TW200540197A - Epoxy resin modified with silicone - Google Patents

Abstract

The present invention relates to a silicone-modified epoxy resin (D) having a structural unit of formula (4) obtained by the epoxidation of the vinyl group of a vinyl-containing polyether compound c having structural unit of formula (3) obtained by the reaction of the epoxy group of 4-vinlycyclohexene-1-oxide (A) represent by formula (1) and the silanol group of a silanol-containing organopolysioxane (B) represented by the average composition formula (2) with an oxidizing agent. , in formula (2) a represents 0.01 to 1.99, b represents 1.99 to 0.01, R represents a residue of a monovalent organic compound having 1 to 9 carbon atoms; and the vinyl group in formula (3) and the epoxy group in formula (4) are bound to the α- or β-position of the formulae respectively.

Description

200540197 IX. Description of the invention: (1) Technical field of the invention The present invention relates to a colorless transparent silicone modified epoxy resin which is excellent in heat resistance and humidity resistance and has less internal stress. (2) The most widely used epoxy resins in the prior art are bisphenol A epoxy resins produced by the reaction of bisphenol A and epichlorohydrin. Depending on the degree of polymerization, a wide range of liquids to solids can be obtained. Products; use of polyamines at room temperature, the more reactive the more hardening. However, although this cured product has excellent water resistance and strength, it has the disadvantages of weather resistance, poor electrical properties, and low heat distortion temperature. As sealing resins such as 1C, LSI, or ultra-LSI, there are phenol / phenol novolac or cresol novolac-type epoxy resins, but the chlorine contained in the resin may reduce the electrical characteristics of 1C, LSI, or ultra-LSI, etc. Problem. On the other hand, alicyclic epoxy resins do not contain chlorine and are epoxy resins having excellent electrical characteristics and heat resistance. As commercially available alicyclic epoxy resins, those having high epoxy group reactivity or hardened glass transition point (Tg) and high transparency are widely used, and are used for hardening of electronic insulating sealants or powder coatings. Or glass fiber bundling agent, such as EHPE Siliz (Japanese Patent Publication No. 63-3493, Japanese Patent Publication No. 4- 1 047 1 and Japanese Patent Publication No. 6-25 1 94) Revealed). In alicyclic epoxy resins, an ethylene oxide ring containing a vinylcyclopentene oxide (such as 4-vinylcyclopentene-1-oxide) in a side chain is ring-opened and has a polymerized polymer Ether structure, and the vinyl group has an epoxidized structure 200540197. In the EHPE series, EHPE3 150 is a solid epoxy resin, which is easy to handle. However, the hardened product has higher water absorption than hardened products such as bisphenol A epoxy resin and novolac epoxy resin. Since the cured product of EHPE 3 150 must have improved electrical characteristics, it cannot be fully explained in the field of an insulating sealant for electronics such as a semiconductor sealing material. It has been found that by leaving a part of the vinyl group in the oxidized cyclohexane skeleton of the cycloaliphatic epoxy resin of the aforementioned E Ε PE series unreacted as it is (ie, relatively reducing the degree of epoxidation), the improvement can be achieved. Water absorption (Japanese Patent Publication No. 7-2 5 8 64), but the softening point of this epoxy resin decreases, and there is a new problem that Tg is extremely easy to agglomerate or its hardened product is greatly reduced at room temperature. Further, in Japanese Patent Application Laid-Open No. 2-2 8 2 1 1, an attempt was made to improve the improvement of the addition of organopolysiloxane compounds to the vinyl groups remaining in the vinyl cyclohexane skeleton of the EHPE series alicyclic epoxy resins. Water absorption. In this method, the water absorption is improved to some extent, but it is not possible to obtain a material having sufficient heat resistance. Furthermore, Japanese Patent Application Laid-Open No. 3- 1 23 775 discloses that in the above-mentioned EHPE series of alicyclic epoxy resins, vinyl cyclohexene-1-oxide which imparts the above-mentioned vinyl-substituted cyclohexane skeleton is added. In order to increase the softening point and improve the blocking resistance, a compound having two epoxy groups coexisted in a small amount to form a cross-linked structure in the molecule, but this method is not able to improve the water absorption of the hardened material. (3) Summary of the Invention Therefore, the inventor's intensive deliberation review found that the silicone resin having a silanol group as a solid at room temperature was used as an initiator, and 4-vinylcyclohexene-1- Oxide, or if necessary, also contains other epoxy compounds with an epoxy group on 200540197 'pre-epoxy ring-opening polymerization' using an oxidant to epoxidize residual vinyl groups' can solve epoxy resins at room temperature The agglomeration of the 'hardened product's water absorption and T g are reduced by the problem', and this invention was invented. That is, the first aspect of the present invention is to provide a silicone-modified epoxy resin (D), which has a 4-vinylcyclohexene-butoxide represented by the following formula (1) by using an oxidizing agent. The epoxy group of (A) reacts with the silanol group of the silanol group-containing organopolysiloxane (B) represented by the following average composition formula (2) and has the structural unit of the following (3) The structural unit of the following (4) is formed by epoxidation of the vinyl group of the vinyl polyether compound (C). ° ^ L ⑴

Ra S i (〇 H) b Οl4-a.b) / 2 (2)

0 — (3)

(In formula (2), 'a is 〇.〇ΐ ～ 1.99, b is 1.99 ~ 〇〇ι, and r is a carbon number-valent organic compound residue. In addition, in formula (3), vinyl group and formula (4) Each epoxy group is bonded to the α position or β position in the formula). 200540197 The second aspect of the present invention is to provide the silicone modified epoxy resin (D) as described in the first aspect of the present invention, wherein the oxidizing agent is an organic percarboxylic acid. The third aspect of the present invention is to provide a silicone modified epoxy resin (D) according to the first or second aspect of the present invention, wherein the organopolysiloxane (B) containing a silanol group is a monomethyl silicon. Ketone resin. The fourth aspect of the present invention is to provide a silicone modified epoxy resin (D) according to any one of the first to third aspects of the present invention, in which 4-vinylcyclohexene · fluorene oxide (A) The contact of the ring-opening reaction of epoxy group uses leucine. The fifth aspect of the present invention is to provide a silicone modified epoxy resin (D) according to the fourth aspect of the present invention, wherein the rosic acid-based Bf3 complex is used. The sixth aspect of the present invention is to provide a silicone modified epoxy resin (D) according to the second aspect of the present invention, wherein the organic percarboxylic acid is obtained by oxidizing the corresponding aldehyde with air or oxygen. The seventh aspect of the present invention is to provide a silicone modified epoxy resin (D) according to the sixth aspect of the present invention, wherein the water content in the organic percarboxylic acid is 0.8 weight. / (> hereinafter. The eighth aspect of the present invention is to provide a silicone modified epoxy resin (D) as the second, sixth, or seventh aspect of the present invention, in which the organic percarboxylic acid is peracetic acid. Item 9 is to provide a silicone modified epoxy resin (D) according to item 8 of the present invention, in which a peracetic acid ethyl acetate solution is provided. Item 10 of the present invention is to provide a item such as items 1 to 9 of the present invention. The ketone modified epoxy resin (D) according to any one, wherein the ethylene oxide oxygen content is 10 to 10% by weight. (4) Best Mode for Carrying Out the Invention in the Embodiment 200540197 The following describes the present invention. Embodiment: In the present invention, it is obtained by reacting 4-vinylcyclohexene-1-oxide (A) with a silanol group-containing organopolysiloxane (B) (first-stage reaction) The vinyl-containing polyether compound (c) can be epoxidized (second-stage reaction) of the vinyl-containing polyether compound (C) to obtain a silicone modified epoxy resin (D). The organopolysiloxane (B) containing a silanol group represented by) is an organopolysiloxane having a silanol group in the molecule, which is replaced by polystyrene A silicone resin having a weight average molecular weight of 500 to 100,000. In the first-stage reaction at the time of manufacturing the silicone-modified epoxy resin (D) of the present invention, a structural formula represented by the following formula (3) is obtained. Unit of vinyl-containing polyether compound (C).

(In the formula, the vinyl system is bonded to the α position or the (3 position). The ethyl ether-containing polyether compound (C) having the structural formula unit represented by the above formula (3) can be obtained by the above organic polymerization. The silanol hydroxyl group of the siloxane (B), 4-vinylcyclohexene-1-oxide of the (A) component, and the epoxy group of other compounds having one or more epoxy groups are used as needed. It is obtained by reaction in the presence of a medium. In the reaction of the first stage, relative to the number of silanol hydroxyl groups of the organopolysiloxane of (B) component, 4-vinylcyclohexene-1-oxide of (A) component And if necessary, the number of epoxy groups of the compound having one or more epoxy groups is equivalent to the reaction ratio. By changing this ratio, various adjustments can be made to the molecular weight. -10- 200540197 For each silanol group, 4-vinylcyclohexene-1-oxide of component (A) and other compounds having one or more epoxy groups may be used in a total amount of 2 to 30. If the sum exceeds 30, it will become a solid with a high melting point, which is not practical. Yes, when explaining that no other compound having one or more epoxy groups is used, the hydrogen structure is bonded to the binding end of the formula (3) in terms of the terminal structure of the structural unit chain of the formula (3). The oxygen atom becomes a hydroxyl group. (A) The proportion of 4-vinylcyclohexene-1-oxide of the component and other compounds having one or more epoxy groups, if necessary, is 100 for the total of the two. In terms of mole%, 4-vinylcyclohexene-1-oxide based on (A) component is 1 to 100 mole%, preferably 20 to 100 mole%. Others used as required have 1 The above epoxy compound is 99 to 0 mole%, preferably 80 to 0 mole%. (A) When the 4-vinylcyclohexene-1 -oxide of the component is less than 1 mole, it cannot be Features based on the cyclohexane skeleton. Other compounds with one or more epoxy groups are used as needed. They are aliphatic epoxy compounds such as glycidyl methacrylate, α-olefin oxide, and epoxidized. Tetrahydrobenzyl alcohol, 3,4-epoxycyclohexylmethyl (meth) acrylate, cyclohexene oxide, dicyclopentadiene diepoxide Is an alicyclic epoxy compound, or an aromatic epoxy compound such as styrene oxide, etc., but is preferably an aliphatic epoxy compound. The component (B) used as the initiator of the ring-opening reaction of the epoxy group The organosilicon system has a silanol group in the molecule, and its average composition is represented by formula (2): R a S i (〇 Η) b〇 (4-ab) / 2 (2) • 11-200540197 (2) 'a and b are arbitrary 値 that conforms to the relational expression of a + b = 2 + 2 / n (n-based degree of polymerization), a is preferably 〇〇〇 ～ 1.99, more preferably 0.5 ～ 1.5 B is preferably 0.01 to 1.99, more preferably 0.01 to 1, and R represents a monovalent organic group having 1 to 9 carbon atoms. This organosiloxane is a silicone resin having a weight-average molecular weight of 500 to 10,000 in terms of polystyrene. The R in the above average composition formula is, for example, an alkyl group such as methyl, ethyl, n-propyl, isopropyl, or butyl, a fluoroalkyl group such as 3,353-trifluoropropyl, or an aryl group such as phenyl 'And γ-chloropropyl, ethylthio, γ-methylpropyloxypropyl, glycidyloxypropyl, β- (3,4-epoxycyclohexyl) ethyl, N_ (β- Aminoethyl) -γ · aminopropyl, γ-fluorenylpropyl and the like. The silicone resin may be a coating intermediate, a varnish for electrical use, or a modification intermediate containing a silanol group sold by a silicone manufacturer. Specific examples are TSR127B, TSR160 (Toshiba Silicone), KR212, KR216, KR311 (Shin-Etsu Chemical Industries) SH6 01 8 (Toray-Dow Corning Silicone), etc. These silicone resins can be supplied in the form of dissolved in organic solvents such as toluene and xylene, or in the form of chips. The catalyst used in the reaction may be, for example, amines such as methylamine, ethylamine, propylamine, piperine, organic bases such as pyridine, imidazole, and quaternary ammonium salts such as tetramethylammonium bromide, formic acid, and acetic acid. Organic acids such as propionic acid, inorganic acids such as sulfuric acid and hydrochloric acid, alkoxides of alkali metals such as sodium methoxide, alkalis such as KOH, NaOH, BF3, ZnCl2, A1C13, SnCl4, etc. Complexes, organometallic compounds such as triethylaluminum and diethylzinc. Among these catalysts, leucoic acid is preferred, and 6-8 etherate is preferred. -12- 200540197 The amount of catalyst varies with its type, and it can be used in the range of 0.01 to 10 wt. It is preferably in the range of 0.1 to 5% by weight. The reaction temperature is -20 to 200C, preferably 0 to 12CTC. The reaction can also be performed using a solvent. Solvents are preferably ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, aromatic hydrocarbons such as benzene, toluene, xylene, aliphatic hydrocarbons such as Kojiri, Cyclo Koji, and ethyl acetate Ester-based solvents such as esters do not have active hydrogen. The polyether compound (C) having a vinyl side bond and having the structural formula unit of the formula (3) obtained by the first-stage reaction of this brother is an oxidant such as a peracid or a hydroperoxide in the second-stage reaction. The epoxy resin thus obtained is a silicone modified epoxy resin (D) of the present invention. The obtained silicone-modified epoxy resin (D) of the present invention is a compound having a structural unit represented by the following formula (4). In addition, 'in the case where no other compound having one or more epoxy groups is used', as far as the terminal structure of the structural unit chain of formula (4) is concerned, a hydrogen system is bonded to an oxygen atom at the binding end of formula (4). And become hydroxyl. Moreover, under the reaction conditions of the ring-opening polymerization of the first-stage epoxy group and / or the second-stage epoxidation reaction, the bonding end of the formula (4) may be partially changed to a methoxy group (carboxylic acid ester) and an alkoxy group. (Alkyl ether) and the like.

(In the formula, an epoxy group is bonded to an α position or a β position.) As peracids, organic percarboxylic acids can be used, and specifically, performic acid, peracetic acid, -13-200540197 perbenzoic acid, trifluoroperacetic acid, and the like can be used. Among the organic percarboxylic acids, the water content of the corresponding aldehyde oxidized by air or oxygen is low, which makes the silicone modified epoxy resin (D) of the present invention have a higher epoxidation rate. of. The organic percarboxylic acid preferably has a moisture content of 0.8% by weight or less. In addition, as for the epoxy group in the above formula (4), a part of the 4-vinylcyclohexene derived from the (A) component of the starting material can also be made by appropriately selecting the conditions of the epoxidation reaction- The vinyl group of the 1-oxide remains unreacted. Among the organic percarboxylic acids, particularly peracetic acid, they are industrially available at low cost and have a high degree of stability, so they are preferred epoxidants. As the hydroperoxides, hydrogen peroxide, third butyl peroxide, cumene hydroperoxide, and the like can be used. Catalysts can be used during epoxidation as needed. For example, in the case of a peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used. In the case of hydroperoxides, a mixture of tungstic acid and caustic soda and hydrogen peroxide, or an organic acid and hydrogen peroxide, or molybdenum hexacarbonyl and a third butyl hydroperoxide can be obtained. Catalyst effect. The epoxidation reaction depends on the physical properties of the device or raw materials, and the presence or absence of a solvent or the reaction temperature is adjusted. The reaction temperature range that can be used depends on the reactivity of the epoxidant used. For the preferred epoxidizing agent peracetic acid, the preferred temperature is 0 ° C to 70 ° C °. If the temperature is below 0 ° C, the reaction is slow. If it is at 7CTC, the peracetic acid will decompose. As for the third butyl hydroperoxide / molybdic acid divinylpyruvate, which is an example of hydroperoxide, it is preferably 200c to 1550. For the purpose of reducing the viscosity of raw materials and diluting the epoxidizer for the purpose of -14-200540197, solvents can be used. In the case of peracetic acid, an aromatic compound, an ether compound, an ester compound, a ketone compound, or the like can be used as a solvent. In order to manufacture the silicone-modified epoxy resin (D) of the present invention, the molar amount of the epoxy agent is preferably 0.9 times or more relative to the vinyl group of the polyether compound (c) having the structural unit of the formula (3). . In the case of peracetic acid, it is more preferable to add Mortar from 0.95 to 1.2. The target compound can be removed from the reaction mucus by means of general chemical engineering such as concentration. Examples The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. [Synthesis Example 1] 187 g of a commercially available silicone resin SH6018 (manufactured by Toray Dow Corning Silicone Co., Ltd., as a component (B), a chip-like solid appearance, a hydroxyl content of 6.4% by weight, and a melting point of 85 ° C), 62 0 g of 4-vinylcyclohexene-buoxide as the component (A), 200 g of a BF3 etherate in 10% ethyl acetate solution was dropped at 50 ° C for 4 hours. Ethyl acetate was added to the obtained reaction slime, washed with water, and then the ethyl acetate layer was condensed to obtain 790 g of a (C) component-containing vinyl polyether compound [having the structural unit of the formula (3) compound of]. The weight average molecular weight of this compound was 2740. 660 g of the same compound having the structural unit of formula (3) was dissolved in 350 g of ethyl acetate, put into the reactor, and 320 g of peracetic acid-15-200540197 acid was dropped at 50 ° C for 4 hours (relative to A solution of vinyl mol ratio of 1.0) in 1067 g of ethyl acetate (peracetic acid concentration was 30% by weight). After the dripping was completed, it was matured at 50 ° C for 2 hours. After removing acetic acid, ethyl acetate and peracetic acid, it is dissolved in ethyl acetate again, washed with distilled water, and then the ethyl acetate layer is concentrated to obtain a compound having the structural unit of the formula (4), that is, the present invention Silicone modified epoxy resin (D). By chemical analysis, it was confirmed that the target object has an ethylene oxide oxygen content of 7.60. The softening point was 73.7 ° C. The W-NMR chart of each compound is shown in the figure, and the characteristics of the peaks are shown in each figure. FIG. 1 is an iH-NMR chart of the corresponding compound (silicone resin S H-6018) of the formula (2) as the component (B). In the 1H-NMR chart of SH-6018, the absorption due to the protons of the Alcohol group of Shayuan was seen at 4.8 ppm. FIG. 2 is a 1H-NMR chart of a compound having a structural unit of formula (3) of the component (C) < Identification of a peak in a 1H-NMR chart of a compound having a structural unit of formula (3) > In the 1H-NMR chart of the compound having the structural unit of the formula (3), the peaks of about 5.7 and 4.9 ppm are based on the ethyl matrix of the 4-vinylcyclohexene-1-oxide derived from the formula (1). As a result, a peak of 3.5 to 3.4 ppm is caused by a methine group generated by ring opening of an epoxy group derived from 4-vinylcyclohexene-oxooxide. It was confirmed that the silanol matrix protons near 4.8 ppm seen in the 1H-NMR chart of SH-6018 disappeared from the second chart after the reaction. Fig. 3 is a -16-200540197 j-NMR chart of a corresponding compound having the structural unit of (4) in the component (D). < Identification of peak in j-NMR chart of corresponding compound having structural unit of formula (4) > From iH-NMR chart of corresponding compound having structural unit of formula (4), from iH-NMR chart of corresponding compound having structural unit of formula (4), ) The compounds with structural formula units strongly see that the crests caused by vinyl protons are almost absent at about 5.7 and 4.9 ppm, and it is confirmed that there are new ones from ethylene at about 2.7 and 2.5 ppm. Epoxy matrix protons caused by epoxidation of radicals. [Comparative Synthesis Example 1] (Based on Synthesis Example 1 of Japanese Patent Publication No. 7-2 5 8 64) 134 g of trimethylolpropane (1 mole) and 1860 g (15 mole) of 4-vinylcyclohexane were mixed. Ene oxide, 4,000 g of BF 3 etherate in 10% ethyl acetate solution was dripped at 50 ° C for 4 hours. Ethyl acetate was added to the obtained reaction slime, washed with water, and then the ethyl acetate layer was concentrated to obtain 1,990 g of a vinyl polyether-containing compound. Next, 500 grams of the compound was dissolved in 250 grams of ethyl acetate, put into the reactor, and 2 8 6 grams of peracetic acid was dripped at 50 ° C for 4 hours (1.0 relative to the vinyl molar ratio). ) In 953 g of ethyl acetate (peracetic acid concentration is 30% by weight). After the dripping was completed, it was matured at 50 ° C for 2 hours. After removing acetic acid, ethyl acetate and peracetic acid, it was dissolved in ethyl acetate again and washed with distilled water, and then the ethyl acetate layer was concentrated to obtain an epoxy resin. By chemical analysis, it was confirmed that the ethylene oxide oxygen content in the epoxy resin was 9.05. The softening point is 呔 68 4 °. [Comparative Synthesis Example 2] -17-200540197 An epoxy resin was obtained in the same manner as in the example, except that the amount of peracetic acid was changed to 1 729 g (mole ratio of 0.6 to ethyl alcohol). It was confirmed by chemical analysis that the oxygen content of the epoxy resin in the epoxy resin was 6.25. The softening point was 5 8.6 TC. < Evaluation of epoxy resin and its cured product > (Evaluation of uncured epoxy resin) Anti-blocking property [Test conditions] In a 250 ml polypropylene container with a screw cap (tubular shape, diameter 6) The epoxy resin obtained in the synthesis example and the comparative synthesis example was filled with "inside" to $ 80 g (about 5 cm in length), and then placed in a desiccator at a temperature of 30, taken out, observed and evaluated. The state of the powder. Evaluation is performed in five levels based on the following criteria. 5: The state of falling smoothly when tilted. 4: Dropped when turned upside down. 3: In a state where it is inverted and dispersed again during vibration. 2: In a state of falling down when knocked upside down, there is a part of molten block. 1: Agglomeration, which cannot fall even when hit. See Table 1 for the anti-caking test sample name 2 hours later '10 hours and 24 hours later 7 hours later Synthesis of the epoxy resin of Example 1 5 5 4 3 Comparative Synthesis of the epoxy resin of Example 1 5 4 3 2 Comparative synthesis Epoxy resin 3 of Example 2 2 1 -18- 200540197 (Evaluated by hardened material) [Solution and hardening of epoxy resin] The hardener and hardening accelerator were dissolved together in acetone to synthesize the synthesis examples and comparative synthesis. The solid content of the synthesized epoxy resin was 75% by weight. Next, necessary amounts were cast into the following containers, respectively. A box of L3 00xW200xH50 (mm) was made from a prototype paper, put into an aluminum container, and the solution prepared above was cast to a net weight of 60 g. After removing acetone and defoaming, the upper epoxy resin is hardened (hardening conditions: 1 1 (TC x 1 hour + 150 ° C x 2 hours). Hardeners and hardening accelerators use the parts shown in Table 2 below. [Measurement of Tg] The DSC measurement was performed according to the method for measuring the transition temperature of plastics (JISK7 121). Heating rate: 5t: / min 30 ° C ~ 38 0 ° C [Measurement of water absorption] at 120 ° C, 90% After standing for 96 hours in an RH environment, the weight increase was measured, and the water absorption (average 値 of the number of tests 3) was calculated from the following formula. (Weight increase after the test) / weight before the test) x 100 (%) Example 1 Comparative Example 1 Comparative Example 2 Epoxy resin (softening point ° Synthetic Example 1 100 (73.7 ° Synthetic Synthesis Example 1 100 (68.4 ° Celsius Comparative Synthetic Example 2 100 (58.6 ° Celsius MH-700 78.8 94.4 62.2 DBU (0.5phr) 0.89 0.97 0.81 Tg (° C) 311.9 320.9 256.3 Water absorption (%) 1.32 2.01 1.21 -19- 200540197 The unit of the amount of each substance in Table 2 is parts by weight, and the substance indicated by the abbreviation symbol is as follows MH-700: methylhexahydrophthalic anhydride (Lika GMH-700 manufactured by Nippon Kayaku Co., Ltd.) (hardener) DBU: 1,8_diazabicyclo (5,4, 〇) undecene-7 (hardening accelerator) Industrial applicability The hardened system of the silicone-modified epoxy resin of the present invention has a high T g With excellent heat resistance and low water absorption, it can be used as an excellent L SI sealing material. Also, the use of the silicone modified epoxy resin of the present invention in impregnated coils can be used as a substitute for the epoxy resin currently used. Since the degree of polymerization can be freely adjusted by the input ratio of the compound (A), it has the advantage of being suitable for performance. Furthermore, it can be applied to a wide range of applications such as LED or semiconductor sealing materials and coatings. (5) Simple diagram 1 illustrates the 1H-NMR chart of the compound corresponding to the formula (2) of the component (B) used in Synthesis Example 1. Figure 2 illustrates the correspondence of the structural formula units having the formula (3) obtained in Synthesis Example 丨. H-NMR chart of the compound. Figure 3 is a W-NMR chart of a corresponding compound having the structural unit of formula (4) of the silicone-modified epoxy resin (D) of the present invention obtained in Synthesis Example 1.- 20-

Claims (1)

200540197 10. Scope of patent application: 1. A silicone modified epoxy resin (D) having 4-vinylcyclohexene-1-oxide represented by the following formula (1) by using an oxidizing agent. The epoxy group of (A) reacts with the silanol group of the silanol group-containing organopolysiloxane (B) represented by the following average composition formula (2), and has the structural unit of the following (3) Structural unit of the following (4) formed by epoxidation of the vinyl group of the vinyl polyether compound (C), (1) Ra s I (〇H) b 〇 (4-a-b, / 2 (2) ο — (3) ο — 〇 (4) (In formula (2), 'a is 0.01 to 1.99', b is 1.99 to 0.001, and R is a monovalent organic compound residue of carbon number ι to ς, and the vinyl group in formula (3) and Each of the epoxy groups in the formula (4) is bonded to an α position or a β position in the formula). 2. The silicone modified epoxy resin (D) according to item 1 of the patent application scope, wherein the oxidizing agent is an organic percarboxylic acid. -21-200540197 3 · If the silicone modified epoxy resin (D) of item 1 or 2 of the patent application scope, the organopolysiloxane (B) containing a silanol group is a monomethyl silicone resin. 4. The silicone-modified epoxy resin (D) according to any one of claims 1 to 3, wherein the ring-opening reaction of the epoxy group of 4-vinylcyclohexene · oxide (A) The catalyst used is leucosic acid. 5. For example, the silicone modified epoxy resin (D) in item 4 of the scope of patent application, in which lauric acid is a BF3 complex. 6. The silicone modified epoxy resin (D) according to item 2 of the patent application, wherein the organic percarboxylic acid is obtained by oxidation of the corresponding aldehyde with air or oxygen. 7. The silicone modified epoxy resin (D) according to item 7 of the patent application scope, wherein the water content in the organic percarboxylic acid is 0.8% by weight or less. 8 · If the silicone modified epoxy resin (D) of the patent application No. 2, 6 or 7 is used, the organic percarboxylic acid is peracetic acid. 9. The silicone modified epoxy resin (D) according to item 8 of the application, wherein the peracetic acid is ethyl acetate solution. 10. The silicone-modified epoxy resin (D) 'according to any one of claims 丨 to 9 in the patent application range, wherein the oxygen content of the ethylene oxide compound is 1.0 to wt%. •twenty two-