in Example 5 except that 34 parts by weight of MH was used. Comparative Example 2 The same procedure as in Comparative Example 1 was carried out except that 20 parts by weight of triglycidyl isocyanurate (ΕρΤ, epoxy equivalent 100 g/eq) was used without using the component (A). The operation is to make a resin plate having a thickness of 1 mm and 4 mm. Comparative Example 3 The use of ((Me2 CHpCFOSiOi/;^. (Me SiOwh.u (Me2 SiO) 0,05) 100 parts by weight of the epoxy resin, vinyl equivalent of 1400 g / eq of both ends containing vinyl 20 parts by weight of dimethyl siloxane oil and 48 parts by weight of methylhydroquinone oxime with a hydrogen group equivalent of 64 g/eq, and added platinum-tetravinyldioxane as a hardening catalyst The benzene solution of the product was 20 ppm with respect to the total weight, vacuum degassed, and was cured in a mold at 120 ° C for 4 hours, and further cured at 160 ° C for 12 hours to prepare a resin plate having a thickness of 1 mm and 4 mm. 4 Adding 16 parts by weight of methylhydroquinone oxy-oil represented by (CeHOo.idCHfCFOmiCHOo.wSiOu, 30 parts by weight of -32-201247746 phenyl sulfonium resin and 矽 hydroxy group equivalent of 163 g/eq) The xylene solution of the catalyst uranium-tetraethyl quinone dioxane complex was 20 Ppm with a total weight of 20 Ppm, vacuum degassed in a mold, hardened at 120 ° C for 4 hours, and further hardened at 160 ° C. A resin plate having a thickness of 1 mm and 4 mm was produced in an hour. Comparative Example 5 The component (A) was not used, but was used in the following general formula (15) with k = 〇, j = 0.8, i = 〇_2, and R7 is a methyl group, and R8 is an epoxy oxirane resin represented by 2-(3,4-epoxycyclohexyl)ethyl group (ESC, epoxy equivalent 207g) /eq) 42 parts by weight and MH 27 parts by weight, the same operation as in Example 6 was carried out to prepare a resin plate having a thickness of 1 mm and 4 mm (R6S i 03/2) k (R7R8s i Ο) (Me 3S i 0 1/2) 丨 (15) Comparative Example 6 The epoxy resin (ES5) obtained in Synthesis Example 1 was used in an amount of 4 〇.6 parts by weight and MH 33.6 parts by weight, without using the component (A). A resin plate having a thickness of 1 mm and 4 mm was produced in the same manner as in Example 6. Comparative Example 7 Using 1,3,5,7-tetramethylcyclotetraoxane and an excess amount of vinylnorzene The resulting hydrogenation reaction product (vinyl equivalent: 25 〇g / eq) 25 parts by weight, and excess 1,3,5,7-tetramethylcyclotetraoxane and vinyl group -33 - 201247746 16 parts by weight of a hydrogenation reaction product (SiH equivalent: 160 g/eq) produced by the olefin, and a xylene solution of a platinum-tetravinyldioxane complex as a hardening catalyst was added at 20 ppm with respect to the total weight. Vacuum degassing in the mold , Cured 4 hours to 1 2 0 ° C, further to 160 sclerosis 2 hours to prepare a resin sheet 1mm thick and 4mm of determination based resin sheet has hardened properties of the carried out as follows. (1) The glass transition temperature (Tg) of the cured product was measured using a thermal stress deformation measuring apparatus TMA/SS 12 0U manufactured by Seiko Electronics Co., Ltd., and was measured at a range of 30 ° C to 2 70 ° C to increase the linear expansion ratio. The varying temperature is taken as the glass transition temperature. The heating speed is 5 °C / min. (2) Measurement of the coefficient of linear expansion is carried out in the range of 30 ° C to 270 ° C using a thermal stress deformation measuring apparatus TMA/SS 120U manufactured by Seiko Electronics Co., Ltd., from 2 ° at 40 ° C and 60 ° C. The slope of the connected straight line calculates the linear expansion ratio. The heating rate was 5 ° C / min. (3) Initial transmittance of the cured product The transmittance of 400 nm of the cured product having a thickness of 1 mm was measured using a self-recording spectrophotometer P-3410 manufactured by Hitachi, Ltd. (4) Measurement of UV resistance The transmittance of 400 nm after UV irradiation of a thickness of 4 mm was measured for 600 hours using a weather resistance tester Q UV manufactured by Q Panel Co., Ltd. in the same manner as the initial penetration. The lamp system used in the QUV uses UVA 340 nm and the black panel temperature is 55 °C. (5) Measurement of initial heat resistance -34- 201247746 The cured product of 1 mm thick was exposed to an environment of 150 ° C, and the penetration of 400 nm after 72 hours was measured in the same manner as the initial penetration. (6) Measurement of long-term heat resistance The cured product of 1 mm thick was exposed to an environment of 150 ° C, and the transmittance of 400 nm after 480 hours was measured in the same manner as the initial penetration. (7) Measurement of hardness The surface hardness of the cured product at room temperature was measured using a Techlock hardness tester TYPE-D. (8) Shape of hardened material after removing the mold When the mold is removed, the uniformity of the cured product or the crack of the cured product of the hardening shrinkage is visually judged. 〇: It is a uniform hardened material. △: The shape of the mold was maintained, but cracks were generated in the cured product. X: The shape of the mold was not maintained, and the resin was cracked. (9) Bending and deformation characteristics test According to JIS-7171, a test piece of 80 mm x 10 mm x 4 mm was used, and the bending elastic modulus, bending strength, and bending deformation were measured by Autograph (manufactured by Shimadzu Corporation). A sputum means that it has not broken. The measurement results of the respective tests of the cured products obtained in Examples 5 to 10 are shown in Table 1. The measurement results of the respective tests of the cured products obtained in Examples 1 to 14 are shown in Table 2. The measurement results of the respective tests of the cured products obtained in Comparative Examples 1 to 7 are shown in Table 3. In Table 3 'NM means not measurable. -35- 201247746 [Table 1] Example 5 6 7 8 9 10 (A) Component ESI ES 2 ES 3 ES 4 ES 2 ES 4 (D) Component _ —. — _ E p CE p C (B) Component ΜΗ ΜΗ MH MH MH MH T g oc) 135 122 107 1 24 16 1 174 Linear expansion ratio (ppm/K) 13 8 18 7 19 2 18 3 110 13 2 400 nm penetration (%) Initial 9 2 9 2 9 1 9 1 9 1 9 0 After UV resistance 8 9 9 0 8 8 8 9 8 9 8 8 After initial heat resistance 8 5 8 6 8 3 9 0 8 8 8 8 After long-term heat resistance 6 2 5 2 3 9 5 9 8 0 8 1 Hardness (Shore D) 7 6 5 8 5 5 5 8 7 9 8 1 Shape of hardened material Bending elastic modulus (MPa) 10 10 3 7 0 17 0 4 2 0 12 3 0 13 4 0 Bending strength (MPa) ) 4 5 19 13 2 1 5 8 6 1 Bending deformability (mm) 〇〇〇〇〇〇-36- 201247746 [Table 2] Example 11 12 13 14 (A) Component ESI ES 2 ES 3 ES 4 (D ) Component (B) Component DETDA DETDA DETDA DETDA Tg (V) 1 27 115 102 118 Linear expansion ratio (ppm/K) 13 1 17 8 18 3 17 4 Hardness (Shore D) 7 8 6 0 5 8 6 2 Hardened material Shape 〇〇〇〇 Bending elastic modulus (MPa) 12 6 0 4 7 0 3 8 0 5 3 0 Bending strength (MPa) 5 4 2 3 2 0 2 5 Flexural deformability (mm) 〇〇〇〇 [Table 3] Comparative Example 1 2 3 4 5 6 7 Tg (°C) 200 235 Below room temperature 2 8 188 182 56 Linear expansion ratio (ppm/K) 5 6 5 5 2 8 0 200 6 4 7 6 9 8 400 nm penetration (%) Initial 8 9 8 8 8 9 8 8 9 0 9 1 8 9 After uv resistance 5 6 7 7 8 9 7 8 8 3 7 6 8 1 After initial heat resistance 8 0 8 3 8 9 8 8 8 2 8 5 8 0 After long-term heat resistance 3 3 3 2 8 9 8 0 3 6 5 3 4 1 Hardness (.Shore D) 8 9 9 1 NM 5 2 8 9 8 9 6 5 Shape of hardened material X 〇X 〇〇〇〇Bending elastic modulus (MPa) 3 14 0 3 3 2 0 NM 2 2 0 3 12 0 2 9 8 0 14 0 0 Bending strength (MPa) 3 1 4 3 NM 6 5 8 9 2 3 0 Bending deformability (mm) 1. 9 2. 2 NM 5. 0 3 . 3 7. 6 3 . 1 -37- 201247746 Examples 15 to 20, Comparative Examples 8 to 14 The blended objects of Examples 5 to 10 and Comparative Examples 1 to 7 were filled with silver-plated blue LEt of the bottom edge by casting, and hardened at 100 ° C for 2 hours, 1 5 with a pre-tanning body. It is hardened at 0 °C for 5 hours to produce an LED device. The physical properties of the packaged LED device were determined as follows. (10) Reflow test When the LED package to be packaged is continuously passed three times in a reflow oven of 15 minutes, the presence or absence of cracking or peeling of the package material is confirmed. The results are shown in Table 4. (11) Measurement of thermal shock test The packaged LED package was supplied to a test of -4 〇t to l〇〇t cycle, and the crack and the peeling of the package were confirmed by a microscope. The results are shown in Table 5. In Tables 4 and 5, 'incorporated Ε5 series means the embodiment is combined' Ε 6 means that the blending of Example 6 'C1 line means comparative convenience, and C2 means the mixing of the comparative example 2. The same as the following. Also, no, X means there is a blend of 丨!1 I cast package ί, system. The method is set in seconds F color, turtle 500 times] with or without. 5 mixed with 丨 1 mixed 〇 means -38- 201247746

[Table 4] Example 15 16 __1_ E 7 18 19 2 0 Miscellaneous E 5 E 6 7 E 8 E 9 E 1 0 Coloring 〇〇〇〇〇〇 cracking 〇〇〇〇〇〇 peeling 〇〇〇〇〇 〇Comparative Example 8 9 10 11 12 13 14 Blending C 1 C 2 C 3 C 4 C 5 C 6 C 7 Coloring XX 〇〇X 〇〇Crack XX 〇XXXX Peel 〇〇XX 〇〇 X

[Table 5] Real m 15 16 17 18 19 2 0 Blending E 5 E 6 E 7 E 8 E 9 E 10 Crack 〇〇〇〇〇〇 Peel 〇〇〇〇〇〇 Comparative Example 8 9 10 11 12 13 14 Miscellaneous C 1 C 2 , C 3 C 4 C 5 C 6 C 7 Crack XX 〇XXXX Peel 〇〇 XX 〇〇 X

[Industrial Applicability] The epoxy-based epoxy resin of the present invention is excellent in surface hardness, strength, and deformability when a cured product obtained by heat is used as a curable resin composition, and has transparency and heat-resistant coloring. A cured or film that is excellent in light and light resistance. Therefore, it can be used for electronic parts such as semiconductors or circuit boards, etc. -39-201247746 materials, or optical lenses, optical sheets, and light-reflecting optical parts materials, and in particular, LED seals can be expected to be colored by heat and light, and reflow soldered packages. Improvements in cracking, wire breakage, and peeling of the substrate have become problems in materials such as white molding materials. Or in a thermal cycle environment -40-

Claims (1)

201247746 VII. Patent application scope 1. An epoxy oxiran resin' is represented by the general formula (1), and the epoxy equivalent is 1 70~2000 g/eq; In the formula, 'Ni is not the same as the nicotine of carbon number 1~10', and m is 〇<mS10〇, n is the number of OgnS100, and E is the diminution shown by formula (2). Glyceryl tripolyisocyanato-propyl; Z represents a divalent organic residue containing a carbon atom at both ends and containing a Si atom in the interior. 2. The epoxy oxirane according to claim 1, wherein Z in the formula (1) is a divalent organic residue represented by the formula (3) or (4); - 201247746 【化2】 (3) In the formula, R 2 represents a hydrocarbon group having a carbon number of 1 to 10, which may be the same or different, and 1 is a number of hackers 1S100: [Chemical 3], (ch2) 2^J/ R3.0- i R3 l./R3 Si O •Si--R3, (CH2)2 - (4) where R3 represents a hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different, and j and k respectively represent 〇~ 4 integer, lSj + k$4. 3. A method for producing an epoxy-oxygen resin represented by the formula (1), which is characterized in that a polyorganosiloxane having SiM at both ends represented by the formula (5) is used in the formula ( 6) or a polyorganosiloxane having an ethyl group at both ends represented by the formula (7) is reacted in a theoretical amount, and then the remaining SiH group is a monoallyl diglycidyl trimeric isocyanate. Perform end capping reaction; -42- 201247746 【化4】 〇γΝγ〇 /ΝγΝ, (CH2)3 H 0 wherein Ri represents a hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different, m represents 0 < mS100, η represents the number of 0Sn'100, and E represents the formula ( 2) a diglycidyl trimeric isocyanato-propyl group; Z represents a divalent organic residue containing a carbon atom at both ends and containing a Si atom therein; In the Ri Η formula, the 11! and η series have the same meaning as the general formula (1); -43- (5) 201247746 [Chem. 6] (6) where R 2 represents a hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different, and 1 represents the number of 0S1S100: [Chemical 7] r3 n ^1/°' 0· r3〆丨Si- r3 Si 0 1 Si r3 \= (7) where R 3 represents a hydrocarbon group with a carbon number of 1 to 10, which can be: the same or different, 'j, k respectively represent an integer of ~4, l^j + k Each 4. 4. A thermosetting resin composition characterized by comprising a epoxy resin, a curing agent (B), and a curing accelerator (C) as a thermosetting resin composition of a must-have component, as described in the patent application scope The epoxy epoxy resin (A) of the first item is used as an epoxy resin component. 5. The thermosetting resin composition of claim 4, wherein the curing agent (B) is an acid anhydride, a compound having an amine group which is liquid at room temperature, or a phenol resin. 6. The thermosetting resin composition according to item 4 of the patent application, wherein the hardening accelerator (C) in -44 to 201247746 is a grade 4 ammonium salt or a grade 4 phosphonium salt. 7. The thermosetting resin composition of claim 4, wherein the epoxy resin component contains 100 parts by weight of the epoxy epoxy resin (A), and contains an epoxy resin which is liquid at room temperature ( D) 5 to 150 parts by weight, and the epoxy equivalent is 180 to 1 〇〇〇g/eq. 8. The thermosetting resin composition according to claim 4, wherein the thermosetting resin composition is a resin composition for an optical component or a resin composition for an electronic component. 9. The thermosetting resin composition according to claim 4, wherein the thermosetting resin composition is a resin composition for an optical semiconductor component. 10. The thermosetting resin composition according to item 4 of the patent application scope, wherein the medium thermosetting resin composition is a liquid encapsulating resin composition for a semiconductor. 1 1. An LED device characterized by being packaged using a thermosetting resin composition as in claim 9 of the patent application. 201247746 IV Designated representative map: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: None 201247746 V If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None