JP2012236893A - Epoxy-modified silicone composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy-modified silicone composition whose cured material has favorable transparency and excellent light resistance, heat-fading resistance, adhesiveness, and has excellent storage stability even when exposed to high-temperature environment in transport or storage, and also to provide a curable epoxy-modified silicone composition containing the above composition.SOLUTION: The epoxy-modified silicone composition contains 0.0005-5 pts.mass of at least one antioxidant selected from the group consisting of phenolic, phosphoric, sulfuric and amine-based antioxidants based on 100 pts.mass of an epoxy-modified silicone represented by an average composition formula (1) [wherein Rs are each independently (A) a monovalent aliphatic organic group, (B) a monovalent aromatic organic group or (C) a monovalent organic group; and Rs are each independently an organic group containing epoxy groups].

Description

  The present invention relates to an epoxy-modified silicone composition having excellent storage stability.

  Conventionally, an epoxy resin composition using an acid anhydride-based curing agent has been suitably used as a sealing material for light-emitting elements such as light-emitting diodes and photodiodes that give a transparent cured product and have high heat resistance. However, in recent years, the performance of optical semiconductors has advanced, and in addition to good transparency and high heat resistance for sealing resins, it also has excellent light resistance, oxidation resistance, and warm / cool cycle accompanying LED on / off cycle Crack resistance (hereinafter abbreviated as “crack resistance”), adhesion during heating / cooling cycle (hereinafter abbreviated as “adhesion”), and solder reflow performed at 250 ° C. or higher Hardened products having crack resistance and adhesiveness (hereinafter abbreviated as “solder reflow resistance”) have been required, and conventionally used bisphenol A epoxy resins, bisphenol F epoxy resins, etc. In the case of the composition mainly composed of the epoxy resin, sufficient characteristics cannot be obtained.

  Epoxy-modified silicones with a siloxane skeleton as a repeating unit and an epoxy group in the organic group not only have the excellent transparency and heat resistance of epoxy resins, but also the light resistance, oxidation resistance, and flexibility of silicone. Therefore, it is attracting attention as a high-performance sealing material, and many techniques have been disclosed.

  For example, Patent Document 1 contains a T structure as an essential repeating unit and contains an epoxy group-containing organic group in the range of 0.1 to 40 mol% with respect to all organic groups bonded to a silicon atom in one molecule. Epoxy-modified silicones have been proposed.

  Patent Document 2 proposes a composition containing a silicone compound having a molecular weight in a specific range and having at least two epoxy groups in one molecule, and its use for an optical semiconductor sealing material. Has been made.

  In the above Patent Documents 1 and 2, a cured product obtained using the epoxy-modified silicone has high heat resistance, high light resistance, or high adhesiveness, or a cured product containing the resulting epoxy-modified silicone. Although there is a description that the curable composition has high curability, the storage stability of the epoxy-modified silicone itself containing a highly reactive epoxy group in the molecule is low, and it is exposed to a high temperature environment during transportation and storage. It could not be said that the storage stability was still sufficient, such as viscosity change when exposed. Further, there is no description or suggestion regarding a composition in which an antioxidant is blended with epoxy-modified silicone, and an effect that is manifested by blending the antioxidant.

  On the other hand, there are many disclosures regarding a method of blending an antioxidant with a curable epoxy resin composition. For example, Patent Document 3 discloses a phenol-based antioxidant, a sulfur-based antioxidant and a phosphorus-based antioxidant for a mixture containing a specific alicyclic epoxy resin, an epoxy resin curing agent, and, if necessary, a cationic polymerization initiator. A composition containing a specific amount of at least one kind of antioxidant selected from the group consisting of a series of antioxidants is disclosed. By blending the antioxidant, coloring during heating is reduced. There is a description. However, in the patent document, there is no description or suggestion regarding a composition in which an antioxidant is blended with the epoxy resin itself and an effect that is manifested by blending the antioxidant.

Japanese Patent No. 3263177 JP 2005-171021 A JP 2010-215924 A

  In the present invention, when cured, the cured product has good transparency, excellent light resistance, excellent heat discoloration, and excellent adhesion, and is exposed to a high temperature environment during transportation and storage. An object of the present invention is to provide an epoxy-modified silicone composition having excellent storage stability, and a curable epoxy-modified silicone composition containing the epoxy-modified silicone composition.

  In view of the above points, as a result of intensive studies by the present inventors, it has been found that an epoxy-modified silicone composition containing a specific amount of a specific antioxidant can solve the above problems, and has led to the completion of the present invention. . That is, the present invention is as follows.

[1] For 100 parts by mass of the epoxy-modified silicone represented by the following average composition formula (1), selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and amine antioxidants. An epoxy-modified silicone composition comprising 0.0005 parts by mass or more and 5 parts by mass or less of at least one antioxidant.

[In the average composition formula (1), each R ¹ independently has (A) a chain, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, and has 1 to 24 carbon atoms. Or a monovalent aliphatic organic group having 0 or more and 5 or less oxygen atoms, (B) monovalent or unsubstituted or substituted carbon atoms having 6 or more and 24 or less, and oxygen atoms having 0 or more and 5 or less A monovalent aromatic organic group having a substituent having a linear, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, when substituted, Or (C) a chain, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, or an unsubstituted or substituted aromatic hydrocarbon structure, having 5 to 26 carbon atoms, oxygen atom Represents a monovalent organic group having a number of 0 to 5 and a silicon atom number of 1 . A plurality of R ¹ in each siloxy unit may be the same or different.
R ² each independently has a chain, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, having 4 to 24 carbon atoms and 1 to 5 oxygen atoms. Represents a monovalent organic group containing an epoxy group. A plurality of R ² in each siloxy unit may be the same or different.
Y is each independently composed of one or more structures selected from the group consisting of unsubstituted or substituted chain, branched and cyclic, having 2 to 70 carbon atoms and 0 to 15 oxygen atoms. Hereinafter, a divalent organic group having 0 or more and 10 or less silicon atoms is represented. A plurality of Y in each siloxy unit may be the same or different.
Z represents a divalent hydrocarbon group bonded to Y.
a, b, c, d, e, f, g, h, i, j, k, l, m, n represent the number of moles of each siloxy unit present in 1 mole of epoxy-modified silicone; , C, d, e, f, g, h, i, j, k, l, m, and n are values that are 0 or more, and satisfy d + h + k> 0, e + f + h + i + j + k> 0, and g = a + f + l at the same time. ]

[2] The epoxy-modified silicone composition according to [1], wherein the total content of transition metal elements is 30 mass ppm or less.
[3] The epoxy-modified silicone composition according to [1] or [2], wherein an epoxy value of the epoxy-modified silicone is in a range of 0.15 to 0.50.
[4] The epoxy modification according to any one of [1] to [3], wherein each R ² is independently any organic group represented by the following general formulas (2) to (5). Silicone composition.

[In General Formulas (2) to (5), each R ³ is independently a chain, branched or cyclic unsubstituted group having 1 to 16 carbon atoms and 1 to 4 oxygen atoms. Alternatively, it represents a substituted divalent organic group. ]
[5] The epoxy-modified silicone composition according to any one of [1] to [4], wherein the content of SiH groups with respect to the total number of Si in the epoxy-modified silicone is less than 2%.
[6] The epoxy-modified silicone composition according to any one of [1] to [5], wherein the viscosity at 25 ° C. is 500,000 mPa · s or less.
[7] The curing catalyst is contained in an amount of 0.001 to 10 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone composition according to any one of [1] to [6]. A curable epoxy-modified silicone composition.

  According to the present invention, when cured, the cured product has good transparency, excellent light resistance, excellent heat discoloration, excellent adhesion, and is exposed to a high temperature environment during transportation and storage. In some cases, an epoxy-modified silicone composition having excellent storage stability and a curable epoxy-modified silicone composition containing the epoxy-modified silicone composition can be provided.

The epoxy-modified silicone composition of the present invention is at least one selected from the group consisting of an epoxy-modified silicone represented by the following average composition formula (1), a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. A kind of antioxidant.

In the average composition formula (1), each R ¹ independently has (A) a chain, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, and has 1 to 24 carbon atoms. And a monovalent aliphatic organic group having 0 to 5 oxygen atoms, (B) a monovalent aliphatic group having 6 to 24 carbon atoms, unsubstituted or substituted, and 0 to 5 oxygen atoms. A monovalent aromatic organic group having a substituent having a linear, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, if the aromatic organic group is substituted, or (C) having a chain, branched, or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, or an unsubstituted or substituted aromatic hydrocarbon structure, having 5 to 26 carbon atoms and the number of oxygen atoms Represents a monovalent organic group having 0 to 5 and 1 silicon atom. A plurality of R ¹ in each siloxy unit may be the same or different.

R ² each independently has a chain, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, having 4 to 24 carbon atoms and 1 to 5 oxygen atoms. Represents a monovalent organic group containing an epoxy group. A plurality of R ² in each siloxy unit may be the same or different.

Y is each independently composed of one or more structures selected from the group consisting of unsubstituted or substituted chain, branched and cyclic, having 2 to 70 carbon atoms and 0 to 15 oxygen atoms. Hereinafter, a divalent organic group having 0 or more and 10 or less silicon atoms is represented. A plurality of Y in each siloxy unit may be the same or different.
Z represents a divalent hydrocarbon group bonded to Y.

  a, b, c, d, e, f, g, h, i, j, k, l, m, n represent the number of moles of each siloxy unit present in 1 mole of epoxy-modified silicone; , C, d, e, f, g, h, i, j, k, l, m, and n are values that are 0 or more, and satisfy d + h + k> 0, e + f + h + i + j + k> 0, and g = a + f + l at the same time.

  Here, in the average composition formula (1), when j, k, l, m, and n simultaneously satisfy the following formulas (I) and (II), the above a, b, c, d, j , K, l, m, and n are numerical values selected from a range that satisfies Formula (III).

j + k + 1 + m> 0 Formula (I)
n> 0 Formula (II)
0 ≦ (b + c + d) ≦ a + (j + k + 1 + m) + 2n + 2 Formula (III)
When j, k, l, m, and n satisfy the following expressions (IV) and (V), the above a, b, c, and d satisfy the following expression (VI). A number selected from a range.

j + k + 1 + m = 0 Formula (IV)
n = 0 Formula (V)
0 ≦ (b + c + d) ≦ a + 2 Expression (VI)
Further, when the above j, k, l, m, and n satisfy the following formulas (I) and (V), respectively, a, b, c, d, j, k, l, m Is a numerical value selected from a range satisfying the following mathematical formula (VII).

j + k + 1 + m> 0 Formula (I)
n = 0 Formula (V)
0 ≦ (b + c + d) ≦ a + (j + k + 1 + m) +2 Equation (VII)
Furthermore, when j, k, l, m, and n simultaneously satisfy the following formulas (IV) and (II), the above a, b, c, d, and n satisfy the following formula (VIII). A number selected from a range.

j + k + 1 + m = 0 Formula (IV)
n> 0 Formula (II)
0 ≦ (b + c + d) ≦ a + 2n + 2 Equation (VIII)

The average composition formula (1) representing the epoxy-modified silicone according to the present invention will be described in detail below.
The siloxane chain of the epoxy-modified silicone according to the present invention may be random or block.

In the present invention, each R ¹ independently has (A) a chain, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, having 1 to 24 carbon atoms and the number of oxygen atoms A monovalent aliphatic organic group in which is 0 or more and 5 or less, (B) a monovalent aromatic organic group having 6 or more and 24 or less unsubstituted or substituted carbon atoms and 0 or more and 5 or less oxygen atoms And when substituted, a monovalent aromatic organic group having a substituent having a linear, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, or (C) chain Having a straight, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure and / or an unsubstituted or substituted aromatic hydrocarbon structure, having 5 to 26 carbon atoms and 0 oxygen atoms A monovalent organic group having 5 or less and 1 silicon atom is represented. A plurality of R ¹ in each siloxy unit may be the same or different.

(A) Monovalent fat having a chain, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, having 1 to 24 carbon atoms and 0 to 5 oxygen atoms Examples of group organic groups include:
(A-1) methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, a chain organic group composed of an aliphatic hydrocarbon such as an n-octadecyl group,
(A-2) a chain organic group composed of an aliphatic hydrocarbon containing a carbon-carbon double bond such as vinyl group, allyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group,
(A-3) an organic group comprising a hydrocarbon containing a cyclic unit such as a cyclopentyl group, a methylcyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a norbornyl group,
(A-4) An organic group containing an ether bond such as methoxyethyl, ethoxyethyl, propoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group,
Etc.

  (B) a monovalent aromatic organic group having 6 or more and 24 or less unsubstituted carbon atoms and 0 or less and 5 or less oxygen atoms, and when substituted, when substituted, Examples of the monovalent aromatic organic group having a substituent having a branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure include a phenyl group, a tolyl group, a xylyl group, a benzyl group, and α-methyl. Examples include a styryl group, a 3-methylstyryl group, and a 4-methylstyryl group.

  (C) a chain, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, or an unsubstituted or substituted aromatic hydrocarbon structure, having 5 to 26 carbon atoms, oxygen atom Examples of the monovalent organic group having a number of 0 or more and 5 or less and the number of silicon atoms of 1 include organic groups represented by the following general formula (6) and general formula (7).

Here, each R ⁴ independently has (D) a chain, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, having 1 to 8 carbon atoms and a number of oxygen atoms. A monovalent aliphatic organic group of 0 or more and 5 or less, or (E) an unsubstituted or substituted aromatic hydrocarbon structure, and an optionally substituted or substituted chain, branched or cyclic A monovalent aromatic organic group having an aliphatic hydrocarbon structure and having 6 to 8 carbon atoms and 0 to 5 oxygen atoms.

Hereinafter, a specific example of R ^4.
(D) Monovalent fat having a chain, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, having 1 to 8 carbon atoms and 0 to 5 oxygen atoms Examples of group organic groups include:
(D-1) methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, a chain organic group comprising an aliphatic hydrocarbon such as an n-octadecyl group,
(D-2) an organic group comprising a hydrocarbon containing a cyclic unit such as a cyclopentyl group, a methylcyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, or a norbornyl group;
(D-3) Methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, alkoxy group such as t-butoxy group, methoxyethyl, ethoxyethyl, propoxyethyl group, methoxypropyl group, ethoxypropyl group An organic group containing an ether bond such as a propoxypropyl group,
Etc.

  And (E) an unsubstituted or substituted aromatic hydrocarbon structure and an optionally substituted or substituted chain, branched or cyclic aliphatic hydrocarbon structure, and a carbon atom Examples of the monovalent aromatic organic group having 6 to 8 and oxygen atoms of 0 to 5 include, for example, phenyl group, tolyl group, xylyl group, benzyl group, α-methylstyryl group, 3-methyl Examples thereof include organic groups composed of aromatic hydrocarbons such as a styryl group and a 4-methylstyryl group. These may be organic groups in which one kind or two or more kinds are mixed.

Next, the organic group R ² in the present invention will be described.
R ² each independently has a chain, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, having 4 to 24 carbon atoms and 1 to 5 oxygen atoms. And a monovalent organic group containing an epoxy group, and examples thereof include the following general formulas (2) to (5), general formula (8), and general formula (9). A plurality of R ² in each siloxy unit may be the same or different.

R ³ in the above general formula has an aliphatic hydrocarbon structure in which R ² is a chain, branched or cyclic unsubstituted or substituted, has 4 to 24 carbon atoms and 1 oxygen atom. There is no particular limitation as long as it is a monovalent organic group containing 5 or less and containing an epoxy group, and it varies depending on the structure of the epoxy group. For example, — (CH ₂ ) ₂ —O—, — (CH ₂ ) _{3 -O -, - (CH 2} ) 4 -O -, - CH 2 -CH (CH 3) -O -, - CH 2 -CH (CH 3) -CH 2 -O -, - CH 2 -CH 2 _{-CH (CH 3) -O -,} - CH 2 -CH (CH 3) -COO -, - CH 2 structure containing an ether bond or an ester bond of -CH 2 -COO-, etc., - _{(CH 2) 2} - _{, -CH (CH 3) -,} - (CH 2) 3 -, - CH (CH 3) -CH 2 -, - C H ₂ —CH (CH ₃ ) —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, — (CH ₂ ) ₆ —, — (CH ₂ ) ₇ —, — (CH ₂ ) ₈ —, _{- (CH 2) 9 -,} - (CH 2) 10 -, - (CH 2) 11 -, - (CH 2) 12 -, - (CH 2) 13 -, - (CH 2) 14 -, - ( Examples thereof include an aliphatic hydrocarbon structure composed of a chain or branched chain such as CH ₂ ) ₁₅ — and — (CH ₂ ) ₁₆ —.

When there are a plurality of R ³ groups in one molecule of the epoxy-modified silicone, they may be the same or different. Furthermore, when an optical isomer exists, it may be an organic group mixed alone or in combination of two or more optical isomers.

Next, the organic group Y and the bond Z in the present invention will be described.
The organic group Y is a linking group formed by hydrosilylation during the production of the epoxy-modified silicone according to the present invention described later, and is independently from the group consisting of an unsubstituted or substituted chain, branched and cyclic group. It is a divalent organic group comprising one or more selected structures, having 2 to 70 carbon atoms, 0 to 15 oxygen atoms, and 0 to 10 silicon atoms. Specific examples include a divalent organic group represented by the following general formula (10).

In general formula (10), p is 0 or a positive number of 10 or less. R ⁵ is each independently a divalent aliphatic organic group having 1 to 10 carbon atoms and 0 to 3 oxygen atoms, and R ⁶ is each independently unsubstituted or substituted. It is a monovalent organic group having 1 or more and 6 or less carbon atoms composed of one or more structures selected from the group consisting of substituted chain, branched and cyclic groups, and Y has 2 to 70 carbon atoms. Hereinafter, the number of oxygen atoms is selected from the range of 0 to 15 and the number of silicon atoms is 0 to 10 inclusive. A plurality of R ⁵ and R ⁶ may be the same or different.

Examples of such R ⁵ include — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, — (CH ₂ ) ₆ —, _{-CH (CH 3) -, -} CH 2 -CH (CH 3) -, - CH 2 -CH (CH 3) -CH 2 -, - CH 2 -CH (CH 3) - (CH 2) 2 -, _{-CH 2 -CH (CH 3) -} (CH 2) 3 -, - CH 2 -CH (CH 3) - (CH 2) 4 -, - CH 2 -CH (CH 3) - (CH 2) 5 - _{, -CH 2 -CH (CH 3)} - (CH 2) 6 -, - CH 2 -CH (CH 3) - (CH 2) 7 -, - CH 2 -CH (CH 3) -CH (CH 3) _{-CH 2 -, - CH 2 -CH} (CH 3) -CH 2 -CH (CH 3) -CH 2 -, - CH 2 -CH (CH 3) - ( _{H 2) 2 -CH (CH 3} ) -CH 2 -, - CH 2 -CH (CH 3) - (CH 2) 3 -CH (CH 3) -CH 2 -, - CH 2 -CH (CH 3) _{- (CH 2) 4 -CH (} CH 3) -CH 2 -, - CH (CH 3) -CH 2 -, - CH (CH 3) - (CH 2) 2 -, - CH (CH 3) - ( _{CH 2) 3 -, - CH} (CH 3) - (CH 2) 4 -, - CH (CH 3) - (CH 2) 5 -, - CH (CH 3) - (CH 2) 6 -, - CH _{(CH 3) - (CH 2} ) 7 -, - CH (CH 3) - (CH 2) 8 -, - CH 2 -CH (CH 3) -CO-O- (CH 2) 2 -, - CH 2 _{-CH (CH 3) -CO-O-} (CH 2) 3 -, - CH 2 -CH (CH 3) -CO-O- (CH 2) 4 -, - CH 2 _{CH (CH 3) -CO-O-} (CH 2) 5 -, - CH 2 -CH (CH 3) -CO-O- (CH 2) 6 -, - (CH 2) 2 -CO-O- ( _{CH 2) 2 -, - (} CH 2) 2 -CO-O- (CH 2) 3 -, - (CH 2) 2 -CO-O- (CH 2) 4 -, - (CH 2) 2 -CO _{-O- (CH 2) 5 -,} - (CH 2) 2 -CO-O- (CH 2) 6 -, - (CH 2) 2 -CO-O- (CH 2) 7 -, etc. can be exemplified .

On the other hand, as R ⁶ , for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, etc. And a chain organic group comprising a hydrocarbon, an organic group comprising a hydrocarbon containing a cyclic unit such as a cyclopentyl group, a methylcyclopentyl group, and a cyclohexyl group.
Z represents a bond with a divalent hydrocarbon group Y.

In the above R ¹ , R ² , R ⁵ , R ⁶ , the above-mentioned carbon number and oxygen number, and if necessary, within the range of the silicon number, a hydroxyl unit, an alkoxy unit, an acyl unit as an organic group, It may contain a carboxyl unit, an alkenyloxy unit, an acyloxy unit, a halogen atom such as fluorine or chlorine, an ester bond, or a heteroatom such as nitrogen, phosphorus or sulfur excluding an oxygen atom or silicon atom.

In the present invention, as the organic groups R ¹ , R ² , R ⁵ , and R ⁶ in the average composition formula (1), the light resistance of the silicone composition of the present invention is improved or the stability during storage is increased. Because of the tendency, the hydroxyl unit, alkoxy unit, acyl unit, carboxyl unit, alkenyloxy unit, acyloxy unit, and fluorine are excluded with respect to the total number of moles of all Si units of the epoxy-modified silicone represented by the average composition formula (1) The total number of moles of silicon atoms bonded with halogen atoms such as chlorine, or ester bonds, and further organic groups containing hetero atoms such as nitrogen, phosphorus and sulfur excluding oxygen atoms and silicon atoms is 10% or less. It is preferably 1% or less, and more preferably not contained at all.

  Further, since the adhesiveness is improved, the total number of moles of silicon atoms bonded with an organic group containing a fluorine atom is preferably 10% or less, more preferably 1% or less, and no inclusion at all. Further preferred.

  On the other hand, when producing a cured product using the silicone composition of the present invention, the epoxy-modified silicone represented by the average composition formula (1) tends to be stably cured with good reproducibility. It consists of one or more types of structures selected from the group consisting of unsubstituted and substituted groups having a carbon-carbon double bond of 2 or more and 6 or less, and a chain and a branch, with respect to the total number of moles of all Si units. The total number of moles of silicon atoms bonded to a monovalent aliphatic organic group is preferably 10% or less, more preferably 5% or less, still more preferably 1% or less, and none at all. It is particularly preferred.

In addition, since the light resistance of the cured product obtained using the silicone composition of the present invention tends to be good and the heat discoloration tends to be improved, the organic group R ¹ of the average composition formula (1) in the present invention. Is preferably selected from the group consisting of (A-1), (A-3), and C) wherein R ⁴ is (D-1) and (D-2). And (A-3) is more preferably an organic group selected from the group consisting of 1 to 8 and 0 oxygen, and the number of carbons in (A-1) and (A-3) Is more preferably an unsubstituted chain organic group selected from the group consisting of 1 to 8 and an oxygen number of 0, and particularly preferably a methyl group.

As the organic group R ² in the epoxy-modified silicone represented by the average composition formula (1) of the present invention, the curing rate when the silicone composition is cured is increased, or a cured product obtained by using the silicone composition. Therefore, those represented by general formula (2) to general formula (5) are preferable, represented by general formula (2) to general formula (5), and R ³ is − _{(CH 2) 2 -, -} CH (CH 3) -, - (CH 2) 3 -, - CH (CH 3) -CH 2 -, - CH 2 -CH (CH 3) -, - (CH 2) _{4 -, - (CH 2)} 5 -, - (CH 2) 6 -, - (CH 2) 7 -, - (CH 2) 8 -, - (CH 2) 9 -, - (CH 2) 10 - _{, - (CH 2) 11 -} , - (CH 2) 12 -, - (CH 2) 13 -, - (CH 2) _{4 -, - (CH 2)} 15 -, - (CH 2) 16 - , more preferably a chain or an aliphatic hydrocarbon structure consisting of branched such as the general formula (2) to the general formula (5) And R ³ is more preferably — (CH ₂ ) ₂ — or —CH (CH ₃ ) —, represented by general formula (2) to general formula (5), and R ^3. Is particularly preferably — (CH ₂ ) ₂ —, represented by the general formula (3), and preferably R ³ is — (CH ₂ ) ₂ —.

As the divalent organic group Y in the present invention, there is a tendency that the light resistance and heat discoloration of a cured product obtained by using the silicone composition of the present invention tend to increase, and the warm / cold cycle accompanying the on / off cycle of the LED. The organic group Y preferably has a value of p of 4 or less, more preferably 2, and a value of p of 2, since the crack resistance and the adhesion to the housing tend to increase. R ⁶ is more preferably one or more structures selected from the group consisting of — (CH ₂ ) ₂ — and —CH (CH ₃ ) —, and the value of p is 2, and R ⁶ is - _{(CH 2) 2} -, especially preferably a value of p is 2, and, ^{R 6} is - _{(CH 2) 2} - and, still, it is desirable that ^{R 7} is a methyl group.

  In the epoxy-modified silicone represented by the average composition formula (1) of the present invention, a, b, c, d, e, f, g, h, i, j, k, l, m, and n are epoxy silicone 1 Represents the number of moles of each siloxy unit present in the mole, a, b, c, d, e, f, g, h, i, j, k, l, m, n are each a value of 0 or more, It is a value that satisfies d + h + k> 0, e + f + h + i + j + k> 0, and g = a + f + l at the same time.

  When all of d, h, and k are zero, there is no epoxy group in the epoxy-modified silicone, and it becomes difficult to stably produce a cured product having adhesiveness with good reproducibility. Further, when all of e, f, h, i, j, and k are zero, the hardness of the cured product is too high, and the crack resistance in the warm / cool cycle accompanying the on / off cycle of the LED is remarkably lowered.

  Since the storage stability at high temperature of the epoxy-modified silicone composition of the present invention is further increased, the content (%) of SiH groups with respect to the total number of Si in the epoxy-modified silicone is preferably less than 2%, preferably 1% More preferably, it is more preferably 0.5% or less. In the present invention, the SiH group content (%) with respect to the total number of Si in the epoxy-modified silicone can be represented by [(c + i + m) / (a + b + c + d + e + f + g + h + i + j + k + l + m + n) × 100].

  In the epoxy-modified silicone according to the present invention, the value of [(j + k + l + m + 2n) / (a + b + c + d + e + f + g + h + i + j + k + l + m + n) × 100] representing the branched chain content (%) improves the handling property of the silicone composition, and further, the curing agent and curing It is preferably 4% or less, more preferably 1% or less, and not included, because the compatibility with the accelerator and uniform mixing properties are good and the crack resistance tends to be good after curing. More preferably.

  Here, calculation of [(c + i + m) / (a + b + c + d + e + f + g + h + i + j + k + l + m + n)] and [(j + k + l + m + 2n) / (a + b + c + d + e + f + g + h + i + j + k + l + m + n)] in the epoxy-modified silicone according to the present invention is performed.

In epoxy-modified silicone according to the present invention [(c + i + m) / (a + b + c + d + e + f + g + h + i + j + k + l + m + n)], [(j + k + l + m + 2n) / (a + b + c + d + e + f + g + h + i + j + k + l + m + n)] is calculated from the spectral pattern obtained by performing ²⁹ Si-NMR measurement according to the following methods described This is a value obtained by calculating the abundance ratio of each siloxy unit corresponding to (c + i + m) and (j + k + l + m + 2n) based on the integrated value.

<Measurement method of ²⁹ Si-NMR>
To a solution obtained by dissolving 0.15 g of epoxy-modified silicone in 1 g of deuterated chloroform, 0.015 g of Cr (acac) ₃ and 10 μL of tetramethylsilane are added to obtain an NMR measurement solution. Using this NMR measurement solution, measurement of ²⁹ Si-NMR under the complete proton decoupling condition is carried out at a total number of 4000 times.

  The epoxy-modified silicone represented by the average composition formula (1) according to the present invention tends to increase the heat resistance of a cured product obtained using the silicone composition of the present invention. It is preferably 0.15 or more, and more preferably 0.20 or more. On the other hand, since the light resistance and heat discoloration of a cured product obtained using the silicone composition of the present invention tend to increase, the epoxy value of the epoxy-modified silicone represented by the average composition formula (1) of the present invention is 0. Is preferably .50 or less, more preferably 0.40 or less, and still more preferably 0.37 or less.

Here, the epoxy value in the present invention will be described.
The epoxy value in the present invention refers to the number of epoxy units present in 100 g of epoxy-modified silicone, and specifically refers to a value measured by the following method.

<Method for measuring epoxy value>
A sample (eg, a resin sample) is dissolved in benzyl alcohol and 1-propanol. To this solution, an aqueous potassium iodide solution and a bromophenol blue indicator are added, followed by titration with 1N hydrochloric acid, and the point where the reaction system turns from blue to yellow is taken as the equivalent point. From the equivalent point, the epoxy value of the epoxy-modified silicone is calculated according to the following formula (IX).

Epoxy value (equivalent / 100 g) = (V × N × F) / (10 × W) Expression (IX)
[W, V, N, and F represent the following values, respectively.
W: weight of sample (g),
V: titer (mL)
N: Normality of hydrochloric acid used for titration (N),
F: Factor of hydrochloric acid used for titration]

  Further, in the present invention, since there is a tendency for the surface of the cured product obtained using the silicone composition to be less sticky, [(the number of epoxy-modified silicones represented by the average composition formula (1) of the present invention). The value of (average molecular weight) / (100 / epoxy value)] is preferably 1 or more, and more preferably 1.5 or more.

  Here, the number average molecular weight of the epoxy-modified silicone represented by the average composition formula (1) in the present invention will be described.

  The number average molecular weight of the epoxy-modified silicone in the present invention refers to a value obtained by gel permeation chromatography (GPC) measurement using chloroform as an eluent and monodisperse polystyrene and styrene monomer as standard substances. Specifically, it refers to the number average molecular weight calculated using the above calibration curve from the elution time and detection intensity of the measurement sample solution prepared in advance from the elution time by RI detection.

Epoxy-modified silicone is, for example,
(F-1) An organic group having an epoxy unit by hydrolyzing as necessary using an organosilicone containing a condensation-reactive group such as an organohalosilane or an organoalkoxysilane as a substrate and then subjecting to a condensation reaction. How to introduce,
(F-2) Cyclic organohydrogensilicone containing Si-H groups and / or chain-like and branched organohydrogensilicones are subjected to a hydrosilylation reaction to form a carbon-carbon double bond and an epoxy group. And a method of adding a compound having a carbon-carbon double bond, if necessary,
(F-3) A cyclic organosilicone containing at least a cyclic organosilicone having an organic group containing an epoxy unit as a substituent, containing a Si-H group in the molecule as necessary, a chain and / Or ring-opening polymerization in the presence of branched siloxanes,
(F-4) a method of synthesizing the modified polysiloxanes obtained by the methods described in (F-1), (F-2) and (F-3) by re-equilibration reaction;
Or the like. Of these, the methods (F-1), (F-3), and (F-4) are often accompanied by side reactions such as ring opening of the epoxy group. -2) is widely used.

  Usually, for example, platinum, ruthenium, rhodium and the like used in the hydrosilylation reaction, Periodic Tables 8th, 9th, and 10th group transition metals, salts of the metals, Alternatively, the transition metal derived from the metal complex or the like remains in the epoxy-modified silicone synthesis product.

  The total content of transition metal elements in the epoxy-modified silicone composition of the present invention is 30 ppm by mass because the heat-resistant yellowing of the cured product obtained by curing the epoxy-modified silicone composition of the present invention is improved. Or less, more preferably 20 ppm by mass or less, still more preferably 10 ppm by mass or less, and particularly preferably 8 ppm by mass or less. The lower limit of the content of the transition metal element contained in the epoxy-modified silicone composition of the present invention is not particularly limited, but in order to reduce the content of the transition metal element to less than 0.01 mass ppm, for example, Since a great amount of labor is required such as adsorption treatment using a significant amount of activated carbon, it is usually in the range of 0.01 mass ppm or more. In addition, 1 mass ppm (hereinafter also simply referred to as “ppm”) corresponds to 0.0001 mass%.

  In the present invention, the epoxy-modified silicone represented by the average composition formula (1) is substituted with a cyclic organohydrogen silicone containing Si—H groups and / or a chain-like or branched organohydrogen silicone and carbon-carbon. As a transition metal catalyst used for hydrosilylation reaction of a compound having a double bond and an epoxy group, and, if necessary, a silicone having a carbon-carbon double bond, group 8 of the periodic table, It is possible to use simple metals of Group 9 and Group 10, those in which the metal solid is supported on a carrier such as alumina, silica, carbon black, a salt of the metal, a complex of the metal, or the like. . Of these, platinum, rhodium, and ruthenium, which have high hydrosilylation activity and are less likely to cause side reactions, are preferred, and platinum is particularly preferred. Examples of the hydrosilylation reaction catalyst using platinum include chloroplatinic acid, complexes of chloroplatinic acid and alcohol, aldehyde, ketone, platinum-vinyl silicone complex, platinum-phosphine complex, platinum-phosphite complex, dicarbonyldichloro. Platinum, dicyclopentadienyl dichloro platinum, etc. are mentioned.

  The amount of the transition metal catalyst used in the hydrosilylation reaction is the amount of the epoxy modification obtained by the hydrosilylation reaction from the viewpoint of producing an epoxy-modified silicone with good reproducibility by suppressing the ring opening of the epoxy group during the hydrosilylation reaction. The amount of transition metal relative to silicone is preferably in the range of 0.01 ppm to 30 ppm, more preferably in the range of 0.1 ppm to 20 ppm, and still more preferably in the range of 0.5 ppm to 10 ppm. A range of 1 ppm or more and 8 ppm or less is particularly preferable. The amount of the transition metal catalyst used in the hydrosilylation reaction is not necessarily constant as long as it is within the above range, and may be changed at the initial stage of the reaction or during the reaction.

  The reaction temperature at the time of hydrosilylation reaction is the type and molecular weight of the organohydrogen silicone used, the compound having a carbon-carbon double bond and an epoxy group, and, if necessary, the silicone having a carbon-carbon double bond. Furthermore, although it varies depending on the reaction mode such as batch, semi-batch, or continuous, the range of 0 ° C. or more and 250 ° C. or less is preferable from the viewpoint of increasing the reaction rate and efficiently completing the reaction. The range of 200 ° C. or lower is more preferable, the range of 20 ° C. or higher and 150 ° C. or lower is further preferable, and the range of 30 ° C. or higher and 120 ° C. or lower is particularly preferable. The reaction temperature does not need to be constant as long as it is within the above range, and may be changed at the initial stage of the reaction or during the reaction.

  When carrying out the hydrosilylation reaction, it is possible to remove the heat of reaction by the hydrosilylation reaction, and use a solvent from the viewpoint of suppressing the modification of the resulting epoxy-modified silicone or suppressing the increase in the viscosity of the reaction system due to the addition reaction. It is preferable.

  Examples of the solvent used include dimethyl ether, diethyl ether, diisopropyl ether, 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, and anisole. Ether solvents, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, aliphatic hydrocarbon solvents such as hexane, cyclohexane, heptane, octane, isooctane, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene Aromatic solvent such as ethyl acetate, ester solvent such as ethyl acetate and butyl acetate, alcohol such as butyl cellosolve and butyl carbitol System solvents. These solvents can be used as one kind or a mixture of two or more kinds.

  Among these, the hydrosilylation reaction rate is relatively high, and ether solvents, ketone solvents, aliphatic hydrocarbon solvents, and aromatic hydrocarbon solvents are preferable from the viewpoints of solubility of raw materials and / or solvent recoverability. , More preferably a solvent containing 50% by mass or more of an ether solvent, and at least one selected from the group consisting of 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol dimethyl ether having a boiling point at atmospheric pressure of 120 ° C. or lower, or Two or more kinds of mixed solvents are more preferable.

  The amount of the solvent used in carrying out the hydrosilylation reaction is the same as that of the organohydrogensilicone used, the compound having a carbon-carbon double bond and an epoxy group, and, if necessary, the silicone having a carbon-carbon double bond. Depending on the type and molecular weight, and also the reaction mode such as batch, semi-batch, or continuous, the mass of the solvent relative to the total mass of the mixture is usually 0.1% by mass during the hydrosilylation reaction. The range is 99.9% by mass or less, preferably 10% by mass or more and 95% by mass or less, and more preferably 20% by mass or more and 90% by mass or less.

  The atmosphere for performing the hydrosilylation reaction is preferably performed in an inert gas atmosphere such as nitrogen, helium, or argon.

  The reaction method for carrying out the hydrosilylation reaction is not particularly limited. For example, a cyclic organohydrogen silicone containing a Si—H group and / or a chain or branched organohydrogen silicone and carbon-carbon 2. One or more combinations selected from the group consisting of batch, semi-batch, and continuous with a compound having a heavy bond and an epoxy group, and, if necessary, a silicone having a carbon-carbon double bond The method of making it react sequentially, continuously or at once can be illustrated by the method of this.

  As a method for adding the hydrosilylation catalyst, a cyclic organohydrogen silicone containing Si-H groups and / or a compound having a chain-like or branched organohydrogen silicone, a carbon-carbon double bond and an epoxy group, In addition, if necessary, a method of previously mixing a silicone having a carbon-carbon double bond and / or a solvent and finally adding a hydrosilylation catalyst is preferably used. In addition, it is essential to add a silicone having a carbon-carbon double bond to a cyclic organohydrogen silicone containing a Si—H group and / or a chain-like or branched organohydrogen silicone. In some cases, a cyclic organohydrogen silicone containing a Si-H group and / or a chain or branched organohydrogen silicone, a compound having a carbon-carbon double bond and an epoxy group, and if necessary Pre-mixed with solvent, and finally hydrosilylation catalyst was added to conduct hydrosilylation reaction, followed by silicone having carbon-carbon double bond, and further hydrosilylation catalyst added if necessary, hydrosilylation A method for completing the reaction is preferably used.

  Cyclic organohydrogensilicone containing Si-H groups and / or chain-like, branched organohydrogensilicones, compounds having carbon-carbon double bonds and epoxy groups, and, if necessary, carbon- When silicone having a carbon double bond is added by a hydrosilylation reaction, moisture in the system may have an effect. From the viewpoint of maintaining the hydrosilylation reaction rate or suppressing the ring opening reaction of the epoxy group, the water content of the reaction system is preferably 2% by mass or less based on the mass of the reaction system, and preferably 1% by mass or less. More preferably, it is more preferably 0.5% by mass or less, still more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less.

Next, the antioxidant used in the present invention will be described.
The epoxy-modified silicone composition in the present invention is at least one selected from the group consisting of a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant and an amine-based antioxidant with respect to 100 parts by mass of the epoxy-modified silicone. It is necessary to contain 0.0005 mass part or more and 5 mass parts or less of this antioxidant. When the content of the antioxidant is less than 0.0005 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone, the storage stability of the epoxy-modified silicone when exposed to a high temperature environment is unfavorable. On the other hand, when the content of the antioxidant exceeds 5 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone, the antioxidant is not completely dissolved in the epoxy-modified silicone, and foreign matter remains in the epoxy-modified silicone. In some cases, the light resistance, crack resistance, adhesion and the like of a cured product obtained by curing the epoxy-modified silicone composition are not preferable.

  Since the storage stability of the epoxy-modified silicone of the present invention is further increased, the content of the antioxidant with respect to 100 parts by mass of the epoxy-modified silicone is preferably 0.001 parts by mass or more, and 0.0015 parts by mass or more. It is more preferable that On the other hand, since the light resistance and moisture resistance of the cured product obtained by curing the epoxy-modified silicone composition of the present invention are enhanced, the content of the antioxidant with respect to 100 parts by mass of the epoxy-modified silicone is 1 part by mass or less. It is preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, particularly preferably 0.05 parts by mass or less, and 0.02 parts by mass. The following is desirable.

  The antioxidant used in the present invention is at least one antioxidant selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and amine antioxidants.

  Examples of the phenolic antioxidant used in the present invention include (G-1) alkylphenols, (G-2) hydroquinones, (G-3) thioalkyl or thioaryls, (G-4) benzyl compounds, (G-5) Triazines, (G-6) Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and mono- or polyhydric alcohols, (G-7) esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and mono- or polyhydric alcohols, (G-8) β- (3,5-dicyclohexyl-4-hydroxyphenyl) ) Esters of propionic acid and mono- or polyhydric alcohols, (G-9) 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and mono- or polyhydric alcohols (G-10) β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amides, (G-11) β- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionic acid vitamins and the like. These can be used as one kind or a mixture of two or more kinds.

Specific examples of (G-1) alkylphenols include, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert. -Butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4 -Methoxymethylphenol, nonylphenols having a linear or branched side chain (eg 2,6-di-nonyl-4-methyl) Phenol), 2,4-dimethyl-6- (1′-methylundec-1′-yl) phenol, 2,4-dimethyl-6- (1′-methylheptade-1′-yl) phenol, 2,4 -Dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures thereof, 4-hydroxylauranilide, 4-hydroxystearanilide and octyl N- (3,5-di-tert-butyl- 4-hydroxyphenyl) carbamate, 2,2′-methylenebis (6-tert-butyl-4-methylphenol), 2,2′-methylenebis (6-tert-butyl-4-ethylphenol), 2,2′- Methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2′-methylenebis (4-methyl-6-cyclohexyl) Ruphenol), 2,2′-methylenebis (6-nonyl-4-methylphenol), 2,2′-methylenebis (4,6-di-tert-butylphenol), 2,2′-ethylidenebis (4,6 -Di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2 , 2′-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-methylenebis (6-tert -Butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6 Bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1, 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3′-tert-butyl-4′-hydroxyphenyl) ) Butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene, bis [2- (3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)- 6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butyl Tan, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n -Dodecyl mercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane, and the like. These can be used as one kind or a mixture of two or more kinds.

Specific examples of (G-2) hydroquinones include, for example, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amyl. Hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl- 4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate, and the like. These can be used as one kind or a mixture of two or more kinds.

(G-3) Specific examples of thioalkyl or thioarylphenols include, for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4- Dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol, 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4 -Octylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3 , 6-di-sec-amylphenol), and 4,4′-bis (2,6-dimethyl-4-hydroxyphenyl) disulfate. De, and the like. These can be used as one kind or a mixture of two or more kinds.

(G-4) Specific examples of benzyl compounds include, for example, 3,5,3 ′, 5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3, 5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4 -Tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl -4-hydroxybenzyl mercaptoacetate, dioctadecyl-2,2-bis (3,5-di- ert-butyl-2-hydroxybenzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, di-dodecylmercaptoethyl-2,2-bis (3,5 -Di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl- 4-hydroxybenzyl) malonate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5- Di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene and 2,4,6-tris (3,5-di-tert-butyl 4-hydroxybenzyl) phenol, and the like. These can be used as one kind or a mixture of two or more kinds.

Specific examples of (G-5) triazines include, for example, 2,4-bis (octyl mercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5. -Triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis ( 3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1, 2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy) -2,6 Dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3 5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate, etc. Can be mentioned. These can be used as one kind or a mixture of two or more kinds.

(G-6) Specific examples of esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and monohydric or polyhydric alcohols include, for example, β- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionic acid and methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1 , 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl hex Diols, trimethylolpropane, and esters with monohydric or polyhydric alcohols selected from 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, and the like. It is done. These can be used as one kind or a mixture of two or more kinds.

(G-7) Specific examples of esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid and monohydric or polyhydric alcohols include, for example, β- (5-tert -Butyl-4-hydroxy-3-methylphenyl) propionic acid, methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1 , 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trime Ruhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, and 3,9-bis [2- {3- (3- tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane and the like And esters with a monohydric alcohol. These can be used as one kind or a mixture of two or more kinds.

(G-8) Specific examples of esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and mono- or polyhydric alcohols include, for example, β- (3,5-dicyclohexyl-4 -Hydroxyphenyl) propionic acid and methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol , Triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oximide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpro And esters with monohydric or polyhydric alcohols selected from bread and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane. These can be used as one kind or a mixture of two or more kinds.

(G-9) Specific examples of esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and mono- or polyhydric alcohols include, for example, 3,5-di-tert-butyl-4 -Hydroxyphenylacetic acid, mono- or polyhydric alcohol, methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol Thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexane Diol, trimethylol Propane, and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] esters with mono- or polyhydric alcohols selected from octane, and the like. These can be used as one kind or a mixture of two or more kinds.

Specific examples of amides of (G-10) β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid include, for example, N, N′-bis (3,5-di-tert -Butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamide, N, N'-bis (3,5 -Di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide and N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide , Etc. These can be used as one kind or a mixture of two or more kinds.

Specific examples of (G-11) β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid vitamins include, for example, α-tocopherol, β-tocopherol, γ-tocopherol, δ- Tocopherols and their mixtures, tocotrienols, ascorbic acid, and the like. These can be used as one kind or a mixture of two or more kinds.

  Examples of the phosphorus-based antioxidant used in the present invention include (H-1) phosphonates, (H-2) phosphites, and (H-3) oxaphosphaphenanthrenes. Can be illustrated. These can be used as one kind or a mixture of two or more kinds.

Specific examples of (H-1) phosphonates include, for example, dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzyl. Phosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, tetrakis (2,4-di- tert-butylphenyl) -4,4′-biphenylenediphosphonate, calcium salt of monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and the like. These can be used as one kind or a mixture of two or more kinds.

Specific examples of (H-2) phosphites include, for example, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, tris (2,4-di-tert-butylphenyl). Phosphite, triphenyl phosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5 -Tert-butyl-4-hydroxyphenyl) butanediphosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropylidenediphenyldiphosphite, tetra (tridecyl) -4,4'-butylidenebis (3- Methyl-6-tert-butylphenol) diphosphine Ite, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, Bis (octylphenyl) -bis [4,4′-butylidenebis (3-methyl-6-tert-butylphenol)]-1,6-hexanediol diphosphite, phenyl-4,4′-isopropylidenediphenol-penta Erythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris [4 , 4′-isopropylidenebis (2-tert-butylphenol)] phospha Ite, phenyl diisodecyl phosphite, di (nonylphenyl) pentaerythritol diphosphite), tris (1,3-di-stearoyloxyisopropyl) phosphite, and 4,4'-isopropylidenebis (2-tert-butylphenol) -Di (nonylphenyl) phosphite etc. can be illustrated. These can be used as one kind or a mixture of two or more kinds.

Specific examples of (H-3) oxaphosphaphenanthrenes include, for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 8-chloro-9,10- Examples include dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 8-t-butyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. it can. These can be used as one kind or a mixture of two or more kinds.

  Examples of the sulfur-based antioxidant used in the present invention include (I-1) dialkylthiopropionates, (I-2) esters of octylthiopropionic acid and polyhydric alcohols, (I- 3) Esters of lauryl thiopropionic acid and polyhydric alcohol, (I-4) esters of stearyl thiopropionic acid and polyhydric alcohol, and the like. These can be used as one kind or a mixture of two or more kinds.

Specific examples of (I-1) dialkylthiopropionates include dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate. These can be used as one kind or a mixture of two or more kinds.

(I-2) Specific examples of esters of octylthiopropionic acid and polyhydric alcohol include, for example, octylthiopropionic acid, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and trishydroxyethyl isocyanurate. Examples thereof include esters with polyhydric alcohols selected from the above. These can be used as one kind or a mixture of two or more kinds.

(I-3) Specific examples of esters of lauryl thiopropionic acid and polyhydric alcohol include, for example, lauryl thiopropionic acid, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate, and the like. Examples thereof include esters with polyhydric alcohols selected from: These can be used as one kind or a mixture of two or more kinds.

(I-4) Specific examples of esters of stearylthiopropionic acid and polyhydric alcohol include, for example, stearylthiopropionic acid, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and trishydroxyethyl isocyanurate. Examples thereof include esters with polyhydric alcohols selected from the above. These can be used as one kind or a mixture of two or more kinds.

  Furthermore, examples of the amine-based antioxidant used in the present invention include N, N′-di-isopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, and N, N. '-Bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) ) -P-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N- Isopropyl-N′-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, N- (1- Tilheptyl) -N′-phenyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N′-dimethyl-N, N ′ -Di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N- Phenyl-2-naphthylamine, octylated diphenylamine (eg, p, p′-di-tert-octyldiphenylamine), 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodeca Noylaminophenol, -Octadecanoylaminophenol, bis (4-methoxyphenyl) -amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ′, N′-tetramethyl-4,4′-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o -Tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, mono- and di-alkylated tert-butyl- / tert-octyl A mixture of diphenylamine, a mixture of mono- and di-alkylated nonyldiphenylamine, mono- and Mixtures of di-alkylated dodecyldiphenylamine, mixtures of mono- and di-alkylated isopropyl / isohexyldiphenylamine, mixtures of mono- and di-alkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl- 4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and di-alkylated tert-butyl / tert-octylphenothiazines, a mixture of mono- and di-alkylated tert-octylphenothiazines, N-allylphenothiazine, N , N, N ′, N′-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperidi-4-yl) hexamethylenediamine, bis (2,2,6,6-Tetramethylpiperidi-4-yl) Sebaka DOO, 2,2,6,6-tetramethyl-4-one, and, 2,2,6,6-tetramethylpiperidine-ol, etc. may be exemplified. These can be used as one kind or a mixture of two or more kinds.

  As the antioxidant used in the present invention, since the storage stability of the epoxy-modified silicone of the present invention is further increased, at least selected from the group consisting of a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant. Since it is preferable that it is 1 type of antioxidant and the light resistance of the hardened | cured material obtained by hardening | curing the epoxy-modified silicone composition of this invention is improved, (G-1), (G-2), ( More preferably, it is selected from the group consisting of (G-6) to (G-9), (H-1), (H-2), and (I-1).

  In the present invention, as a preferable combination in the case of using a combination of different types of antioxidants such as phenolic antioxidants, phosphorus antioxidants, and sulfurous antioxidants, phenolic antioxidants and phosphorus antioxidants are used. Examples thereof include a combination of an agent or a phenol-based antioxidant and a sulfur-based antioxidant.

  In the present invention, at least one kind of antioxidant selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants and amine antioxidants is added to 100 parts by mass of epoxy-modified silicone. There is no particular limitation on the method for containing 0005 parts by mass to 5 parts by mass, for example,

  (J-1) Cyclic organohydrogensilicone containing Si-H groups and / or organohydrogensilicone having a chain or branched structure, a compound having a carbon-carbon double bond and an epoxy group, and necessary Accordingly, a silicone having a carbon-carbon double bond is hydrosilylated in the presence of a transition metal catalyst for hydrosilylation reaction and a solvent to produce an epoxy-modified silicone, and then 100 parts by mass of the resulting epoxy-modified silicone is produced. In contrast, 0.0005 parts by mass or more and 5 parts by mass or less of at least one antioxidant selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and amine antioxidants is added. And uniformly mixing and dissolving, the solvent, a compound having an unreacted carbon-carbon double bond, and the like,

  (J-2) A group consisting of phenolic antioxidant, phosphorus antioxidant, sulfur antioxidant and amine antioxidant for 100 parts by mass of the epoxy-modified silicone produced in (J-1) above After adding 5 parts by mass or more of at least one antioxidant selected from the above, uniformly mixing and dissolving, the solvent, the compound having an unreacted carbon-carbon double bond, and the like are distilled off. A part of at least one antioxidant selected from the group consisting of an antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant and an amine-based antioxidant is distilled off to obtain a content of the antioxidant. 0.0005 parts by mass to 5 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone,

(J-3) After the epoxy-modified silicone is dissolved in a solvent, the phenol-based antioxidant, phosphorus-based antioxidant, sulfur-based antioxidant and amine-based antioxidant are added to 100 parts by mass of the epoxy-modified silicone. A method of distilling off the solvent after adding 0.0005 parts by mass to 5 parts by mass of at least one antioxidant selected from the group and uniformly mixing and dissolving the mixture,

(J-4) After the epoxy-modified silicone is dissolved in a solvent, the phenol-based antioxidant, phosphorus-based antioxidant, sulfur-based antioxidant and amine-based antioxidant are added to 100 parts by mass of the epoxy-modified silicone. After adding 5 parts by mass or more of at least one antioxidant selected from the group and uniformly mixing and dissolving, the solvent and a part of the antioxidant are distilled off, and the content of the antioxidant is changed to epoxy. A method of 0.0005 parts by mass to 5 parts by mass with respect to 100 parts by mass of the modified silicone;

(J-5) At least one antioxidant selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants and amine antioxidants with respect to 100 parts by mass of the epoxy-modified silicone. A method of adding 0.0005 parts by mass to 5 parts by mass and uniformly mixing and dissolving;
Etc. can be exemplified.

  After adding the antioxidant in the above methods (J-1) to (J-5), the operation of uniformly mixing and dissolving is performed in air and / or in an inert gas atmosphere such as nitrogen, helium, and argon. be able to. Among these atmospheres, it is preferable to perform the operation in an inert gas atmosphere since the modification of the resulting silicone composition can be suppressed.

  After adding the antioxidant, the temperature when uniformly mixing and dissolving is -50 ° C or higher because the viscosity of the epoxy-modified silicone composition or the solution after the reaction is lowered and the uniform mixing operation can be easily performed. The range is preferably 0 ° C. or higher. On the other hand, in order to suppress modification of the silicone composition, a range of 250 ° C. or lower is preferable, a range of 200 ° C. or lower is more preferable, a range of 150 ° C. or lower is further preferable, and a range of 120 ° C. or lower is particularly preferable. The temperature does not have to be constant as long as it is within the above range, and may be changed in the middle.

  In the above methods (J-1) to (J-4), from the solution containing the epoxy-modified silicone, a solvent, and if necessary, a compound having an unreacted carbon-carbon double bond or an antioxidant. The temperature at which the components such as part are separated is preferably in the range of −50 ° C. or more and 250 ° C. or less, more preferably 0 ° C. or more and 200 ° C. from the viewpoint of suppressing the modification of the epoxy-modified silicone or the epoxy-modified silicone composition. The following range, more preferably the range of 10 ° C. or more and 150 ° C. or less, particularly preferably the range of 20 ° C. or more and 120 ° C. or less. Within the above range, when separating components such as a solvent, a compound having an unreacted carbon-carbon double bond, and a part of an antioxidant as necessary, from a solution containing an epoxy-modified silicone. The temperature does not have to be a constant temperature, and the temperature can be changed along the way.

  These separation operations are preferably performed in an inert gas atmosphere such as nitrogen, helium, or argon.

  In the step of separating components such as a solvent, a compound having an unreacted carbon-carbon double bond, and a part of an antioxidant, if necessary, from the solution containing the epoxy-modified silicone, the solvent, unreacted Even when the viscosity of the mixture containing the epoxy-modified silicone composition is increased by reducing the content of components such as a compound having a carbon-carbon double bond and, if necessary, a part of the antioxidant, etc. In particular, it is preferable to use an apparatus capable of separating low boiling compounds and volatile compounds. Examples of such apparatuses include vertical stirring tanks, surface renewal stirring tanks, thin film evaporators, surface renewal biaxial kneaders, biaxial horizontal stirrers, wet wall reactors, free-falling perforated plates Examples thereof include a type reactor, and a reactor in which volatile components are distilled off while dropping a compound along a support. These apparatuses can be used alone or in combination of two or more.

  The epoxy-modified silicone composition of the present invention is an epoxy in which components other than inevitable impurities such as metal components such as the above-described antioxidants and transition metals and coloring components are represented by the average composition formula (1) according to the present invention. A modified silicone is preferred. For example, the content of the epoxy-modified silicone in the epoxy-modified silicone composition of the present invention is preferably 95% by mass or more, more preferably 99% by mass or more, and 99.5% by mass or more. More preferably, it is particularly preferably 99.9% by mass or more, and more preferably 99.95% by mass or more.

  In the epoxy-modified silicone composition of the present invention, the viscosity of the epoxy-modified silicone composition is 500,000 mPa · s or less as a measured value at 25 ° C. from the viewpoint of improving the handleability and processability due to fluidity and the like. The range is preferably 200,000 mPa · s or less, and more preferably 100,000 mPa · s or less.

  Here, the viscosity of the epoxy-modified silicone composition is a temperature of 25 ° C. using a rotary E-type viscometer (for example, “TV-22 type” manufactured by Toki Sangyo Co., Ltd., rotor: 3 ° × R14). Is a measured value.

  The epoxy-modified silicone composition of the present invention has excellent storage stability even when exposed to high-temperature environments during transportation and storage, and is obtained by curing the epoxy-modified silicone composition. Since the product has good transparency and excellent light resistance, heat discoloration, and adhesion, it is a sealing material for light emitting elements, spectacle lenses, lenses for optical devices, and lenses for picking up CDs and DVDs. It is also suitably used as a lens material for automobile headlamp lenses, projector lenses, and the like. Furthermore, it can also be used as various optical members such as optical fibers, optical waveguides, optical filters, optical adhesives, die bonding agents, underfill materials for optical semiconductor elements, optical disk substrates, display substrates, antireflection coatings and other coating materials. It is.

  When used in the above-mentioned applications, the epoxy-modified silicone composition of the present invention contains an epoxy resin, a curing agent for epoxy resin, a curing catalyst, a modifying agent, a silane coupling agent, an antifoaming agent, a colorant, a fluorescent agent, if necessary. It is used as a curable composition in which conventionally known additives such as a body, a light diffusing agent, an ultraviolet absorber, an inorganic filler, and a heat conductive filler are appropriately blended. Furthermore, an antioxidant, a heat stabilizer, etc. can be newly blended as necessary. The curable composition is preferably a curable resin composition.

  Examples of the epoxy resin that can be used in the present invention include aromatic epoxy resins represented by conventionally known aromatic glycidyl ethers, glycidyl ethers obtained by hydrogenating aromatic rings of the aromatic epoxy resins, and alicyclic rings. Formula epoxy resins, other epoxy resins and the like. These can be used as one kind or a mixture of two or more kinds.

  Examples of the aromatic epoxy resin include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetra Bisphenol-type epoxy resin obtained by glycidylation of bisphenols such as chlorobisphenol A and tetrafluorobisphenol A, and other dihydric phenols such as biphenol, dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene were glycidylated. Epoxy resin, 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) Epoxy resin obtained by glycidylation of trisphenols such as phenyl) ethylidene) bisphenol, epoxy resin obtained by glycidylation of tetrakisphenol such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane, phenol novolac, cresol Examples thereof include novolak type epoxy resins obtained by glycidylating novolaks such as novolak, bisphenol A novolak, brominated phenol novolak and brominated bisphenol A novolak.

  The aromatic ring hydrogenation reaction of the aromatic epoxy resin can be carried out by a conventionally known method using, for example, a ruthenium catalyst or a rhodium catalyst.

  Examples of the alicyclic epoxy resins include conventionally known compounds such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate and 2,2-bis (hydroxymethyl) -1-butanol. , 2-epoxy-4- (2-oxiranyl) cyclohexane adduct, bis (3,4-epoxycyclohexylmethyl) adipate, and the like.

  Other epoxy resins include glycidyl esters such as dimer acid glycidyl ester and hexahydrophthalic acid glycidyl ester, glycidyl amines such as triglycidyl isocyanurate, linear aliphatic epoxies such as epoxidized soybean oil and epoxidized polybutadiene. A compound etc. can be illustrated.

  When an aromatic epoxy resin is used as the epoxy resin, the light resistance of the cured product obtained by curing the curable resin composition of the present invention is increased, and therefore the aromatic with respect to the total mass of the epoxy resin used. The proportion of the epoxy resin is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 10% by mass or less. As the epoxy resin, an aromatic epoxy resin is used. It is particularly preferable to use an epoxy resin that does not contain at all.

  Other epoxy resins include glycidyl esters such as dimer acid glycidyl ester and hexahydrophthalic acid glycidyl ester, glycidyl amines such as triglycidyl isocyanurate, linear aliphatic epoxies such as epoxidized soybean oil and epoxidized polybutadiene. A compound etc. can be illustrated.

  When an aromatic epoxy resin is used as the epoxy resin, the light resistance tends to be good, so the ratio of the aromatic epoxy resin to the total mass of the epoxy resin used is 50% by mass or less. It is preferably 30% by mass or less, more preferably 10% by mass or less, and it is particularly preferable to use an epoxy resin containing no aromatic epoxy resin as the epoxy resin.

  The amount of the epoxy resin in the curable composition is preferably in the range of 0.1 to 400 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone composition of the present invention. The range is more preferably 200 parts by mass or less, and still more preferably 1 part by mass or more and 100 parts by mass or less.

  The curing agent for epoxy resin that can be used in the present invention is not particularly limited, and any one of commonly used amine curing agents, phenol curing agents, and acid anhydride curing agents should be used. Can do. These can be used as one kind or a mixture of two or more kinds.

  Specific examples of the amine curing agent include, for example, bis (4-aminocyclohexyl) methane, bis (aminomethyl) cyclohexane, m-xylylenediamine, 3,9-bis (3-aminopropyl) -2,4, Aliphatic and alicyclic amines such as 8,10-tetraspiro [5,5] undecane, aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzyldimethylamine, 2,4,6-tris Tertiary amines such as (dimethylaminomethyl) phenol, 1,8-diazabicyclo- (5,4,0) -undecene-7,1,5-azabicyclo- (4,3,0) -nonene-7, and the like And salts. These can be used as one kind or a mixture of two or more kinds.

  Specific examples of the phenolic curing agent include, for example, catechol, resorcin, hydroquinone, bisphenol F, bisphenol A, bisphenol S, biphenol, phenol novolacs, cresol novolacs, bisphenol A novolak compounds, tris, etc. Examples thereof include hydroxyphenylmethanes, aralkyl polyphenols, dicyclopentadiene polyphenols, and the like. These can be used as one kind or a mixture of two or more kinds.

  Specific examples of the acid anhydride curing agent include, for example, succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, hydrogen anhydride Nadic acid, hydrogenated methyl nadic acid, norbornane-2,3-dicarboxylic acid anhydride, methylnorbornane-2,3-dicarboxylic acid anhydride, methylcyclohexenedicarboxylic acid anhydride, two or more acids in one molecule Examples include silicones having anhydride-containing functional groups as substituents, etc. It is done. These can be used as one kind or a mixture of two or more kinds.

  Of these curing agents, the light resistance of cured products obtained by curing the epoxy-modified silicone composition of the present invention tends to increase, so that hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl -Hexahydrophthalic anhydride or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, hydrogenated nadic acid, hydrogenated methylnadic acid anhydride, norbornane -Alicyclic acid anhydrides such as 2,3-dicarboxylic acid anhydride, methylnorbornane-2,3-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, and two or more acid anhydrides in one molecule More preferred are silicones having a functional group as a substituent. More preferred are taric acid, hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, and methylnorbornane-2,3-dicarboxylic anhydride.

  The compounding amount of the curing agent for epoxy resin in the curable composition is preferably in the range of 1 part by mass or more and 200 parts by mass or less, more preferably 10 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone composition of the present invention. The range is 150 parts by mass or less, more preferably 20 parts by mass or more and 100 parts by mass or less.

  If necessary, the epoxy-modified silicone composition of the present invention can be blended with a curing catalyst. As the curing catalyst to be used, it is preferable to use at least one compound selected from the group consisting of a curing accelerator and a cationic polymerization catalyst.

  Examples of the curing accelerator include imidazole compounds, quaternary ammonium salts, phosphonium salts, amine compounds, aluminum chelate compounds, organic phosphine compounds, metal carboxylates and acetylacetone chelate compounds. These curing accelerators can be used as one kind or a mixture of two or more kinds.

  Specific examples of these compounds include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1,8-diaza-bicyclo (5,4,0) undecene-7, trimethylamine, benzyldimethylamine, triethylamine, 2 , 4,6-tris (dimethylaminomethyl) phenol, amine compounds such as 2- (dimethylaminomethyl) phenol and salts thereof, quaternary ammonium salts such as tetramethylammonium chloride, benzyltrimethylammonium bromide, tetrabutylammonium bromide, Organic phosphine compounds such as aluminum chelate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium-0,0-diethyl phosphorodithioate, chromium (III) tricarboxylate, octyl Tin, metal carboxylate and acetylacetone chelate compounds such as chromium acetylacetonate can be exemplified. Moreover, as a commercial item, U-CAT SA1, U-CAT 2026, U-CAT 18X etc. can be illustrated from a San Apro company. Among these, an imidazole compound, a quaternary ammonium salt, a phosphonium salt, an organic phosphine compound, and the like are preferably used from the viewpoint of giving a cured product with less coloring.

Examples of the cationic polymerization catalyst include Lewis acid catalysts represented by BF ₃ · amine complexes, PF ₅ , BF ₃ , AsF ₅ , SbF _{5 and the} like, phosphonium salts, quaternary ammonium salts, sulfonium salts, benzyl ammonium salts, Benzylpyridinium salt, benzylsulfonium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, thermosetting cationic polymerization catalyst represented by amine imide, diaryliodonium hexafluorophosphate, hexafluoroantimonic acid bis (dodecylphenyl) iodonium, etc. The ultraviolet curable cationic polymerization catalyst etc. which are represented are mentioned.

  Among these, a thermosetting cationic polymerization catalyst is preferably used because a transparent cured product having a high glass transition temperature and excellent solder heat resistance and adhesion and less coloring is obtained. As such a thermosetting cationic polymerization catalyst, for example, SI-100L, SI-60L (manufactured by Sanshin Chemical Co., Ltd.), CP-66, CP-77 (and above) which are sulfonium salt-based cationic polymerization initiators. Asahi Denka Kogyo).

  In general, the amount of the curing catalyst is preferably 0.001 part by mass or more and 0.005 part by mass or more from the viewpoint of increasing the curing rate with respect to 100 parts by mass of the epoxy-modified silicone composition. Is more preferably 0.01 parts by mass or more. On the other hand, from the viewpoint of moisture resistance and coloration of the cured product, it is preferably 10 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.8 part by mass or less, 0.5 It is particularly preferable that the amount is not more than part by mass.

  The viewpoint that the curable composition obtained by using the epoxy-modified silicone composition of the present invention imparts flexibility to the cured product obtained by curing the epoxy-modified silicone composition of the present invention and improves the adhesion. Therefore, a modifier may be contained as necessary. Examples of the modifier used include polyols containing two or more hydroxyl groups in one molecule, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3- Propanediol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,2-butanediol, 1,4-butanediol, neopentyl glycol, glycerin, erythritol, trimethylolpropane, 1,2,4-butanetriol, etc. Aliphatic polyols, polycarbonate diols, and silicones having a silanol group at the terminal are preferably used. These modifiers can be used as one kind or a mixture of two or more kinds.

  Since the compounding amount of the polyols containing two or more hydroxyl groups in one molecule in the curable composition increases the adhesion of the cured product obtained by curing the epoxy-modified silicone composition of the present invention, From 100 parts by weight of the epoxy-modified silicone composition, preferably 0.1 parts by weight or more, preferably because the heat resistance and moisture resistance of the cured product obtained by curing the epoxy-modified silicone composition of the present invention can be improved. Is 50 parts by mass or less, more preferably 0.5 parts by mass or more and 30 parts by mass or less, further preferably 1 part by mass or more and 20 parts by mass or less, particularly preferably 1.5 parts by mass or more and 10 parts by mass or less. The range is as follows.

  In the epoxy-modified silicone composition of the present invention, various silane coupling agents can be used for the purpose of improving the adhesion of a cured product obtained by curing the epoxy-modified silicone composition. Examples of silane coupling agents that can be used in the present invention include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyl. Methyldiethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, N- (2-aminoethyl) aminomethyltrimethyl Xisilane, N- (2-aminoethyl) (3-aminopropyl) trimethoxysilane, N- (2-aminoethyl) (3-aminopropyl) triethoxysilane, N- (2-aminoethyl) (3-amino Propyl) methyldimethoxysilane, N- [N ′-(2-aminoethyl) (2-aminoethyl)] (3-aminopropyl) trimethoxysilane, 2- (2-aminoethyl) thioethyltriethoxysilane, 2 -(2-aminoethyl) thioethylmethyldiethoxysilane, 3- (N-phenylamino) propyltrimethoxysilane, 3- (N-cyclohexylamino) propyltrimethoxysilane, (N-phenylaminomethyl) trimethoxysilane , (N-phenylaminomethyl) methyldimethoxysilane, (N-cyclohexylaminomethyl), ) Triethoxysilane, (N-cyclohexylaminomethyl) methyldiethoxysilane, piperazinomethyltrimethoxysilane, piperazinomethyltriethoxysilane, 3-piperazinopropyltrimethoxysilane, 3-piperazinopropyl Methyldimethoxysilane, 3-ureidopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltri Ethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3- (trimethoxysilyl) propylsuccinic anhydride, 3- ( Triethoxysilyl) propyl succinic anhydride, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, vinyltri Methoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylvinyldimethoxy Silane, methylvinyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane Methylcyclohexyldimethoxysilane, methylcyclohexyldiethoxysilane, methylcyclopentyldimethoxysilane, methylcyclopentyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, Examples include 3-methacryloxypropyltriethoxysilane. Moreover, the partial condensate of these silane coupling agents can also be used.

  The compounding amount of the silane coupling agent is 0.1 mass with respect to 100 parts by mass of the epoxy-modified silicone composition because the adhesion of a cured product obtained by curing the epoxy-modified silicone composition of the present invention is enhanced. On the other hand, since the heat discoloration of the cured product obtained by curing the epoxy-modified silicone composition of the present invention can be enhanced, the content is preferably 10 parts by mass or less. More preferably, it is the range of 0.3 mass part or more and 5 mass parts or less, More preferably, it is the range of 0.5 mass part or more and 3 mass parts or less.

The epoxy-modified silicone composition of the present invention can be blended with a phosphor that absorbs part or all of the energy of the light emitted from the light-emitting element and converts the emission wavelength. As the phosphor, either an inorganic phosphor or an organic phosphor can be used. Of these, inorganic phosphors that generally exhibit excellent light-emitting properties are preferred. As a typical yellow phosphor, for example, general formula A ₃ B ₅₀ O ₁₂ : M (wherein component A is at least one selected from the group consisting of Y, Gd, Tb, La, Lu, Se and Sm) And the component B represents at least one element selected from the group consisting of Al, Ga and In, and the component M represents at least one element selected from the group consisting of Ce, Pr, Eu, Nd and Er). Those containing phosphor particles composed of a garnet group are preferably used.

As a phosphor for a light emitting diode element that emits white light including a light emitting diode chip that emits blue light, Y ₃ Al ₅ O ₁₂ : Ce phosphor and / or (Y, Gd, Tb) ₃ (Al, Ga) ₅ O ₁₂ : Ce phosphor is preferably used. Other phosphors include, for example, CaGa ₂ S ₄ : Ce ³⁺ and SrGa ₂ S ₄ : Ce ³⁺ , YAlO ₃ : Ce ³⁺ , YGaO ₃ : Ce ³⁺ , Y (Al, Ga) O ₃ : Ce ³⁺ , Y ₂ SiO ₅ : Ce ³⁺ is preferably used. In addition to these phosphors, aluminates doped with rare earths, orthosilicates doped with rare earths, and the like are preferably used for producing mixed color light.
The compounding quantity of fluorescent substance is the range of 0.1 to 100 mass parts normally with respect to 100 mass parts of epoxy-modified silicone compositions of this invention.

  A known method can be used as a curing method of the curable composition obtained by using the epoxy-modified silicone composition of the present invention. Among the above-mentioned known techniques, the method of curing by heating or the method of curing by irradiating with ultraviolet rays (UV) is a method generally used as a method for curing an epoxy resin, and is a preferable method in the present invention. It can be illustrated. The temperature for curing by heating is not particularly limited because it depends on the epoxy resin and the curing agent used, but is usually in the range of 20 to 200 ° C.

  The curing reaction can be performed in air or in an inert gas atmosphere such as nitrogen, helium, or argon as necessary.

  The curable composition containing the epoxy-modified silicone composition of the present invention can be suitably used as a sealing material for a light emitting device. Further, by sealing the light emitting element using the light emitting element sealing material, a light emitting component such as an optical semiconductor light emitting element (for example, a light emitting diode) can be manufactured.

  The emission wavelength of the light emitting device sealed using the sealing material for light emitting device comprising the curable composition containing the epoxy-modified silicone composition of the present invention is wide from infrared to red, green, blue, purple and ultraviolet. It can be used, and light having a wavelength of 250 nm to 550 nm, which is deteriorated due to insufficient light resistance, can be practically used. As a result, a white light-emitting diode having a long life, high energy efficiency, and high color reproducibility can be obtained. Here, the emission wavelength refers to the main emission peak wavelength.

  As a specific example of the light emitting element to be used, for example, a light emitting element formed by stacking semiconductor materials on a substrate can be exemplified. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.

  Examples of the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. If necessary, a buffer layer may be formed between the substrate and the semiconductor material. Examples of these buffer layers include GaN and AlN.

  The method for laminating the semiconductor material on the substrate is not particularly limited, but for example, MOCVD method, HDVPE method, liquid phase growth method and the like are used.

  Examples of the structure of the light emitting element include a homojunction having a MIS junction, a PN junction, and a PIN junction, a heterojunction, and a double heterostructure. A single or multiple quantum well structure may also be used.

  An optical semiconductor light emitting device (for example, a light emitting diode) can be produced by sealing the light emitting device using a sealing material for a light emitting device comprising a curable composition containing the epoxy-modified silicone composition of the present invention. . In this case, the light-emitting element can be sealed only with the light-emitting element sealing material, but it is also possible to use another sealing material in combination. When other sealing materials are used in combination, after sealing with the sealing material for light emitting elements obtained by using the silicone composition of the present invention, the periphery is sealed with other sealing materials, or other After sealing with a sealing material, it is also possible to seal the circumference | surroundings with the sealing material for light emitting elements obtained using the silicone composition of this invention. Examples of the other sealing material include an epoxy resin, a silicone resin, an acrylic resin, a urea resin, an imide resin, and glass.

  Examples of a method for sealing a light emitting element with a light emitting element sealing material obtained using the curable composition containing the epoxy-modified silicone composition of the present invention include, for example, a light emitting element sealing material in a mold frame. Examples thereof include a method of injecting in advance and immersing a lead frame or the like on which the light emitting element is fixed, and then curing, and a method of injecting a sealing material for a light emitting element into a mold in which the light emitting element is inserted and curing. At this time, examples of the method for injecting the sealing material for the light emitting element include injection by a dispenser, transfer molding, injection molding and the like. As other sealing methods, a sealing material for a light emitting element is dropped onto the light emitting element, and is applied by stencil printing, screen printing, or applying and curing through a mask, or a cup having a light emitting element disposed in the lower part. For example, a method of injecting a sealing material for a light-emitting element into a liquid using a dispenser or the like and curing it.

The curable composition containing the epoxy-modified silicone composition of the present invention can also be used as a die bond material for fixing a light emitting element to a lead terminal or a package, a passivation film on the light emitting element, and a package substrate.
Examples of the shape of the sealing portion include a bullet-shaped lens shape, a plate shape, and a thin film shape.

  A light-emitting diode obtained by encapsulating a light-emitting element using a sealing material for a light-emitting element comprising a curable composition containing the epoxy-modified silicone composition of the present invention should have improved performance by a conventionally known method. Can do. As a method for improving the performance, for example, a method of providing a light reflecting layer or a light collecting layer on the back surface of the light emitting element, a method of forming a complementary colored portion on the bottom, and a layer that absorbs light having a wavelength shorter than the main emission peak is emitted. Method of providing on the element, sealing the light emitting element, molding with a hard material, inserting the light emitting diode into the through hole and fixing, connecting the light emitting element to the lead member by flip chip connection, etc. For example, a method of extracting light from the substrate direction.

  A light-emitting diode obtained by sealing a light-emitting element using a sealing material for a light-emitting element comprising a curable composition containing the epoxy-modified silicone composition of the present invention includes, for example, a backlight such as a liquid crystal display, illumination, It is useful as light sources for various sensors, printers, copiers, etc., instrument light sources for vehicles, signal lights, indicator lights, display devices, light sources for planar light emitters, displays, decorations, various lights, and the like.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples described below.
The composition and properties of the block type organohydrogen silicone and the epoxy-modified silicone were determined by the following method.

(1) Composition of block type organohydrogen silicone
Each component constituting 1 mol of block type organohydrogensilicone represented by the average composition formula (11) by measurement methods of ²⁹ Si-NMR measurement, gel permeation chromatography (GPC) measurement, and ¹ H-NMR measurement. The number of moles of the unit was calculated.

(R ¹ ₃ SiO _1/2 ) _p (R ¹ ₂ HSiO _1/2 ) _q (R ¹ ₂ SiO _2/2 ) _r
(R ¹ HSiO _2/2 ) _s (R ¹ SiO _3/2 ) _t (HSiO _3/2 ) _u (SiO _4/2 ) _v (11)
Specifically, first, ²⁹ Si-NMR measurement of a block-type organohydrogensilicone was performed according to the method described below, and an integrated value calculated from the obtained spectrum pattern was analyzed to obtain hydrogen alkylsiloxy units, dialkylsiloxy. The content such as units was calculated as a percentage.

Next, ¹ H-NMR measurement was performed according to the method described below, and the abundance of alkylsiloxy units having each organic group was calculated as a percentage based on the integral value calculated from the obtained spectrum pattern.

  Using the abundance ratio of each siloxy unit obtained from the above and the theoretical formula amount of each siloxy unit, the average formula amount of the siloxy unit was calculated.

  Subsequently, gel permeation chromatography (GPC) measurement of the block type organohydrogen silicone was performed according to the method described below, and the obtained number average molecular weight was represented by the average composition formula (11). The molecular weight per mole of each of the units constituting the block-type organohydrogensilicone represented by the average composition formula (11) divided by the average formula weight considering the abundance of each unit calculated above The total number of moles was calculated. The block represented by the average composition formula (11) from the total number of moles of each unit constituting the block-type organohydrogensilicone represented by the obtained average composition formula (11) and the abundance of each unit. The number of moles of each unit constituting 1 mol of the type organohydrogensilicone was calculated.

Thereafter, based on the number of moles of each unit constituting 1 mol of the block type organohydrogensilicone represented by the average composition formula (11) obtained above,
-T structural units [(R ¹ SiO _3/2 ) and (HSiO _3/2 )] and Q structural units [(SiO ₂ ) contained in the block type organohydrogen silicone represented by the average composition formula (11) _4/2 )] total number of moles: (t + u + v),
-Number of moles of dialkylsiloxy unit [(R ¹ ₂ SiO _2/2 )]: r,
-Number of moles of alkyl hydrogen siloxy unit [(R ¹ HSiO _2/2 )]: s,
-Mole fraction of dialkyl hydrogen siloxy end [(R ¹ ₂ HSiO _1/2 )] relative to all ends [(R ¹ ₃ SiO _1/2 ) and (R ¹ ₂ HSiO _1/2 )]: q / (p + q) ,
-Content ratio of SiH unit to total Si constituting block type organohydrogensilicone: (q + s + u) / (p + q + r + s + t + u + v),
Was calculated.

^<29 Si-NMR measurement method>
0.15 g of epoxy-modified silicone was dissolved in 1 g of deuterated chloroform. To the solution obtained by adding 0.015 g of Cr (acac) ₃ to the solution, 10 μL of tetramethylsilane was further added to prepare an NMR measurement solution. Using this NMR measurement solution, ²⁹ Si-NMR measurement under proton complete decoupling conditions was performed with a cumulative number of 4000 times (apparatus: α-400 manufactured by JEOL Ltd.).

^<1 H-NMR measurement method>
A solution in which 30 mg of epoxy-modified silicone was dissolved in 1 mL of deuterated chloroform was used as a measurement sample. Using this measurement sample, ¹ H-NMR measurement at 400 MHz (α-400, manufactured by JEOL Ltd.) was performed at a total number of 200 times.

<Gel permeation chromatography (GPC) measurement>
Using a gel permeation chromatography (GPC) analyzer 8020GPC system manufactured by Tosoh Corporation, the following conditions were used.
A 0.5 mass% tetrahydrofuran solution of epoxy-modified silicone was prepared, and then filtered through a 0.45 μm filter to obtain a measurement sample solution.
The number average molecular weight was calculated from the elution time and detection intensity by RI detection at a column temperature of 40 ° C. and through the column with an eluent (tetrahydrofuran) at a flow rate of 1 mL / min.

The column configuration uses TSKguardcolumnH _XL- H (registered trademark) manufactured by Tosoh Corporation as a guard column, TSKgel (registered trademark) G5000H _XL manufactured by Tosoh Corporation, TSKgel (registered trademark) G3000H _XL manufactured by Tosoh Corporation, And one each of TSKgel (registered trademark) G1000H _XL manufactured by Tosoh Corporation was used in series. Further, the molecular weights manufactured by Polymer Laboratories are 7,500,000, 2,560,000, 841,700, 320,000, 148,000, 59,500, 28,500, 10,850, 2,930, A number average molecular weight was calculated from a calibration curve prepared in advance using 580 monodisperse polypolystyrene standard substance and styrene monomer (molecular weight 104).

(2) Calculation of average chain length of block-type organohydrogensilicone It calculated | required by the measurement of ²⁹ Si-NMR shown below.
0.15 g of a block type organohydrogen silicone was dissolved in 1 g of deuterated chloroform. Ten microliters of tetramethylsilane was further added to a solution obtained by adding 0.015 g of Cr (acac) ₃ to the dissolved organohydrogensilicone and dissolving it in the solution to prepare an NMR measurement solution. Using the NMR measurement solution, measurement of ²⁹ Si-NMR under proton complete decoupling conditions was performed with 4,000 times of integration (apparatus: α-400 manufactured by JASCO Corporation), and calculated from the obtained spectrum pattern. The integrated value was analyzed, and the average composition in one molecule of the block type organohydrogensilicone and the average chain length of each of the (R ¹ ₂ SiO _2/2 ) unit and (R ¹ HSiO _2/2 ) unit were calculated.

  Here, the block type organohydrogen silicone produced in the synthesis example, specifically, the case where the siloxy unit excluding the terminal of the silicone is a cyclohexylmethylsiloxy unit, a dimethylsiloxy unit, and a hydrogen methylsiloxy unit is exemplified. The method for calculating the average chain length will be specifically described below.

  When the cyclohexylmethylsiloxy unit and the dimethylsiloxy unit are dialkylsiloxy units (D1), and the hydrogenmethylsiloxy unit is (H1), the chemical shift value of silicon located at the center corresponding to the three chains of D1 and H1 is The following ranges are obtained based on tetramethylsilane silicon.

-D1-D1-D1-: -26.5 ppm excess -23.9 ppm or less -D1-D1-H1-: -23.9 ppm excess -21.5 ppm or less -H1-D1-H1-: -38.5 ppm excess- 37.4 ppm or less -H1-H1-H1-: -35.5 ppm excess-33.0 ppm or less -H1-H1-D1-: -37.4 ppm excess-35.5 ppm or less-D1-H1-D1-: -21 More than 5ppm-19.5ppm or less

  -D1-D1-D1-unit, -D1-D1-H1-unit, -H1-D1-H1-unit, -H1-H1-H1-unit, -H1-H1-D1-unit, -D1- Assuming that the integrated values of the peaks corresponding to the H1-D1-unit are A (D1D1D1), A (D1D1H1), A (H1D1H1), A (H1H1H1), A (H1H1D1), A (D1H1D1), dimethylsiloxy units The average chain length (γD1) and the average chain length (δD1) of hydrogen methylsiloxy units can be calculated by the following formulas (X) and (XI), respectively.

γD1 = 1 + A (D1D1D1) / {A (D1D1H1) + A (H1D1H1)} Expression (X)
δD1 = 1 + {A (H1H1H1) + A (H1H1D1)} / A (D1H1D1) Expression (XI)

(3) Composition of epoxy-modified silicone
It calculated using the result obtained by < ²⁹ > Si-NMR measurement, a gel permeation chromatography (GPC) measurement, and < ¹ > H-NMR measurement.

Specifically, first, ²⁹ Si-NMR measurement of the epoxy-modified silicone was performed according to the method described below, and the integrated value calculated from the obtained spectrum pattern was analyzed to obtain hydrogen alkylsiloxy units, dialkylsiloxy units, and the like. The content fraction was calculated as a percentage.

Next, ¹ H-NMR measurement was performed according to the method described below, and the abundance of alkylsiloxy units having each organic group was calculated as a percentage based on the integral value calculated from the obtained spectrum pattern.

  Using the abundance ratio of each siloxy unit obtained from the above and the theoretical formula amount of each siloxy unit, the average formula amount of the siloxy unit was calculated.

  Subsequently, gel permeation chromatography (GPC) measurement of the epoxy-modified silicone was performed according to the method described below, and the obtained number-average molecular weight per mole of the epoxy-modified silicone represented by the following average composition formula (1) As the molecular weight, the total number of moles of each unit constituting the epoxy-modified silicone represented by the average composition formula (1) was calculated by dividing by the average formula amount considering the abundance of each unit calculated above. From the total number of moles of each unit constituting the epoxy-modified silicone represented by the obtained average composition formula (1) and the abundance of each unit, the epoxy-modified silicone 1 represented by the average composition formula (1) The number of moles of each unit constituting the mole was calculated.

 In addition, in the epoxy-modified silicone represented by the average composition formula (1), the SiH group content (%) with respect to the total number of Si contained in the epoxy-modified silicone represented by the average composition formula (1). The branched chain content (%) relative to the total number of Si contained was calculated by the following formula.

SiH group content (%) with respect to the total number of Si = [(c + i + m) / (a + b + c + d + e + f + g + h + i + j + k + l + m + n) × 100]
Branched chain content (%) = [(j + k + l + m + 2n) / (a + b + c + d + e + f + g + h + i + j + k + l + m + n) × 100]

^<29 Si-NMR measurement method>
0.15 g of epoxy-modified silicone is dissolved in 1 g of deuterated chloroform. To the solution obtained by adding 0.015 g of Cr (acac) ₃ to the solution, 10 μL of tetramethylsilane was further added to prepare an NMR measurement solution. Using this NMR measurement solution, ²⁹ Si-NMR measurement under proton complete decoupling conditions was performed with a cumulative number of 4000 times (apparatus: α-400 manufactured by JEOL Ltd.).

^<1 H-NMR measurement method>
A solution in which 30 mg of epoxy-modified silicone was dissolved in 1 mL of deuterated chloroform was used as a measurement sample. Using this measurement sample, ¹ H-NMR measurement at 400 MHz (α-400, manufactured by JEOL Ltd.) was performed at a total number of 200 times.

<Gel permeation chromatography (GPC) measurement>
Using a gel permeation chromatography (GPC) analyzer 8020GPC system manufactured by Tosoh Corporation, the following conditions were used.

A 0.5 mass% tetrahydrofuran solution of epoxy-modified silicone was prepared, and then filtered through a 0.45 μm filter to obtain a measurement sample solution.
The number average molecular weight was calculated from the elution time and detection intensity by RI detection at a column temperature of 40 ° C. and through the column with an eluent (tetrahydrofuran) at a flow rate of 1 mL / min.

The column configuration uses TSKguardcolumnH _XL- H (registered trademark) manufactured by Tosoh Corporation as a guard column, TSKgel (registered trademark) G5000H _XL manufactured by Tosoh Corporation, TSKgel (registered trademark) G3000H _XL manufactured by Tosoh Corporation, And one each of TSKgel (registered trademark) G1000H _XL manufactured by Tosoh Corporation was used in series. Further, the molecular weights manufactured by Polymer Laboratories are 7,500,000, 2,560,000, 841,700, 320,000, 148,000, 59,500, 28,500, 10,850, 2,930, A number average molecular weight was calculated from a calibration curve prepared in advance using 580 monodisperse polypolystyrene standard substance and styrene monomer (molecular weight 104).

(4) Measurement of low-boiling compound amount remaining in epoxy-modified silicone Using a gas chromatography analyzer GC-14B manufactured by Shimadzu Corporation, the amount was determined under the following conditions.
After weighing about 2 g of epoxy-modified silicone and 0.015 g of n-octane as an internal standard in a 5 mL volumetric flask, a solution diluted to 5 mL with chloroform was used as a measurement sample.

Column: DB-1 (registered trademark) manufactured by J & W Scientific,
Length 30m, inner diameter 0.25mm, liquid film 1μm
Carrier gas: Helium Detector: FID
Injection temperature: 250 ° C
Detector temperature: 300 ° C
Temperature raising condition: After holding at 50 ° C. for 5 min, the temperature was raised from 50 ° C. to 300 ° C. at 10 ° C./min.

  From the obtained results, the content of each component contained in the epoxy-modified silicone was quantified and summed up using a separately prepared calibration curve by an internal standard method. In addition, a numerical value is represented with the mass fraction with respect to epoxy-modified silicone.

(5) Epoxy value Determined by the following procedure and calculation method.
Epoxy-modified silicone was dissolved in benzyl alcohol and 1-propanol. A potassium iodide aqueous solution and a bromophenol blue indicator were added to this solution, followed by titration with 1N hydrochloric acid, and the point where the reaction system turned from blue to yellow was defined as the equivalent point. From the equivalent point, the epoxy value of the epoxy-modified silicone was calculated according to the following formula.

Epoxy value (equivalent / 100 g) = (V × N × F) / (10 × W)
[W, V, N, and F represent the following values, respectively.
W: Weight of sample (g)
V: Titration volume (mL)
N: Normality of hydrochloric acid used for titration (N)
F: Factor of hydrochloric acid used for titration]

(6) Content of transition metal element The content of the transition metal element was analyzed using a quadrupole ICP mass spectrometer (manufactured by Thermo Elemental: X7-ICP-MS).

(7) 0.4 ml of a resin composition sample was charged in a viscosity rotating E-type viscometer of an epoxy-modified silicone composition (manufactured by Toki Sangyo Co., Ltd., “TV-22 type”, rotor: 3 ° × R14). The resin composition was measured at a temperature of 25 ° C.

(8) Storage stability at high temperature of the epoxy-modified silicone composition The storage stability at high temperature of the epoxy-modified silicone composition was evaluated by a storage stability index α represented by the following formula (XII).
Storage stability index α = (storage viscosity) / (starting viscosity) Formula (XII)

  The container containing the epoxy-modified silicone composition immediately after production was sealed and the temperature was adjusted at 25 ° C. for 2 hours, and then the viscosity at 25 ° C. was measured, which was defined as “starting viscosity”. Further, the container containing the silicone composition was sealed and stored in a constant temperature incubator at 80 ° C. for 24 hours. After storage for a predetermined period, the viscosity at 25 ° C. was measured in the same manner as above, and this was defined as “storage viscosity”.

  When the storage stability index α is 1.2 or less, it is judged as having excellent storage stability, and ◎, and when the index α is more than 1.2 and 1.5 or less, it has storage stability. Judgment was made ◯, and when it exceeded 1.5, it was judged that there was no storage stability and x was given.

The viscosity was measured by the following measurement method.
A 0.4 ml resin composition sample was placed in a rotary E-type viscometer (manufactured by Toki Sangyo Co., Ltd., “TV-22 type”, rotor: 3 ° × R14), and the resin composition was measured at a temperature of 25 ° C. did.

(9) Transparency Using a cured product having a thickness of 3 mm, the light transmittance at 350 nm, 400 nm, and 450 nm in the thickness direction was measured with JASCO V-550 manufactured by JASCO Corporation. The initial light transmittance of 80% or more was evaluated as ◎, 70% or more and less than 80% as ○, and less than 70% as ×.

(10) Light resistance It set so that UV light could be irradiated to the hardened | cured material of thickness 3mm in a constant temperature dryer made 50 degreeC constant from UV irradiation apparatus (Ushio Electric make: SP-7) via the optical fiber. Using a 365 nm band pass filter, light of 330 to 410 nm was irradiated so as to be 3 W / cm ² .
After the start of irradiation, ◎ indicates that the cured product is not colored for 250 hours or more, ○ indicates that the cured product is colored in 200 hours or more and less than 250 hours, and × indicates that the cured product is colored in less than 200 hours.

(11) Heat-resistant discoloration Using a cured product having a thickness of 3 mm, the light transmittance at 400 nm in the thickness direction was measured with JASCO V-550 manufactured by JASCO Corporation. Next, the cured product was subjected to heating conditions at 150 ° C. for 100 hours under air, and then allowed to cool at room temperature. Thereafter, the light transmittance at 400 nm in the thickness direction of the sample was measured again. The ratio of the light transmittance of the sample after the heat treatment to the light transmittance of the sample before the heat treatment was calculated as the light transmittance retention. The light transmission retention was 90% or more, ◎, 85% or more and less than 90%, and ○ or less than 85%.

(12) Crack resistance and adhesion 5 mm x 5 mm in a resin mold made of polyphthalamide (Solvay Amodel 4122) with a recess of 10 mmφ and 1 mm depth in the center of a 20 mm x 20 mm x 2 mm flat plate A test piece was obtained by placing a silicon chip of × 0.2 mm, casting the resin composition, and heating and curing. The obtained test piece was held at −40 ° C. for 15 minutes with a thermal cycle tester (Espec Corp. TSE-11-A), then heated up to 120 ° C. in an average of 3 minutes, and held at 120 ° C. for 15 minutes. Then, the test was performed in a cycle in which the temperature was lowered to -40 ° C in an average of 3 minutes.

  The presence or absence of cracks in the cured resin was visually observed to evaluate crack resistance. The case where cracks did not occur for 40 cycles or more was rated as ◎, the case where cracks occurred in 20 cycles or more and less than 40 cycles, and the case where cracks occurred in less than 5 cycles were marked as x.

  In addition, the adhesion is evaluated by the number of occurrences of peeling between the cured resin and the polyphthalamide resin mold, and ◎ indicates that peeling did not occur for 40 cycles or more, and peeling occurred for 20 cycles or more and less than 40 cycles. The case where peeling occurred in less than 5 cycles was evaluated as x.

[Example of catalyst synthesis]
Under a nitrogen atmosphere, in a 50 ml two-necked flask equipped with a reflux tube and a stirrer bar, 8.34 g of phosphorus pentachloride (Wako Pure Chemicals reagent), 1.06 g of ammonium chloride (Wako Pure Chemicals reagent special grade) and tetra After charging 20 ml of chloroethane (aldrich reagent), the reaction was carried out at 160 ° C. for 15 hours while flowing atmospheric nitrogen at 20 ml / min to obtain a yellow solution. After completion of the reaction, 20 ml of petroleum ether (Wako Pure Chemicals Reagent) was added to the system while stirring under an atmospheric pressure of nitrogen atmosphere to precipitate a solid. Subsequently, the obtained solid was filtered under reduced pressure in a nitrogen atmosphere, washed with 100 ml of n-hexane (dehydrated grade for reagent organic synthesis manufactured by Wako Pure Chemical Industries, Ltd.), and then filtered again under nitrogen. Thereafter, it was dried under reduced pressure to obtain 7.1 g of a phosphazene compound as a pale yellow powder. In the following Reference Examples 1 and 2, a solution in which 60 mg of the obtained phosphazene compound was dissolved per 1 g of dichloromethane (dehydrate grade for reagent organic synthesis manufactured by Wako Pure Chemical Industries, Ltd.) was used as the phosphazene solution.

[Reference Example 1: Synthesis of polydialkylsiloxane]
<Synthesis of hydrolyzate>
Distilled water 1500 g was charged into a baffled separable flask having an internal volume of 3 liters equipped with a stirring blade, and then the interior was heated to 60 ° C. While rotating the stirring blade of the separable flask at 600 rpm, a solution in which 500 g of cyclohexylmethyldichlorosilane (Shin-Etsu Chemical Co., Ltd. reagent) and 36.4 g of dimethyldichlorosilane were uniformly mixed was added dropwise at 2 g / min. . After completion of the dropwise addition, the reaction was continued for 2 hours, heating and stirring were stopped, the inner solution was phase-separated, and the aqueous phase was discarded. Next, at room temperature, 500 g of toluene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) and 1 liter of 0.02 mol / liter sodium formate aqueous solution were added, and the stirring blade was rotated at 600 rpm, and stirring was stopped. The inner solution was phase separated and the aqueous phase was discarded. Subsequently, 1 liter of distilled water was added at room temperature, the stirring blade was rotated at 600 rpm, the stirring was stopped, the inner solution was phase-separated, and the aqueous phase was discarded twice. A toluene solution was recovered from the separable flask, and toluene was distilled off at 65 ° C. under reduced pressure using an evaporator to obtain a hydrolyzate.

<Synthesis of polydialkylsiloxane>
A 500 ml separable flask equipped with a distillation tube and a stirring blade was charged with 300 g of the obtained hydrolyzate and 1 g of the phosphazene solution obtained in the catalyst synthesis example, and then the system was purged with nitrogen under reduced pressure. Subsequently, the system was heated to 120 ° C. and subjected to a polycondensation reaction at a pressure of 150 torr for 45 minutes, and then the reaction system was returned to atmospheric pressure with nitrogen and cooled to 60 ° C. Next, 7 g of 1,1,3,3-tetramethyl-disiloxane (reagent manufactured by Shin-Etsu Chemical Co., Ltd.) purified by distillation under dry nitrogen was added to the system under a nitrogen atmosphere, and stirring was continued for 3 hours. After end-capping reaction, the mixture was cooled to room temperature. The contents were dissolved and recovered using a total of 500 ml of toluene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.), and the toluene was distilled off from the resulting solution with an evaporator at 65 ° C. under reduced pressure to obtain a polydialkylsiloxane. It was.

All terminal structures of the obtained polydialkylsiloxane were H—Si (CH ₃ ) ₂ —O—, and the composition other than the terminal groups was 20 mol% of dimethylsiloxy units and 80 mol% of cyclohexylmethylsiloxy units. It was. As a result of molecular weight measurement, the elution curve was bimodal, the number average molecular weight of the peak on the high molecular weight side was 11,700, and the area area was 65% with respect to all peaks.
If necessary, the above synthesis operation was repeated to obtain a polydialkylsiloxane, which was used in the following reaction.

[Reference Example 2: Synthesis of polyhydrogenmethylsiloxane]
In a 0.5 liter reactor equipped with a reflux condenser, thermometer and stirrer bar, 1,3,5,7-tetramethylcyclotetrasiloxane (reagent manufactured by Shin-Etsu Chemical Co., Ltd.) purified by distillation under dry nitrogen was added. 145 g, 145 g of 1,1,3,3-tetramethyl-disiloxane purified by distillation under nitrogen (reagent manufactured by Shin-Etsu Chemical Co., Ltd.), activated clay (TONSIL OPTIMUM 230FF) dried at 110 ° C. for 5 hours under vacuum: 0.42 g (made by Zude Chemie) was charged, and the reaction was carried out under stirring at 65 ° C. under nitrogen for 24 hours. The obtained reaction solution was passed through a 1 μm filter under dry nitrogen to remove the catalyst, and then the low molecular weight oligomer was distilled off over 3 hours at 50 ° C. under 2 kPa to obtain polyhydrogenmethylsiloxane. .

All terminal structures of the obtained polyhydrogenmethylsiloxane were H—Si (CH ₃ ) ₂ —O—, and the main chain structure was only hydrogen methylsiloxy units. The number average molecular weight was 600.
If necessary, the above synthesis operation was repeated to obtain polyhydrogenmethylsiloxane, which was used in the following reaction.

[Synthesis Example 1: Synthesis of organohydrogensilicone having hydrogen methyl units and dialkyl units alternately as block units]
<Equilibration reaction>
A 300 ml separable flask equipped with a stirring blade was charged with 95 g of the polydialkylsiloxane obtained in Reference Example 1 and 35.1 g of the polyhydrogenmethylsiloxane obtained in Reference Example 2 under dry nitrogen. The inside of the system was cooled to 20 ° C. After the system is uniformly mixed and dispersed, trifluoromethanesulfonic acid (special grade product manufactured by Wako Pure Chemical Industries, Ltd.) is mixed with polydialkylsiloxane and polyhydrogenmethylsiloxane under dry nitrogen conditions while continuing stirring under dry nitrogen. After adding 0.25 wt% with respect to the total weight of the mixture and carrying out the equilibration reaction for 15 minutes, equimolar amount of triethylamine (reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.) is added with the added trifluoromethanesulfonic acid. The stirring was continued for 30 minutes. After 30 minutes, stirring was stopped to bring the reaction system to room temperature, and the contents were dissolved and recovered using a total of 600 ml of toluene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.). The recovered solution is transferred to a 2 liter separatory funnel, and 700 ml of a 0.02 mol / liter aqueous sodium hydrogen carbonate solution is added for separation and washing, and then the phases are separated and the aqueous phase is discarded. Subsequently, 700 ml of distilled water was added, followed by separation and washing, and then the phase separation was performed and the aqueous phase was discarded twice. The toluene solution was recovered, and toluene was distilled off at 65 ° C. under reduced pressure using an evaporator to obtain silicone.

<Evaporation of low molecular weight components>
A glass tube oven [GTO-350RG manufactured by Shibata Kagaku Co., Ltd.] having the surface silicone heater prepared by charging the silicone obtained above into a cylindrical tube made of Pyrex (registered trademark) glass having an inner diameter of 70 mm and an effective length of 200 mm. Set. After replacing the interior with nitrogen under room temperature conditions, the internal cylindrical tube started to rotate, and under a pressure of 0.1 kPa, the temperature was raised to 200 ° C. for 1 hour, and then the temperature was raised to 250 ° C. The temperature was raised to 300 ° C. for 3 hours, and the low molecular weight component was distilled off over 3 hours. After completion of low boiling distillation, after cooling to room temperature, the pressure is reduced to atmospheric pressure with dry nitrogen, and hydrogen alkylsiloxane having hydrogen methyl unit chains and dialkyl unit chains alternately as block units (hereinafter abbreviated as “block type organohydrogen silicone”). .)

As a result of molecular weight measurement, the number average molecular weight of the obtained block type organohydrogensilicone was 7,200. Also, all of the end structure of the resulting block-type organohydrogensilicone _{is, [H-Si (CH 3} ) 2 -O 1/2 -] is the composition of the block type organohydrogensilicone, [H- _{Si (CH 3) 2 -O 1/2} -] units 2.3 mol%, hydrogen methylsiloxy units 29.3 mol% dimethylsiloxy units 14.2 mol%, cyclohexylmethyl siloxy units 54.2 mol%, a dialkyl The average chain lengths of siloxy units and hydrogen methylsiloxy units were 40 and 4.3, respectively.

In the obtained block-type organohydrogensilicone: Sum of the number of moles of each of the T structural unit and the Q structural unit [(R ¹ SiO _3/2 ), (HSiO ₃ in the average composition formula (11) in the present invention) _{/ 2} ), the total number of moles of (SiO _4/2 ) units: (t + u + v)] is zero,
Number of moles of dialkylsiloxy units [in the average composition formula (11) in the present invention
The number of moles of (R ¹ ₂ SiO _2/2 ) units: r] is 59.5,
Number of moles of alkyl hydrogen siloxy units [in the average composition formula (11) in the present invention
The number of moles of (R ¹ HSiO _2/2 ): s] is 25.5,
-Mole fraction of dialkyl hydrogen siloxy terminals relative to all terminals [based on the total number of moles of (R ¹ ₃ SiO _1/2 ) and (R ¹ ₂ HSiO _1/2 ) units in average composition formula (11) in the present invention ( R ¹ ₂ HSiO _1/2 ) unit molar fraction: q / (p + q)] is 1,
-Content ratio of SiH unit to the total Si constituting the block type organohydrogen silicone [based on the total number of moles of Si in the average composition formula (11) in the present invention
The total number of moles of (R ¹ ₂ HSiO _1/2 ), (R ¹ HSiO _2/2 ), (HSiO _3/2 ) units: q + s + u) / (p + q + r + s + t + u + v)] is 0.316
Met.

  Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.

[Example 1]
<Production of epoxy-modified silicone composition>
A 1 liter reactor with a reflux condenser, thermometer and stirrer was replaced with dry nitrogen. Under dry nitrogen conditions, 60 g of the block-type organohydrogensilicone produced in Synthesis Example 1 was added to the apparatus, and 217.8 g of 4-vinylcyclohexene oxide (reagent manufactured by Aldrich) purified by dehydration distillation under dry nitrogen. Then, 328 g of 1,4-dioxane (reagent special grade manufactured by Wako Pure Chemical Industries, Ltd.) dehydrated and purified under nitrogen was charged, and the temperature was raised to 65 ° C. with stirring in an atmospheric pressure dry nitrogen atmosphere.

  To this, 0.5 g of a 1,4-dioxane diluted solution of platinum divinyltetramethyldisiloxane complex containing 500 ppm of platinum in terms of platinum element was added under dry nitrogen, and the hydrosilylation reaction was carried out for 60 hours. Then, it was left to cool to room temperature. When sampling was performed immediately before the heating was stopped, the hydrosilylation reaction progressed quantitatively, and unreacted SiH units were not detected.

  1,4-dioxane was distilled off from the reaction mixture using an evaporator at a heating temperature of 40 ° C. under reduced pressure to obtain an epoxy-modified silicone.

  100 g of the resulting epoxy-modified silicone was placed in a Pyrex (registered trademark) glass cylindrical tube having an inner diameter of 70 mm and an effective length of 200 mm, and set in a glass tube oven (GTO-350 manufactured by Shibata Kagaku). After starting rotation of the internal cylindrical tube and substituting the inside with dry nitrogen at room temperature, dry nitrogen at a temperature of 35 ° C. and a pressure of 0.1 kPa at a flow rate of 10 ml / min in terms of atmospheric pressure inside. The epoxy-modified silicone (1a) in which the low boiling point compound was reduced was obtained by treating for 80 hours while introducing.

  All terminal structures of the resulting epoxy-modified silicone (1a) were modified to trialkylsiloxy groups by a hydrosilylation reaction.

  Further, in the obtained epoxy-modified silicone (1a), the content of SiH groups relative to the total number of Si [(c + i + m) / (a + b + c + d + e + f + g + h + i + j + k + l + m + n) × 100 in the average composition formula (1) of the present invention], and The values of the contents [(j + k + l + m + 2n) / (a + b + c + d + e + f + g + h + i + j + k + l + m + n) × 100 in the average composition formula (1) of the present invention] were all zero.

  The composition excluding the terminal group was 30.0 mol% of units in which vinylcyclohexene oxide was added to hydrogen methylsiloxy units, 14.5 mol% of dimethylsiloxy units, and 55.5 mol% of cyclohexylmethylsiloxy units. As a result of the molecular weight measurement, the number average molecular weight was 9,700. In addition, formation of a high molecular weight part accompanying the ring opening of the epoxy group was not observed at all.

  Examples of low boiling compounds remaining in the epoxy-modified silicone (1a) include 4-vinylcyclohexene oxide and 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide. As a result, the residual amounts were 40 ppm and 30 ppm, respectively. Other compounds were not detected.

  Moreover, the epoxy value of the epoxy-modified silicone (1a) was 0.214, the transition metal element contained was only platinum, and the content of the element was 5 ppm.

  The above synthetic operation was repeated to obtain an epoxy-modified silicone (1a), and the following treatment was performed.

  1,000 g of epoxy-modified silicone (1a) and octadecyl-3- (3,5-di-tert-butyl-) as an antioxidant in a 2 liter Pyrex (registered trademark) glass stirring tank equipped with a stirring blade 4-hydroxyphenyl) -propionate 0.008 g [corresponding to 0.0008 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone (1a)], and uniformly mixed at 30 ° C. for 2 hours in a nitrogen atmosphere, A colorless and transparent epoxy-modified silicone composition (1b) in which octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate was uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (1b) was 100,000 mPa · s or less. Table 1 shows the storage stability evaluation results of the epoxy-modified silicone composition (1b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the resulting epoxy-modified silicone composition (1b), 36 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 18 parts by mass of U-CAT 18X0.25 were mixed under nitrogen. After stirring until the whole became uniform, defoaming was performed to obtain a curable composition (1). The curable composition (1) was poured into a mold having a depth of 3 mm under nitrogen, and a curing reaction was performed at 120 ° C. for 1 hour and further at 150 ° C. for 3 hours to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Example 2]
<Production of epoxy-modified silicone composition>
0.020 g of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate as an antioxidant [corresponds to 0.002 parts by mass with respect to 100 parts by mass of epoxy-modified silicone (1a) A colorless and transparent epoxy-modified silicone composition in which octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate was uniformly dissolved in the same manner as in Example 1 except that it was used (2b) was obtained. The viscosity of the epoxy-modified silicone composition (2b) was 100,000 mPa · s or less. Table 1 shows the storage stability evaluation results of the epoxy-modified silicone composition (2b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the resulting epoxy-modified silicone composition (2b), RIKACID MH-700G (product of Shin Nippon Rika Co., Ltd .; methyl hexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 38.1 parts by mass, 1,2-propane 3 parts by mass of a diol and 18 parts by mass of U-CAT 18X0.25 were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition (2). The curable composition (2) was poured into a mold having a depth of 3 mm under nitrogen and subjected to a curing reaction at 120 ° C. for 1 hour and further at 150 ° C. for 3 hours to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Example 3]
<Production of epoxy-modified silicone composition>
0.150 g of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate as an antioxidant [corresponds to 0.015 parts by mass with respect to 100 parts by mass of epoxy-modified silicone (1a) A colorless and transparent epoxy-modified silicone composition in which octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate was uniformly dissolved in the same manner as in Example 1 except that it was used (3b) was obtained. The viscosity of the epoxy-modified silicone composition (3b) was 100,000 mPa · s or less. Table 1 shows the storage stability evaluation results of the epoxy-modified silicone composition (3b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the resulting epoxy-modified silicone composition (3b), Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methyl hexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 38.1 parts by mass, 1,2-propane A diol (3 parts by mass) and U-CAT 18X0.25 parts by mass were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition (3). The curable composition (3) was poured into a mold having a depth of 3 mm under nitrogen, and a curing reaction was performed at 120 ° C. for 1 hour and further at 150 ° C. for 3 hours to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Example 4]
<Production of epoxy-modified silicone composition>
In the same manner as in Example 1, except that 4 g of dilauryl thiodipropionate (corresponding to 0.4 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone (1a)) was used as an antioxidant, dilauryl thiol was used. A colorless and transparent epoxy-modified silicone composition (4b) in which dipropionate was uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (4b) was 100,000 mPa · s or less. Table 1 shows the storage stability evaluation results of the epoxy-modified silicone composition (4b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the resulting epoxy-modified silicone composition (4b), Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methyl hexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 38.1 parts by mass, 1,2-propane 3 parts by mass of a diol and 18 parts by mass of U-CAT 18X0.25 were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition (4). The curable composition (4) was poured into a mold having a depth of 3 mm under nitrogen and subjected to a curing reaction at 120 ° C. for 1 hour and further at 150 ° C. for 3 hours to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Example 5]
<Production of epoxy-modified silicone composition>
Dilauryl thiodipropionate was used in the same manner as in Example 1 except that 40 g of dilauryl thiodipropionate (corresponding to 4 parts by mass with respect to 100 parts by mass of epoxy-modified silicone (1a)) was used as an antioxidant. A colorless and transparent epoxy-modified silicone composition (5b) in which the nitrate was uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (5b) was 100,000 mPa · s or less. Table 1 shows the storage stability evaluation results of the epoxy-modified silicone composition (5b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the resulting epoxy-modified silicone composition (5b), Ricacid MH-700G (product of Shin Nippon Chemical Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 38.1 parts by mass, 1,2-propane 3 parts by mass of a diol and 18 parts by mass of U-CAT 18X0.25 were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition (5). The curable composition (5) was poured into a mold having a depth of 3 mm under nitrogen, and a curing reaction was performed at 120 ° C. for 1 hour and further at 150 ° C. for 3 hours to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Example 6]
<Production of epoxy-modified silicone composition>
Except for using 0.040 g of tris (2,4-di-tert-butylphenyl) phosphite as an antioxidant (equivalent to 0.004 parts by mass with respect to 100 parts by mass of epoxy-modified silicone (1a)), In the same manner as in Example 1, a colorless and transparent epoxy-modified silicone composition (6b) in which tris (2,4-di-tert-butylphenyl) phosphite was uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (6b) was 100,000 mPa · s or less. Table 1 shows the storage stability evaluation results of the epoxy-modified silicone composition (6b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the resulting epoxy-modified silicone composition (6b), Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methyl hexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 38.1 parts by mass, 1,2-propane 3 parts by mass of a diol and 18 parts by mass of U-CAT 18X0.25 were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition (6). The curable composition (6) was poured into a mold having a depth of 3 mm under nitrogen, and a curing reaction was performed at 120 ° C. for 1 hour and further at 150 ° C. for 3 hours to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Example 7]
<Production of epoxy-modified silicone composition>
Except for using 0.020 g of N, N′-di-sec-butyl-p-phenylenediamine as an antioxidant (equivalent to 0.002 parts by mass with respect to 100 parts by mass of epoxy-modified silicone (1a)), In the same manner as in Example 1, a colorless and transparent epoxy-modified silicone composition (7b) in which N, N′-di-sec-butyl-p-phenylenediamine was uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (7b) was 100,000 mPa · s or less. Table 1 shows the storage stability evaluation results of the epoxy-modified silicone composition (7b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the resulting epoxy-modified silicone composition (7b), Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methyl hexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 38.1 parts by mass, 1,2-propane 3 parts by mass of a diol and 18 parts by mass of U-CAT 18X0.25 were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition (7). The curable composition (7) was poured into a mold having a depth of 3 mm under nitrogen and subjected to a curing reaction at 120 ° C. for 1 hour and further at 150 ° C. for 3 hours to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Example 8]
<Production of epoxy-modified silicone composition>
0.10 g of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate as an antioxidant [corresponds to 0.01 parts by mass with respect to 100 parts by mass of epoxy-modified silicone (1a) ] And 0.05 g of dilauryl thiodipropionate
[Equivalent to 0.005 parts by mass with respect to 100 parts by mass of epoxy-modified silicone (1a)] In the same manner as in Example 1, octadecyl-3- (3,5-di-tert-butyl- A colorless and transparent epoxy-modified silicone composition (8b) in which 4-hydroxyphenyl) -propionate and dilaurylthiodipropionate were uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (8b) was 100,000 mPa · s or less. Table 3 shows the storage stability evaluation results of the epoxy-modified silicone composition (8b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the resulting epoxy-modified silicone composition (8b), Rikacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methyl hexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 38.1 parts by mass, 1,2-propane 3 parts by mass of a diol and 18 parts by mass of U-CAT 18X0.25 were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition (8). The curable composition (8) was poured into a mold having a depth of 3 mm under nitrogen, and a curing reaction was performed at 120 ° C. for 1 hour and further at 150 ° C. for 3 hours to obtain a cured product. Table 4 shows the performance of the obtained cured product.

[Example 9]
<Production of epoxy-modified silicone composition>
0.20 g of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate as an antioxidant [corresponding to 0.02 parts by mass with respect to 100 parts by mass of epoxy-modified silicone (1a) ] And dilauryl thiodipropionate in the same manner as in Example 1 except that 0.10 g [corresponding to 0.01 part by mass with respect to 100 parts by mass of the epoxy-modified silicone (1a)] is used. A colorless and transparent epoxy-modified silicone composition (9b) in which-(3,5-di-tert-butyl-4-hydroxyphenyl) -propionate and dilaurylthiodipropionate were uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (9b) was 100,000 mPa · s or less. Table 3 shows the storage stability evaluation results of the epoxy-modified silicone composition (9b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
90 parts by mass of the resulting epoxy-modified silicone composition (9b), 10 parts by mass of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanedicarboxylate, Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methyl) Hexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 41 parts by mass, 1,2-propanediol 3 parts by mass, U-CAT 18X0.25 parts by mass under nitrogen, and stirred until the whole is uniform The curable composition (9) was obtained by defoaming. The curable composition (9) was poured into a mold having a depth of 3 mm under nitrogen, and a curing reaction was performed at 120 ° C. for 1 hour and further at 150 ° C. for 3 hours to obtain a cured product. Table 4 shows the performance of the obtained cured product.

[Example 10]
<Production of epoxy-modified silicone composition>
0.10 g of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate as an antioxidant [corresponds to 0.01 parts by mass with respect to 100 parts by mass of epoxy-modified silicone (1a) ] And tris (2,4-di-tert-butylphenyl) phosphite were used except that 0.05 g [corresponding to 0.005 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone (1a)] was used. 1 colorless, in which octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate and tris (2,4-di-tert-butylphenyl) phosphite were uniformly dissolved A transparent epoxy-modified silicone composition (10b) was obtained. The viscosity of the epoxy-modified silicone composition (10b) was 100,000 mPa · s or less. Table 3 shows the storage stability evaluation results of the epoxy-modified silicone composition (10b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the resulting epoxy-modified silicone composition (10b), Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methyl hexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 38.1 parts by mass, 1,2-propane 3 parts by mass of a diol and 18 parts by mass of U-CAT 18X0.25 were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition (10). The curable composition (10) was poured into a mold having a depth of 3 mm under nitrogen, and a curing reaction was performed at 120 ° C. for 1 hour and further at 150 ° C. for 3 hours to obtain a cured product. Table 4 shows the performance of the obtained cured product.

[Comparative Example 1]
<Production of epoxy-modified silicone composition>
In the same manner as in Example 1, except that 0.0010 g of dilauryl thiodipropionate (corresponding to 0.0001 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone (1a)) was used as an antioxidant. A colorless and transparent epoxy-modified silicone composition (1c) in which lauryl thiodipropionate was uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (1c) was 100,000 mPa · s or less. Table 3 shows the storage stability evaluation results of the epoxy-modified silicone composition (1c) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the resulting epoxy-modified silicone composition (1c), Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methyl hexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 38.1 parts by mass, 1,2-propane 3 parts by mass of a diol and 18 parts by mass of U-CAT 18X0.25 were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition (1d). The curable composition (1d) was poured into a mold having a depth of 3 mm under nitrogen, and a curing reaction was performed at 120 ° C. for 1 hour and further at 150 ° C. for 3 hours to obtain a cured product. Table 4 shows the performance of the obtained cured product.

[Comparative Example 2]
<Production of epoxy-modified silicone composition>
Dilauryl thiodipropionate was used in the same manner as in Example 1 except that 60 g of dilauryl thiodipropionate (corresponding to 6 parts by mass with respect to 100 parts by mass of epoxy-modified silicone (1a)) was used as an antioxidant. An epoxy-modified silicone composition (2c) mixed with an ate was prepared. In the obtained epoxy-modified silicone composition (2c), undissolved dilauryl thiodipropionate remained, and the epoxy-modified silicone composition (2c) was cloudy and was not transparent. The viscosity of the epoxy-modified silicone composition (2c) was 100,000 mPa · s or less. Table 3 shows the storage stability evaluation results of the epoxy-modified silicone composition (2c) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the resulting epoxy-modified silicone composition (2c), Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methyl hexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 38.1 parts by mass, 1,2-propane A diol (3 parts by mass) and U-CAT 18X0.25 parts by mass were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition (2d). The curable composition (2d) was poured into a mold having a depth of 3 mm under nitrogen, and a curing reaction was performed at 120 ° C. for 1 hour and further at 150 ° C. for 3 hours to obtain a cured product. Table 4 shows the performance of the obtained cured product.

[Example 11]
<Production of epoxy-modified silicone composition>
A 3 L reactor with reflux condenser, thermometer and stirrer was replaced with dry nitrogen. Under dry nitrogen conditions, 80 g of 1,3,5,7-tetramethylcyclotetrasiloxane (reagent manufactured by Shin-Etsu Chemical Co., Ltd.) purified by dehydration distillation under dry nitrogen in the above apparatus, dehydration distillation purification under dry nitrogen 77 g of 1,3-divinyltetramethyldisiloxane (Shin-Etsu Chemical reagent), 81.5 g of 4-vinylcyclohexene oxide (Aldrich reagent) purified by dehydration distillation under dry nitrogen, dehydration distillation under nitrogen After charging 954 g of purified 1,4-dioxane (a reagent manufactured by Wako Pure Chemical Industries, Ltd.), the mixture was heated in an oil bath heated to 70 ° C. with stirring in an atmospheric pressure dry nitrogen atmosphere.

  After the temperature of the inner solution exceeds 65 ° C., 2.0 g of a 1,4-dioxane solution of platinum divinyltetramethyldisilicone complex containing 500 ppm of platinum in terms of platinum element is added to the solution under dry nitrogen, The hydrosilylation reaction was performed for 90 hours. At this time, the temperature of the reaction solution was between 65 ° C and 75 ° C. After the reaction for 90 hours, the hydrosilylation reaction proceeded quantitatively, and no unreacted SiH unit was detected. Subsequently, the heating of the reaction solution was stopped and the mixture was allowed to cool to room temperature.

After the cooling was completed, 954 g of acetonitrile (reagent manufactured by Wako Pure Chemical Industries, Ltd.) dehydrated and purified under dry nitrogen was added to the reaction solution, and the mixture was stirred for 2 hours under an atmospheric pressure dry nitrogen atmosphere, and then the stirring was stopped. . Next, 790 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd .: granular) heated and dried at 150 ° C. for 3 hours under a dry nitrogen stream was added, and activated carbon treatment was performed for 48 hours under a dry nitrogen atmosphere. After the activated carbon treatment was completed, the activated carbon was filtered using a PTFE membrane filter having a pore size of 1 μm to collect the filtrate. Furthermore, the activated carbon separated by the above operation was washed with 1500 g of 1,4-dioxane (reagent manufactured by Wako Pure Chemical Industries, Ltd.) purified by dehydration distillation under nitrogen, and the activated carbon was similarly filtered using a membrane filter. The washing liquid was collected and mixed with the previously obtained filtrate.
1,4-dioxane and acetonitrile were distilled off from the collected liquid mixture using an evaporator at a heating temperature of 40 ° C. under reduced pressure to obtain an epoxy-modified silicone-containing component.

  A part of the obtained epoxy-modified silicone-containing component was placed in a Pyrex (registered trademark) glass cylindrical tube having an inner diameter of 70 mm and an effective length of 200 mm, and set in a glass tube oven (GTO-350 manufactured by Shibata Kagaku). After starting rotation of the internal cylindrical tube and substituting the inside with dry nitrogen under room temperature conditions, at a temperature of 40 ° C. and a pressure of 0.2 kPa, the dry nitrogen was supplied at a flow rate of 10 mL / min in terms of atmospheric pressure. An epoxy-modified silicone with reduced low-boiling compounds was obtained by heating under reduced pressure for 80 hours while introducing. This operation was repeated for the remaining epoxy-modified silicone-containing component obtained by distilling off 1,4-dioxane and acetonitrile obtained above to obtain 190 g of an epoxy-modified silicone (2a) with reduced low boiling point compounds.

The resulting epoxy-modified silicone (1a) has a structure represented by the following average composition formula (11) having a number average molecular weight of 2,100, and no formation of a high molecular weight portion due to the ring opening of the epoxy group is observed at all. It was.
(Me ₂ YSiO _1/2 ) _7.91 (MeZSiO _2/2 ) _7.91 (Me [VCHO] SiO _2/2 ) _4.83 (11)
Here, Y in the average composition formula (11) represents a divalent organic group represented by —CH ₂ —CH ₂ —, and Z represents a bond with a divalent hydrocarbon group Y. In addition, (Me [VCHO] SiO _2/2 ) represents a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit by an anti-markovnikov by a hydrosilylation reaction. ]

  Further, in the obtained epoxy-modified silicone (2a), the content of SiH groups relative to the total number of Si [(c + i + m) / (a + b + c + d + e + f + g + h + i + j + k + l + m + n) × 100 in the average composition formula (1) of the present invention], and The values of the contents [(j + k + l + m + 2n) / (a + b + c + d + e + f + g + h + i + j + k + l + m + n) × 100 in the average composition formula (1) of the present invention] were all zero.

  Examples of the low-boiling compound remaining in the epoxy-modified silicone (2a) include 4-ethylidenylcyclohexene oxide formed by internal transition of a carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide. The residual amounts were detected as 20 ppm and 20 ppm, respectively. Other compounds were not detected.

Moreover, the epoxy value of the epoxy-modified silicone (2a) was 0.23, the transition metal element contained was only platinum, and the content of the element was 0.5 ppm.
The above synthesis operation was repeated to obtain an epoxy-modified silicone (2a), and the following treatment was performed.

  1,000 g of epoxy-modified silicone (2a) and octadecyl-3- (3,5-di-tert-butyl-) as an antioxidant in a Pyrex (registered trademark) glass stirring tank having a stirring capacity of 2 liters equipped with a stirring blade 4-hydroxyphenyl) -propionate 0.20 g [equivalent to 0.02 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone (2a)], and uniformly mixed at 30 ° C. for 2 hours in a nitrogen atmosphere, A colorless and transparent epoxy-modified silicone composition (11b) in which octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate was uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (11b) was 100,000 mPa · s or less. Table 3 shows the storage stability evaluation results of the epoxy-modified silicone composition (11b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the resulting epoxy-modified silicone composition (11b), Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 40.9 parts by mass, 1,2-propane 3 parts by mass of a diol and 18 parts by mass of U-CAT 18X0.25 were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition (1d). The curable composition (1d) was poured into a mold having a depth of 3 mm under nitrogen, and a curing reaction was performed at 120 ° C. for 1 hour and further at 140 ° C. for 3 hours to obtain a cured product. Table 4 shows the performance of the obtained cured product.

  When cured, the cured product has good transparency, excellent light resistance, excellent heat discoloration, and excellent adhesion, and also excellent when exposed to high temperature environments during transportation and storage It is possible to provide an epoxy-modified silicone composition having excellent storage stability and a curable epoxy-modified silicone composition containing the epoxy-modified silicone composition.

Claims (7)

At least 1 selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and amine antioxidants with respect to 100 parts by mass of the epoxy-modified silicone represented by the following average composition formula (1) An epoxy-modified silicone composition comprising 0.0005 to 5 parts by mass of a seed antioxidant.

[In the average composition formula (1), each R ¹ independently has (A) a chain, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, and has 1 to 24 carbon atoms. Or a monovalent aliphatic organic group having 0 or more and 5 or less oxygen atoms, (B) monovalent or unsubstituted or substituted carbon atoms having 6 or more and 24 or less, and oxygen atoms having 0 or more and 5 or less A monovalent aromatic organic group having a substituent having a linear, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, when substituted, Or (C) a chain, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, or an unsubstituted or substituted aromatic hydrocarbon structure, having 5 to 26 carbon atoms, oxygen atom Represents a monovalent organic group having a number of 0 to 5 and a silicon atom number of 1 . A plurality of R ¹ in each siloxy unit may be the same or different.
R ² each independently has a chain, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, having 4 to 24 carbon atoms and 1 to 5 oxygen atoms. Represents a monovalent organic group containing an epoxy group. A plurality of R ² in each siloxy unit may be the same or different.
Y is each independently composed of one or more structures selected from the group consisting of unsubstituted or substituted chain, branched and cyclic, having 2 to 70 carbon atoms and 0 to 15 oxygen atoms. Hereinafter, a divalent organic group having 0 or more and 10 or less silicon atoms is represented. A plurality of Y in each siloxy unit may be the same or different.
Z represents a divalent hydrocarbon group bonded to Y.
a, b, c, d, e, f, g, h, i, j, k, l, m, n represent the number of moles of each siloxy unit present in 1 mole of epoxy-modified silicone; , C, d, e, f, g, h, i, j, k, l, m, and n are values that are 0 or more, and satisfy d + h + k> 0, e + f + h + i + j + k> 0, and g = a + f + l at the same time. ] The epoxy-modified silicone composition according to claim 1, wherein the total content of the transition metal elements is 30 ppm by mass or less. The epoxy-modified silicone composition according to claim 1 or 2, wherein an epoxy value of the epoxy-modified silicone is in a range of 0.15 to 0.50. The epoxy-modified silicone composition according to any one of claims 1 to 3, wherein R ² is each independently any organic group represented by the following general formulas (2) to (5). .

[In General Formulas (2) to (5), each R ³ is independently a chain, branched or cyclic unsubstituted group having 1 to 16 carbon atoms and 1 to 4 oxygen atoms. Alternatively, it represents a substituted divalent organic group. ] The epoxy-modified silicone composition according to any one of claims 1 to 4, wherein the content of SiH groups relative to the total number of Si in the epoxy-modified silicone is less than 2%. The epoxy-modified silicone composition according to any one of claims 1 to 5, wherein the viscosity at 25 ° C is 500,000 mPa · s or less. Curability characterized by containing 0.001 to 10 parts by mass of a curing catalyst with respect to 100 parts by mass of the epoxy-modified silicone composition according to any one of claims 1 to 6. Epoxy-modified silicone composition.