JP2014218679A - Silicone composition, curable composition, and light-emitting component using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicone composition in which a cured product, when the composition is cured, has satisfactory transparency, excellent light resistance, excellent thermal discoloration resistance and excellent adhesiveness, and is excellent storage stability in high temperature during transportation, storage or the like.SOLUTION: A silicone composition contains epoxy-modified silicone expressed by the following average composition formula (1) and a nitryl compound, and content of the nitryl compound is 0.1 mass ppm or more and 50 mass ppm or less. [in the average composition formula (1), Reach independently denotes (A) a monovalent aliphatic organic group, (B) a monovalent aromatic organic group or (C) a monovalent organic group. Reach independently denotes an organic group containing an epoxy group. Y each independently denotes a divalent organic group. Z denotes bond with Y. a to n denote mol numbers in each siloxy unit that is present in 1 mol of epoxy-modified silicone]

Description

  The present invention relates to a silicone composition, a curable composition, and a light-emitting component using the same.

  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.

  Further, Patent Document 3 proposes an epoxy siloxane composed of a reaction product of vinyl silicone, silyl hydride functional silicone, and olefin epoxy compound.

  Patent Document 4 proposes an epoxy group-containing organopolysiloxane comprising a reaction product of an organopolysiloxane having a hydroxyl group at both ends, an organohydropolysiloxane, and an epoxy group and alkenyl group-containing compound.

  Patent Document 5 discloses a telechelic siloxane having a plurality of terminal epoxy groups, which is obtained from a reaction between a polyorganosiloxane having a vinyl group at the terminal, an organosiloxane oligomer having an SiH unit, and an excess of an alkenyl group-containing epoxy compound. Polymers have been proposed.

  Patent Document 6 discloses a modified polysiloxane having at least two epoxy groups in one molecule containing a component in a specific molecular weight range in a specific range, and a thermosetting composition containing the modified polysiloxane. Compositions have been proposed.

  In said patent documents 1-6, the hardened | cured material obtained using the epoxy-modified silicone obtained has high heat resistance, high light resistance, or high adhesiveness, or contains the epoxy-modified silicone obtained. Although there is a description that the curable composition has high curability, the storage stability of the epoxy-modified silicone itself has not yet been sufficient.

  Further, Patent Document 7 discloses a siloxane having a cyclic structure and an organopolysiloxane having an epoxy group unit as a substituent. By curing the organopolysiloxane, transparency, heat resistance, thermal shock resistance are disclosed. It is described that a cured product with high adhesion can be obtained. In addition, the publication discloses that the organopolysiloxane obtained has high storage stability at room temperature, but the storage stability at high temperatures such as during transportation and storage has not yet been sufficient.

  On the other hand, in the hydrosilylation reaction, a method of adding a cyano compound is known in order to suppress gelation and thickening due to reaction of an epoxy group. For example, in Patent Document 8 and Patent Document 9, a cyano group-containing compound coexists in the addition reaction using an addition reaction catalyst between an SiH group of an organohydropolysiloxane or organohydrosilane and an alkenyl group of an alkenyl group-containing epoxy compound. Is disclosed. The publication also discloses that after the addition reaction, an epoxy-modified silicone can be obtained by distilling off a low boiling component under heating and under reduced pressure. However, there is no description regarding the amount of cyano compound remaining in the epoxy-modified silicone obtained after the obtained treatment. Moreover, there is no description or suggestion about the influence of the amount of the cyano compound remaining in the epoxy-modified silicone on the properties of the cured product obtained by curing the epoxy-modified silicone.

Japanese Patent No. 3263177 JP 2005-171021 A JP 7-216308 A Japanese Patent Laid-Open No. 10-182826 US Pat. No. 6,313,255 JP 2008-255295 A International Publication No. 2007/46399 JP-A-8-27165 Japanese Patent No. 4141547

  The present invention, when cured, the cured product has good transparency, excellent light resistance, excellent heat discoloration, excellent adhesion, and storage stability at high temperatures such as during transportation and storage. It aims at providing the silicone composition which is excellent in. The present invention also provides a curable composition suitably used for sealing a light-emitting element that has excellent adhesion to an element or a package material and can suppress a decrease in luminance over a long period of time, and the curable composition. It is an object of the present invention to provide a light emitting component.

  Another object of the present invention is to provide a curable composition suitable as a lens material that is suitable for injection molding, is hard after curing, and has excellent step stability.

［平均組成式（１）中、Ｒ^１は、各々独立に、（Ａ）鎖状、分岐状又は環状の無置換又は置換された脂肪族炭化水素構造を有し、炭素原子数が１以上２４以下及び酸素原子数が０以上５以下である１価の脂肪族有機基、（Ｂ）無置換又は置換された炭素原子数が６以上２４以下及び酸素原子数が０以上５以下である１価の芳香族有機基であって、置換された場合には、鎖状、分岐状又は環状の無置換又は置換された脂肪族炭化水素構造を有する置換基を有する、１価の芳香族有機基、又は（Ｃ）鎖状、分岐状若しくは環状の無置換若しくは置換された脂肪族炭化水素構造、又は無置換若しくは置換された芳香族炭化水素構造を有する、炭素原子数が５以上２６以下、酸素原子数が０以上５以下、及び珪素原子数が１である１価の有機基を表す。各シロキシ単位中に複数あるＲ１は、それぞれ同一でも異なっていてもよい。
Ｒ^２は、各々独立に、鎖状、分岐状又は環状の無置換又は置換された脂肪族炭化水素構造を有し、炭素原子数が４以上２４以下及び酸素原子数が１以上５以下であり、エポキシ基を含有する１価の有機基を表す。各シロキシ単位中に複数あるＲ^２は、それぞれ同一でも異なっていてもよい。
Ｙは、各々独立に、無置換又は置換された鎖状、分岐状及び環状からなる群より選ばれる１種以上の構造からなり、炭素原子数が２以上７０以下、酸素原子数が０以上１５以下、及び珪素原子数が０以上１０以下である２価の有機基を表す。各シロキシ単位中に複数あるＹは、それぞれ同一でも異なっていてもよい。
ＺはＹとの結合を表す。
ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈ、ｉ、ｊ、ｋ、ｌ、ｍ、ｎは、エポキシ変性シリコーン１モル中に存在する各シロキシ単位のモル数を表し、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈ、ｉ、ｊ、ｋ、ｌ、ｍ、ｎは各々０以上の値でｄ＋ｈ＋ｋ＞０、ｅ＋ｆ＋ｈ＋ｉ＋ｊ＋ｋ＞０、ｇ＝ａ＋ｆ＋ｌを同時に満足する値である。］
［２］ 遷移金属元素の含有量の合計値が３０質量ｐｐｍ以下である、［１］に記載のシリコーン組成物。
［３］ 前記エポキシ変性シリコーンのエポキシ価が０．１５以上０．５０以下の範囲である、［１］又は［２］に記載のシリコーン組成物。
［４］ Ｒ^２が、各々独立に、下記一般式（２）〜（５）で表されるいずれかの有機基である、［１］〜［３］のいずれか１項に記載のシリコーン組成物。

［一般式（２）〜（５）中、Ｒ^３は、各々独立に、炭素原子数が１以上１６以下及び酸素原子数が１以上４以下であり、鎖状、分岐状又は環状の無置換又は置換された２価の有機基を表す。］
［５］ 前記ニトリル化合物が、下記一般式（６）で表される化合物である、［１］〜［４］のいずれか１項に記載のシリコーン組成物。

［一般式（６）中、Ｒ^４は、各々独立に、水素原子、シアノ基、炭素原子数が１以上２以下及び酸素原子数が０以上２以下である１価の脂肪族有機基を表す。］
［６］ 前記エポキシ変性シリコーン中の全Ｓｉ数に対するＳｉＨ基の含有率が２％未満である、［１］〜［５］のいずれか１項に記載のシリコーン組成物。
［７］ ２５℃における粘度が、５００，０００ｍＰａ・ｓ以下である、［１］〜［６］のいずれか１項に記載のシリコーン組成物。
［８］ ［１］〜［７］のいずれか１項に記載のシリコーン組成物を含む硬化性組成物。
［９］ 前記シリコーン組成物１００質量部に対し、エポキシ樹脂用硬化剤１質量部以上２００質量部以下、及び硬化促進剤０．００１質量部以上１０質量部以下を含む、［８］に記載の硬化性組成物。
［１０］ 前記シリコーン組成物１００質量部に対し、カチオン重合触媒０．００１質量部以上１０質量部以下を含む、［８］に記載の硬化性組成物。
［１１］ ［８］〜［１０］のいずれか１項に記載の硬化性組成物を用いて発光素子を封止して製造した発光部品。
［１２］ ［８］〜［１０］のいずれか１項に記載の硬化性組成物を用いて得られるレンズ。
［１３］ ［１１］に記載の発光部品を用いた表示機器。 In view of the above points, as a result of intensive studies by the present inventors, it was found that a silicone composition containing a specific amount of a nitrile compound can solve the above problems, and the present invention has been completed. That is, the present invention is as follows.
[1] A silicone composition comprising an epoxy-modified silicone represented by the following average composition formula (1) and a nitrile compound, wherein the content of the nitrile compound is 0.1 mass ppm or more and 50 mass ppm or less.

[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 R1s 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 bond with 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 silicone composition according to [1], wherein the total content of the transition metal elements is 30 mass ppm or less.
[3] The 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 silicone composition according to any one of [1] to [3], wherein R ² is each independently any organic group represented by the following general formulas (2) to (5). object.

[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 silicone composition according to any one of [1] to [4], wherein the nitrile compound is a compound represented by the following general formula (6).

[In General Formula (6), each R ⁴ independently represents a hydrogen atom, a cyano group, a monovalent aliphatic organic group having 1 to 2 carbon atoms and 0 to 2 oxygen atoms. . ]
[6] The silicone composition according to any one of [1] to [5], wherein the content of SiH groups relative to the total number of Si in the epoxy-modified silicone is less than 2%.
[7] The silicone composition according to any one of [1] to [6], wherein the viscosity at 25 ° C. is 500,000 mPa · s or less.
[8] A curable composition comprising the silicone composition according to any one of [1] to [7].
[9] The composition according to [8], including 1 to 200 parts by mass of an epoxy resin curing agent and 0.001 to 10 parts by mass of a curing accelerator with respect to 100 parts by mass of the silicone composition. Curable composition.
[10] The curable composition according to [8], including 0.001 part by mass or more and 10 parts by mass or less of a cationic polymerization catalyst with respect to 100 parts by mass of the silicone composition.
[11] A light-emitting component produced by sealing a light-emitting element using the curable composition according to any one of [8] to [10].
[12] A lens obtained using the curable composition according to any one of [8] to [10].
[13] A display device using the light-emitting component according to [11].

  According to the present invention, when cured, the cured product has good transparency, excellent light resistance, excellent heat discoloration, excellent adhesion, and storage at high temperatures such as during transportation and storage. It becomes possible to provide a silicone composition having excellent stability. In addition, according to the present invention, there is provided a curable composition suitably used for sealing a light-emitting element that has excellent adhesion to an element or a package material and can suppress a decrease in luminance over a long period of time, and the curable composition. It becomes possible to provide a light emitting component formed by using the same.

  In addition, the present invention can provide a curable composition suitable as a lens material that is suitable for injection molding, hard after curing, and excellent in step stability.

1 is a schematic cross-sectional view of an optical semiconductor light emitting device according to an embodiment. 1 is a schematic cross-sectional view of an optical semiconductor light emitting device according to an embodiment.

The silicone composition of the present invention contains an epoxy-modified silicone and a nitrile compound. The epoxy-modified silicone according to the present invention is represented by the following average composition formula (1).

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 bond with 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 R1s 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 to 5 and the number of silicon atoms of 1 include organic groups represented by the following general formula (7) and general formula (8).

Here, each R ⁵ 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 ^5.

(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 formula (2) to general formula (5), general formula (9), and general formula (10). 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 (11).

一般式（１１）中、ｐは０又は１０以下の正数である。また、Ｒ^６は、各々独立に、炭素原子数が１以上１０以下及び酸素原子数が０以上３以下である２価の脂肪族有機基であり、Ｒ^７は、各々独立に、無置換又は置換された鎖状、分岐状及び環状よりなる群から選ばれる１種以上の構造からなる炭素原子数が１以上６以下である１価の有機基であり、Ｙとして炭素原子数が２以上７０以下、酸素原子数が０以上１５以下、及び珪素原子数が０以上１０以下の範囲から選ばれる。複数存在するＲ^６、Ｒ^７は、それぞれ同一でも異なっていてもよい。

In general formula (11), p is 0 or a positive number of 10 or less. R ⁶ is each independently a divalent aliphatic organic group having 1 to 10 carbon atoms and 0 to 3 oxygen atoms, and R ⁷ is each independently unsubstituted or 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 ⁶ and R ⁷ may be the same or different.

Examples of such R ⁶ 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) - ( _{CH 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) -COO- (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 -COO- (CH 2) 3 -, - (CH 2) 2 -CO-O- (CH 2) 4 -, - (CH 2) 2 -CO- Examples include O— (CH ₂ ) ₅ —, — (CH ₂ ) ₂ —CO—O— (CH ₂ ) ₆ —, — (CH ₂ ) ₂ —CO—O— (CH ₂ ) ₇ —, and the like.

On the other hand, as R ⁷ , 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 Y. Specifically, it means a Si—Y—Z—Si structure, where Z represents a direct bond.

R ¹ , R ² , R ⁶ , and R ⁷ include the hydroxyl number, alkoxy unit, acyl unit as an organic group within the range of the number of carbons and oxygen, and if necessary, the number of silicons. 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 ⁶ , and R ⁷ 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. As (A-1), (A-3), and R ⁵ are preferably selected from the group consisting of C) wherein (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 a high temperature of the silicone composition of the present invention is further increased, the SiH group content (%) with respect to the total number of Si in the epoxy-modified silicone is preferably less than 2%, preferably 1% or less. 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.

  Here, the number average molecular weight of the epoxy-modified silicone represented by the average composition formula (1) in the present invention, the content of components having a molecular weight of 800 or less in the epoxy-modified silicone represented by the average composition formula (1), and The content of components having a molecular weight of 10,000 or more in the epoxy-modified silicone represented by the average composition formula (1) will be described.

  The number average molecular weight in the epoxy-modified silicone is 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.

  On the other hand, the content of components having a molecular weight of 800 or less in the epoxy-modified silicone refers to the elution peak area obtained by connecting the elution start point and elution end point of the epoxy-modified silicone in the elution curve obtained by the above GPC measurement ( The ratio of the peak area (peak area 2) corresponding to a molecular weight of 800 or less to the peak area 1) expressed as a percentage [ie, expressed as (peak area 2) / (peak area 1) × 100 (%)] Number].

  The content of components having a molecular weight of 10,000 or more in the epoxy-modified silicone is the elution peak obtained by connecting the elution start point and the elution end point of the epoxy-modified silicone in the elution curve obtained by the GPC measurement. A numerical value expressed as a percentage of the peak area (peak area 3) corresponding to a molecular weight of 10,000 or more to the area (peak area 1) [ie, (peak area 3) / (peak area 1) × 100 (% )].

  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, more preferably 0.20 or more, and further preferably 0.23 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.

  The silicone composition of the present invention has a viscosity of 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. Is preferable, it is more preferable that it is in the range of 200,000 mPa · s or less, and it is more preferable that it is in the range of 100,000 mPa · s or less.

  Here, the viscosity of the silicone composition is measured at 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 the value to be

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 silicone composition of the present invention is 30 ppm by mass or less because the heat-resistant yellowing of the cured product obtained by curing the silicone composition of the present invention is improved. Is preferably 20 ppm by mass or less, 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 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, a significant amount Since it requires a lot of labor such as adsorption treatment using 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%.

  Next, the nitrile compound used in the present invention will be described.

ただし、Ｒ^８は、炭素原子数が１以上１０以下、酸素原子数が０以上２以下、及び窒素原子数が０以上２以下である、無置換又は置換された１価の脂肪族有機基を表す。 In the present invention, the nitrile compound is an organic compound having one or more cyano groups in one molecule, and examples thereof include those represented by the general formula (12).

R ⁸ represents an unsubstituted or substituted monovalent aliphatic organic group having 1 to 10 carbon atoms, 0 to 2 oxygen atoms, and 0 to 2 nitrogen atoms. Represent.

In the present invention, R ⁸ represents an unsubstituted or substituted monovalent aliphatic group having 1 to 20 carbon atoms, 0 to 2 oxygen atoms, and 0 to 2 nitrogen atoms. / Or an aromatic organic group, as long as the number of carbon atoms, oxygen atoms, and nitrogen atoms is within the above range, an organic group such as a hydroxyl group, an acetyl group, an acyl group, an amino group, a cyano group, In addition, halogen atoms such as fluorine and chlorine may be contained.

Specific examples of R ⁸ include, for example, methyl group, ethyl group, 2-cyanoethyl group, n-propyl 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 Group, alkyl group such as n-heptadecyl group, n-octadecyl group, cyclopentyl group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, etc., cycloalkyl group, vinyl group, allyl group, etc., alkenyl group, naphthyl group, Phenyl, tolyl, benzyl, xylyl, cyanophenyl, aminophenyl, acetylphenyl, etc. A reel group, and the like.

一般式（６）中、Ｒ^４は、各々独立に、水素、シアノ基、炭素原子数が１以上２以下及び酸素原子数が０以上２以下である１価の脂肪族有機基を表す。 The nitrile compound is preferably a compound represented by the following general formula (6), since the storage stability of the silicone composition of the present invention at a high temperature is further increased.

In General Formula (6), each R ⁴ independently represents hydrogen, a cyano group, or a monovalent aliphatic organic group having 1 to 2 carbon atoms and 0 to 2 oxygen atoms.

Specific examples of R ⁴ include hydrogen, cyano group, methyl group, ethyl group, acetyl group, and the like.

  Specific examples of such a nitrile compound include benzonitrile, o-tolunitrile, m-tolunitrile, p-tolunitrile, phthalonitrile, isophthalonitrile, and the like.

  In the silicone composition of the present invention, as the nitrile compound, one of the above-described compounds may be used alone, or a mixture of two or more may be used.

  In the present invention, the silicone composition must contain the above nitrile compound in an amount of 0.1 ppm to 50 ppm. When the content of the nitrile compound is less than 0.1 ppm, the storage stability at high temperature of the silicone composition of the present invention is lowered, and gelation or the like occurs. On the other hand, when the content of the nitrile compound exceeds 50 ppm, the light resistance of a cured product obtained by curing the silicone composition of the present invention is remarkably lowered, which is not preferable.

In the present invention, the method for containing the nitrile compound in the silicone composition at 0.1 ppm to 50 ppm is not particularly limited. For example,
(G-1) Cyclic organohydrogen silicone containing Si-H groups and / or compounds having a chain-like or branched organohydrogen silicone, a carbon-carbon double bond and an epoxy group, and as required Accordingly, a silicone having a carbon-carbon double bond is subjected to a hydrosilylation reaction in the presence of a transition metal catalyst for hydrosilylation reaction and a solvent to produce an epoxy-modified silicone. A method in which a nitrile compound is added so as to have a concentration of 0.1 ppm to 50 ppm and uniformly mixed with an epoxy-modified silicone obtained by distilling off a low-boiling component containing a compound having a carbon-carbon double bond,
(G-2) Cyclic organohydrogen silicone containing Si-H groups and / or compounds having a chain-branched organohydrogen silicone, a carbon-carbon double bond and an epoxy group, and as required Accordingly, a silicone having a carbon-carbon double bond is subjected to a hydrosilylation reaction in the presence of a transition metal catalyst for hydrosilylation reaction and a solvent to produce an epoxy-modified silicone. A method of distilling off a solvent and a compound having an unreacted carbon-carbon double bond after adding a nitrile compound of 0.1 ppm or more and 50 ppm or less and uniformly mixing the mixture;
(G-3) Cyclic organohydrogensilicone containing Si-H groups and / or organohydrogensilicone having a chain or branch, a compound having a carbon-carbon double bond and an epoxy group, and as required Accordingly, a silicone having a carbon-carbon double bond is subjected to a hydrosilylation reaction in the presence of a transition metal catalyst for hydrosilylation reaction and a solvent to produce an epoxy-modified silicone. After adding nitrile compound in excess of 50 ppm and mixing uniformly, the solvent, the compound having an unreacted carbon-carbon double bond, and the nitrile compound were distilled off, and the residual amount of the nitrile compound was reduced to epoxy. A method of 0.1 ppm to 50 ppm with respect to the modified silicone;
Etc. can be illustrated.

  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 still more 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.

  Prior to the addition of the nitrile compound in the above methods (G-1) to (G-2), a metal component such as a transition metal containing a hydrosilylation reaction catalyst or a colored component is adsorbed and removed as necessary. Is also possible. Examples of the adsorbent used include activated carbon, celite, silica gel, alumina powder, and ion exchange resin. These post-treatment operations are preferably performed in an inert gas atmosphere such as nitrogen, helium, or argon.

  In addition, the temperature at the time of performing the treatment for adsorbing and removing metal components such as transition metals and coloring components is reduced because the viscosity of the epoxy-modified silicone or the solution after the reaction is lowered and the operation can be easily performed. The range of 50 ° C or higher is preferable, and 0 ° C or higher is more preferable. On the other hand, in order to suppress modification of the epoxy-modified silicone, 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 at the initial stage of the reaction or during the reaction.

  In the above methods (G-1) to (G-2), after the nitrile compound is added, the operation of uniformly mixing is performed in air and / or in an inert gas atmosphere such as nitrogen, helium, or argon. Can do. 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.

  The temperature at which the nitrile compound is added and then uniformly mixed has a range of −50 ° C. or more because the viscosity of the silicone composition or the solution after the reaction is lowered and the uniform mixing operation can be easily performed. Preferably, it is 0 degreeC or more. 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 at the initial stage of the reaction or during the reaction.

In the above methods (G-1) to (G-2), when separating components such as a solvent, a compound having an unreacted carbon-carbon double bond, and, if necessary, a nitrile compound from the reaction solution. The temperature is preferably in the range of −50 ° C. or more and 250 ° C. or less, more preferably in the range of 0 ° C. or more and 200 ° C. or less, and still more preferably in the range of 10 ° C. or more and 150 ° C., from the viewpoint of suppressing the modification of the epoxy-modified silicone or silicone composition. The following range, particularly preferably the range of 20 ° C. or more and 120 ° C. or less. If it is in the said range, the temperature at the time of isolate | separating an epoxy-modified silicone or a silicone composition from the mixture containing an epoxy-modified silicone or a silicone composition does not need to be constant temperature, and can also change temperature on the way. Is possible.
These separation operations are preferably performed in an inert gas atmosphere such as nitrogen, helium, or argon.

  In the step of separating the epoxy-modified silicone or silicone composition from the epoxy-modified silicone or mixture containing the silicone composition, the content of the low-boiling compound and the volatile compound is reduced to reduce the content of the epoxy-modified silicone or silicone composition. Even when the viscosity increases, it is preferable to use an apparatus capable of efficiently separating a low boiling point compound and a volatile compound. 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 silicone composition of the present invention is an epoxy-modified silicone in which the nitrile compound and components other than inevitable impurities such as metal components such as transition metals and coloring components are represented by the average composition formula (1) according to the present invention. Preferably there is. For example, the content of the epoxy-modified silicone in the silicone composition of the present invention is preferably 98% by mass or more, more preferably 99% by mass or more, and further preferably 99.9% by mass or more. 99.99% by mass or more is particularly preferable.

  The silicone composition of the present invention is excellent in storage stability at high temperatures such as during transportation and storage, and the cured product obtained by curing the silicone composition has excellent transparency and is excellent. Because it has high light resistance, heat discoloration, and adhesion, it can be used as a sealing material for light emitting elements, spectacle lenses, lenses for optical devices, CD and DVD pickup lenses, automotive headlamp lenses, projector lenses, etc. It is also suitably used as a lens material. 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 for the above applications, the silicone composition of the present invention comprises an epoxy resin and / or a curing agent for an epoxy resin, a curing accelerator, a cationic polymerization catalyst, a modifier, an antioxidant, a thermal stabilizer, if necessary. It is used as a curable composition in which conventionally known additives such as a silane coupling agent, an antifoaming agent, a colorant, a phosphor, a light diffusing agent, an inorganic filler, and a heat conductive filler are appropriately blended. The curable composition is preferably a curable resin composition. In this case, it is preferable that the epoxy-modified silicone described above is an epoxy-modified silicone resin.

  Epoxy resins used include aromatic epoxy resins represented by conventionally known aromatic glycidyl ethers, glycidyl ethers obtained by hydrogenating aromatic rings of aromatic epoxy resins, alicyclic epoxy resins, and others Epoxy resin and the like. These can be used as one kind or a mixture of two or more kinds.

  Examples of the aromatic glycidyl ether include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, and tetrachloro. Bisphenol type epoxy resin obtained by glycidylation of bisphenols such as bisphenol A and tetrafluorobisphenol A, and epoxy obtained by glycidylation of other dihydric phenols such as biphenol, dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene Resin, 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methyl ester) Epoxy resin obtained by glycidylation of trisphenol such as l) phenyl) ethylidene) bisphenol, epoxy resin obtained by glycidylation of tetrakisphenol such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane, phenol novolac Novolak type epoxy resins obtained by glycidylating novolaks such as cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, and the like.

  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 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 compounding amount of the epoxy resin in the curable composition is preferably 0.1 to 100 parts by mass, more preferably 1 to 100 parts by mass, and still more preferably 1 with respect to 100 parts by mass of the silicone composition of the present invention. ~ 80 parts by mass.

  The curing agent for epoxy resin that can be used in the present invention is not particularly limited, and conventionally known general ones can be used. However, since there is a tendency to obtain a cured product that is transparent and not colored, an acid anhydride is used. A system curing agent is preferably used. Specifically, polyazeline acid anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2 , 3-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, alicyclic acid anhydrides such as methyl-norbornane-2,3-dicarboxylic acid anhydride, phthalic anhydride, anhydrous Examples thereof include aromatic acid anhydrides such as trimellitic acid and pyromellitic anhydride, silicones having two or more acid anhydride-containing functional groups as a substituent in one molecule, and the like.

  Among these curing agents, the light resistance of the cured product obtained by curing the silicone composition of the present invention tends to increase. Therefore, alicyclic acid anhydrides, two or more acid anhydrides per molecule Silicones having a functional group as a substituent are more preferable, and methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride are further included. preferable. These curing agents can be used as one kind or a mixture of two or more kinds.

  The amount of the epoxy resin curing agent in the curable composition is preferably in the range of 0.1 to 3 equivalents, more preferably 0.5 to 2 equivalents, relative to the epoxy groups of the silicone composition of the present invention. The amount is preferably 1 part by mass to 200 parts by mass, more preferably 10 parts by mass to 150 parts by mass, and still more preferably 20 parts by mass to 100 parts by mass with respect to 100 parts by mass of the silicone composition.

  The curable composition obtained by using the silicone composition of the present invention may contain a curing accelerator as necessary. Examples of the curing accelerator used 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, oct Le stannous, 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.

  The blending amount of these curing accelerators in the curable composition is preferably 0.001 part by mass or more and 0.01 part by mass or more from the viewpoint of increasing the curing rate with respect to 100 parts by mass of the silicone composition. More preferably, it is more preferably 0.1 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 5 parts by mass or less, still more preferably 3 parts by mass or less, and 1 part by mass or less. It is particularly preferred.

  Further, the silicone composition of the present invention can be made into a curable composition by blending a conventionally known cationic polymerization catalyst.

Examples of cationic polymerization catalysts that can be used include Lewis acid catalysts such as BF ₃ / amine complexes, PF ₅ , BF ₃ , AsF ₅ , SbF ₅ , phosphonium salts, quaternary ammonium salts, sulfonium salts, benzyl ammonium Salt, benzylpyridinium salt, benzylsulfonium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, thermosetting cationic polymerization catalyst represented by amine imide, diaryliodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate And UV curable cationic polymerization catalysts represented by the above.

  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 cationic polymerization catalyst in the curable composition is preferably 0.001 part by mass or more and 0.005 part by mass from the viewpoint of increasing the curing rate with respect to 100 parts by mass of the silicone composition. More preferably, it 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 0.5 parts by mass or less, and 0.2 It is particularly preferable that the amount is not more than part by mass.

  As the curing agent and curing accelerator suitably used for the curable composition of the present invention, in addition to the above, for example, aluminum as described in JP-A-4-84444 and JP-A-2005-93569 Examples thereof include a combination of an aluminum compound having an organic group such as trisacetylacetonate and a compound having an OH group or an alkoxy group directly bonded to Si such as diphenylsilanediol and diphenyldiethoxysilane.

  The curable composition obtained by using the silicone composition of the present invention may contain a modifier as necessary from the viewpoint of imparting flexibility to the cured product and improving the peel adhesion. . 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.

  The blending amount of polyols containing two or more hydroxyl groups in one molecule in the curable composition is preferably 0.1 parts by mass or more from the viewpoint of improving adhesion with respect to 100 parts by mass of the silicone composition. From the viewpoint of heat resistance and moisture resistance, the amount is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, still more preferably 3 to 20 parts by weight, and particularly preferably 3 to 10 parts by weight.

  Various silane coupling agents can be used in the curable composition of the present invention for the purpose of improving physical properties such as adhesion. Suitable silane coupling agents for the present invention include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldisilane. Ethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Ethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, N- (2-aminoethyl) aminomethyltrimethoxysilane N- (2-aminoethyl) (3-aminopropyl) trimethoxysilane, N- (2-aminoethyl) (3-aminopropyl) triethoxysilane, N- (2-aminoethyl) (3-aminopropyl) 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) trie Xylsilane, (N-cyclohexylaminomethyl) methyldiethoxysilane, piperazinomethyltrimethoxysilane, piperazinomethyltriethoxysilane, 3-piperazinopropyltrimethoxysilane, 3-piperazinopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3 -Mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3- (trimethoxysilyl) propyl succinic anhydride, 3- (triethoxy Silyl) propyl succinic anhydride, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, vinyltrimethoxysilane , Vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylvinyldimethoxysilane, Methylvinyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methyl Hexyldimethoxysilane, methylcyclohexyldiethoxysilane, methylcyclopentyldimethoxysilane, methylcyclopentyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3 -Methacryloxypropyltriethoxysilane and the like. Moreover, the partial condensate of these silane coupling agents can also be used.

  A known method can be used as a method for curing the curable composition obtained using the 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 silicone composition of this invention can be used suitably as a sealing material for light emitting elements. 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 silicone composition of the present invention is widely used from infrared to red, green, blue, purple and ultraviolet. The conventional sealing material can be practically used even for light having a wavelength of 250 nm to 550 nm, which deteriorates due to insufficient light resistance. 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 element (for example, a light-emitting diode) can be produced by sealing the light-emitting element using a sealing material for a light-emitting element comprising a curable composition containing the 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.

  FIG. 1 is a schematic cross-sectional view of an optical semiconductor light emitting device according to an embodiment. The optical semiconductor light emitting device of FIG. 1 is laminated on a housing material 7 to which a lead electrode 5 is attached, a light emitting device die bond material 2 electrically connected to one lead electrode 5, and a light emitting device die bond material 2. The light emitting element 1, the gold wire 4 electrically connected to the light emitting element 1 and the other lead electrode 5, the light emitting element 1, the die bond material 2 for the light emitting element, the gold wire 4 and the lead electrode 5 are sealed. And an element sealing material 3. Here, the sealing material 3 for light emitting elements consists of hardened | cured material which hardened the curable composition of this invention.

  FIG. 2 is a schematic cross-sectional view of an optical semiconductor light emitting device according to another embodiment. The optical semiconductor light emitting device of FIG. 2 is provided with a lead electrode 5 and a housing material 7 having a heat radiating plate 6 in part, a gold wire 4 electrically connected to the lead electrode 5 and the light emitting device 1, and a heat radiating plate. The light emitting element die-bonding material 2 disposed on the light emitting element 1, the light emitting element 1 laminated on the light emitting element die bonding material 2, the light emitting element 1, the light emitting element die bonding material 2, the gold wire 4 and the lead electrode 5 are sealed. The light-emitting element sealing material 3 is provided. Here, the sealing material 3 for light emitting elements consists of hardened | cured material which hardened the curable composition of this invention.

  As a method for sealing a light emitting element with a light emitting element sealing material obtained by using the silicone composition of the present invention, for example, a light emitting element sealing material is injected in advance into a mold mold, and the light emitting element is injected there. Examples include a method of curing after immersing a lead frame or the like to which a light emitting element is fixed, a method of injecting a sealing material for a light emitting element into a mold frame in which the light emitting element is inserted, and a method of 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 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.

  The performance of the light-emitting diode obtained using the curable composition of the present invention can be improved by a conventionally known method. 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.

  The light-emitting diode obtained by using the curable composition of the present invention includes, for example, a backlight such as a liquid crystal display, illumination, various sensors, a light source such as a printer and a copying machine, an instrument light source for a vehicle, a signal lamp, a display lamp, and a display. It is useful as a device, a light source for a planar light emitter, a display, a decoration, 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 silicone were determined by the following method.

(1) 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 was the molecular weight per mole of the epoxy-modified silicone represented by the average composition formula (1). As the above, 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.

^<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.).

<1H-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 TSK guard column HXL-H (registered trademark) manufactured by Tosoh Corporation as a guard column, TSK gel (registered trademark) G5000HXL manufactured by Tosoh Corporation, TSK gel (registered trademark) G 3000 HXL manufactured by Tosoh Corporation, and Tosoh ( One each of TSKgel (registered trademark) G1000HXL manufactured by Co., Ltd. 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 organohydrogensilicone
^It was determined by ²⁹ Si-NMR measurement.
0.15 g of organohydrogensilicone was dissolved in 1 g of deuterated chloroform. Ten microliters of tetramethylsilane was further added to the solution obtained by adding 0.015 g of Cr (acac) ₃ to the organohydrogensilicone and dissolving the solution 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 to calculate the average composition of each organohydrogensilicone molecule and the average chain length of each of (R ¹ ₂ SiO _2/2 ) units and (R ¹ HSiO _2/2 ) units.
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 -5 ppm -19.5 ppm or less Above -D1-D1-D1-unit, -D1-D1-H1-unit, -H1-D1-H1-unit, -H1-H1-H1-unit, -H1-H1 The integrated values of the peaks corresponding to -D1-unit and -D1-H1-D1-unit are respectively A (D1D1D1), A (D1D1H1), A (H1D1H1), A (H1H1H1), A (H1H). When D1) and A (D1H1D1), the average chain length (γD1) of dimethylsiloxy units 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) 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.

(4) Epoxy value Determined by the following operation 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]

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

(6) Storage stability at high temperature of the silicone composition The storage stability at high temperature of the silicone composition was evaluated by a storage stability index α shown by the following formula (XII).
Storage stability index α = (storage viscosity) / (starting viscosity) Formula (XII)
The container containing the 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”. Furthermore, the container containing the silicone composition was sealed and stored in a constant temperature incubator at 60 ° C. for 1 week. After storage for a predetermined period, the viscosity at 25 ° C. was measured in the same manner as described above, and this was designated as “storage viscosity”.
When the storage stability index α was 4 or less, it was judged as having good storage stability, and when the index α exceeded 4, it was judged that there was no storage stability, and x.
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.

(7) 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 by 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 ×.

(8) Light resistance It set so that UV light could be irradiated to the hardened | cured material of thickness 3mm in the constant temperature dryer made 50 degreeC constant from the UV irradiation apparatus (product made from Ushio Electric: 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.

(9) 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%.

(10) Crack resistance and adhesion 5 mm × 5 mm in a resin mold made of polyphthalamide (Solvay Amodel 4122) with a 10 mmφ, 1 mm deep recess in the center of a 20 mm × 20 mm × 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”). .) Was obtained.
As a result of molecular weight measurement, the number average molecular weight of the obtained block type organohydrogensilicone was 7,200, and the average chain lengths of the dialkylsiloxy unit and the hydrogen methylsiloxy unit were 40 and 4.3, respectively.
All terminal structures of the obtained block-type organohydrogensilicone are [H—Si (CH ₃ ) ₂ —O _1/2 —], and the composition of the block-type organohydrogensilicone is [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%, dialkylsiloxy units The average chain lengths of the hydrogen methylsiloxy units were 40 and 4.3, respectively.
Further, the block type organohydrogen silicone did not contain trifluoromethanesulfonic acid or triethylamine-derived compound used for the siloxane exchange reaction.

[Example 1]
<Manufacture of 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) have been modified to trialkylsiloxy groups by hydrosilylation reaction, and the content (%) of SiH units relative to the total Si constituting the epoxy-modified silicone (1a) [(C + i + m) / (a + b + c + d + e + f + g + h + i + j + k + l + m + n) × 100] and branched chain content (%) [(j + k + l + m + 2n) / (a + b + c + d + e + f + g + h + i +)
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 0.045 g of o-tolunitrile (Aldrich) were charged into a high-viscosity stirrer having an internal volume of 2 liters made of SUS316 and a sigma blade at 30 ° C. in a nitrogen atmosphere. By mixing for 2 hours, a silicone composition (1b) in which o-tolunitrile was uniformly mixed was obtained. As a result of measuring the o-tolunitrile content in the silicone composition (1b) by gas chromatography, it was 40 ppm. Table 1 shows the storage stability evaluation results of the silicone composition (1b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the obtained silicone composition (1b), 36 parts by mass of methylhexahydrophthalic anhydride, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate are added under nitrogen. The mixture was stirred until the whole became uniform and then defoamed 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]
<Manufacture of silicone composition>
When uniformly mixing o-tolunitrile with the epoxy-modified silicone (1a), a silicone composition in which o-tolunitrile was uniformly mixed was obtained in the same manner as in Example 1 except that 0.0003 g of o-tolunitrile was used. 2b) was obtained. As a result of measuring the o-tolunitrile content in the silicone composition (2b) by gas chromatography, it was 0.3 ppm. Table 1 shows the storage stability evaluation results of the silicone composition (2b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the obtained silicone composition (2b), Rikacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 38.1 parts by mass, 1,2-propanediol 3 Part by mass and 0.25 parts by mass of diazabicycloundecene octylate 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]
<Manufacture of silicone composition>
When uniformly mixing o-tolunitrile with the epoxy-modified silicone (1a), a silicone composition in which o-tolunitrile was uniformly mixed was obtained in the same manner as in Example 1 except that 0.008 g of o-tolunitrile was used. 3b) was obtained. As a result of measuring the o-tolunitrile content in the silicone composition (3b) by gas chromatography, it was 8 ppm. Table 1 shows the storage stability evaluation results of the silicone composition (3b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the obtained silicone composition (3b), Rikacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 38.1 parts by mass, 1,2-propanediol 3 Part by mass and 0.25 parts by mass of diazabicycloundecene octylate 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.

[Comparative Example 1]
<Manufacture of silicone composition>
When uniformly mixing o-tolunitrile with the epoxy-modified silicone (1a), a silicone composition in which o-tolunitrile was uniformly mixed was obtained in the same manner as in Example 1 except that 0.060 g of o-tolunitrile was used. 1c) was obtained. As a result of measuring the o-tolunitrile content in the silicone composition (1c) by gas chromatography, it was 60 ppm. Table 1 shows the storage stability evaluation results of the silicone composition (1c) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the obtained silicone composition (1c), Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 38.1 parts by mass, 1,2-propanediol 3 Part by mass and 0.25 parts by mass of diazabicycloundecene octylate were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition (1c). The curable composition (1c) 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.

[Comparative Example 2]
<Manufacture of silicone composition>
Storage stability evaluation at high temperature was performed without mixing o-tolunitrile with the epoxy-modified silicone (1a). The results are shown in Table 1.

<Manufacture and characteristic evaluation of cured product>
Epoxy-modified silicone (1a) 100 parts by mass, Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 38.1 parts by mass, 1,2-propanediol 3 parts by mass, 0.25 parts by mass of diazabicycloundecene octylate was mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition (1c). The curable composition (1c) 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]
<Manufacture of silicone composition>
A silicone composition (4b) in which benzonitrile is uniformly mixed is obtained in the same manner as in Example 1 except that 0.005 g of benzonitrile manufactured by Aldrich is used as a nitrile compound uniformly mixed with epoxy-modified silicone (1a). Obtained. As a result of measuring the benzonitrile content in the silicone composition (4b) by gas chromatography, it was 5 ppm. Table 3 shows the storage stability evaluation results of the silicone composition (4b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the obtained silicone composition (4b), Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 38.1 parts by mass, 1,2-propanediol 3 Part by mass and 0.25 parts by mass of diazabicycloundecene octylate 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 4 shows the performance of the obtained cured product.

[Example 5]
<Manufacture of silicone composition>
A silicone composition (5b) in which phthalonitrile was uniformly mixed was obtained in the same manner as in Example 1 except that 0.010 g of phthalonitrile manufactured by Aldrich was used as a nitrile compound to be uniformly mixed with epoxy-modified silicone (1a). Obtained. As a result of measuring the phthalonitrile content in the silicone composition (5b) by gas chromatography, it was 10 ppm. Table 3 shows the storage stability evaluation results of the silicone composition (5b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
90 parts by mass of the silicone composition (5b) obtained, 10 parts by mass of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanedicarboxylate, Ricacid MH-700G (manufactured by Shin Nippon Rika Co., Ltd .; methylhexahydro Phthalic anhydride / hexahydrophthalic anhydride mixture) 41 parts by mass, 3 parts by mass of 1,3-propanediol, and 0.25 parts by mass of diazabicycloundecene octylate are mixed under nitrogen, and the whole becomes uniform. The mixture was stirred until defoaming 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 4 shows the performance of the obtained cured product.

[Example 6]
<Manufacture of silicone composition>
A 1 liter reactor with reflux condenser, thermometer and stirrer is 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. . When the solution after the reaction for 60 hours was sampled, the hydrosilylation reaction progressed quantitatively, and unreacted SiH units were not detected.
To the reaction solution, 25 g of o-tolunitrile manufactured by Aldrich was added, stirred at 65 ° C. for 3 hours, and then cooled to room temperature.
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 is put into 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. Was introduced for 120 hours to obtain a silicone composition (6b) in which low boiling point compounds were reduced.
All terminal structures of the obtained silicone composition (6b) have been modified to trialkylsiloxy groups by a hydrosilylation reaction, and the content (%) of SiH units relative to the total Si constituting the silicone composition (6b) [(C + i + m) / (a + b + c + d + e + f + g + h + i + j + k + l + m + n) × 100] and branched chain content (%) [(j + k + l + m + 2n) / (a + b + c + d + e + f + g + h + i +)
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 the low-boiling compound remaining in the silicone composition (6b) include 4-ethylidenylcyclohexene oxide formed by causing internal transition of a carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide, o-Tolunitrile was detected, and the residual amounts thereof were 10 ppm, 10 ppm and 28 ppm, respectively.
Moreover, the epoxy value of the silicone composition (6b) was 0.214, the transition metal element contained was only platinum, and the content of the element was 5 ppm.
The following evaluation was performed using the silicone composition (6b) produced by repeatedly performing the above operations as necessary.
Table 3 shows the storage stability evaluation results of the silicone composition (6b) at high temperatures.

<Manufacture and characteristic evaluation of cured product>
100 parts by mass of the obtained silicone composition (6b), 36 parts by mass of methylhexahydrophthalic anhydride, 6 parts by mass of 1,3-propanediol, 0.25 parts by mass of diazabicycloundecene octylate under nitrogen The mixture was 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 4 shows the performance of the obtained cured product.

[Example 7]
(1) Manufacture of die-bonding material To the silicone composition (4b) manufactured in Example 4, Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 71.3 mass Part, 1,2-propanediol 3 parts by mass, diazabicycloundecene octylate 0.3 part by mass under nitrogen, stirred until the whole becomes uniform, defoamed and die-bonded for light emitting device Material 2 was obtained.

(2) Manufacture of optical semiconductor light emitting device Main emission peak using die bond material 2 for light emitting device manufactured in (1) above for polyphthalamide housing material 7 with lead electrode 5 heated and dried at 150 ° C. for 2 hours. Was mounted with a light-emitting element 1 of 460 nm and cured at 120 ° C. for 1 hour and further at 150 ° C. for 2 hours to fix the light-emitting element 1. Then, after electrically connecting the light emitting element 1 and the lead electrode 5 with the gold wire 4, the curable composition (1) created in Example 1 was poured into the mold under nitrogen, and at 120 ° C. A curing reaction is performed for 1 hour and further at 150 ° C. for 2 hours to form the light-emitting element sealing material 3, and the optical semiconductor light-emitting element 10 (hereinafter also referred to as “optical semiconductor element”) having the structure shown in FIG. 20 pieces were produced. Even if the optical semiconductor light-emitting device 10 obtained by this operation is energized at room temperature at 3 V and 80 mA for 1,000 hours, the sealing portion between the light-emitting device 1 and the light-emitting device sealing material 3 is peeled off. There was no decrease in brightness.

[Example 8]
Twenty optical semiconductor elements 10 having the structure shown in FIG. 1 were produced in the same manner as in Example 7 except that the curable composition (2) prepared in Example 2 was used. Even if the optical semiconductor light-emitting device 10 obtained by this operation is energized at room temperature at 3 V and 80 mA for 1,000 hours, the sealing portion between the light-emitting device 1 and the light-emitting device sealing material 3 is peeled off. There was no decrease in brightness.

[Example 9]
Twenty optical semiconductor elements 10 having the structure shown in FIG. 1 were produced in the same manner as in Example 7 except that the curable composition (3) prepared in Example 3 was used. Even if the optical semiconductor light-emitting device 10 obtained by this operation is energized at room temperature at 3 V and 80 mA for 1,000 hours, the sealing portion between the light-emitting device 1 and the light-emitting device sealing material 3 is peeled off. There was no decrease in brightness.

[Example 10]
Twenty optical semiconductor elements 10 having the structure shown in FIG. 1 were produced in the same manner as in Example 7 except that the curable composition (4) prepared in Example 4 was used. Even if the optical semiconductor light-emitting device 10 obtained by this operation is energized at room temperature at 3 V and 80 mA for 1,000 hours, the sealing portion between the light-emitting device 1 and the light-emitting device sealing material 3 is peeled off. There was no decrease in brightness.

[Example 11]
Twenty optical semiconductor elements 10 having the structure shown in FIG. 1 were produced in the same manner as in Example 7 except that the curable composition (5) prepared in Example 5 was used. Even if the optical semiconductor light-emitting device 10 obtained by this operation is energized at room temperature at 3 V and 80 mA for 1,000 hours, the sealing portion between the light-emitting device 1 and the light-emitting device sealing material 3 is peeled off. There was no decrease in brightness.

[Example 12]
Twenty optical semiconductor elements 10 having the structure shown in FIG. 1 were produced in the same manner as in Example 7 except that the curable composition (6) prepared in Example 6 was used. Even if the optical semiconductor light-emitting device 10 obtained by this operation is energized at room temperature at 3 V and 80 mA for 1,000 hours, the sealing portion between the light-emitting device 1 and the light-emitting device sealing material 3 is peeled off. There was no decrease in brightness.

According to the present invention, when cured, the cured product has good transparency, excellent light resistance, excellent heat discoloration, excellent adhesion, and storage at high temperatures such as during transportation and storage. It becomes possible to provide a silicone composition having excellent stability. In addition, according to the present invention, there is provided a curable composition suitably used for sealing a light-emitting element that has excellent adhesion to an element or a package material and can suppress a decrease in luminance over a long period of time, and the curable composition. It becomes possible to provide a light emitting component formed by using the same.
In addition, the present invention can provide a curable composition suitable as a lens material that is suitable for injection molding, hard after curing, and excellent in step stability.

  DESCRIPTION OF SYMBOLS 1 ... Light emitting element, 2 ... Die bond material for light emitting elements, 3 ... Sealing material for light emitting elements, 4 ... Gold wire, 5 ... Lead electrode, 6 ... Heat sink, 7 ... Housing material, 10 ... Optical semiconductor light emitting element (light) Semiconductor element).

Claims (6)

A silicone composition comprising an epoxy-modified silicone represented by the following average composition formula (1) and a nitrile compound, wherein the content of the nitrile compound is 0.1 mass ppm or more and 50 mass ppm or less.

[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 independently represents any organic group represented by the following general formulas (2) to (5).

In general formulas (2) to (5), each R ³ independently has 1 to 16 carbon atoms and 1 to 4 oxygen atoms, and is a chain, branched or cyclic unsubstituted or Represents a substituted divalent organic 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 bond with 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 silicone composition according to claim 1, wherein the total content of the transition metal elements is 30 ppm by mass or less.   The 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 silicone composition according to any one of claims 1 to 3, wherein the nitrile compound is a compound represented by the following general formula (6).

[In General Formula (6), each R ⁴ independently represents a hydrogen atom, a cyano group, a monovalent aliphatic organic group having 1 to 2 carbon atoms and 0 to 2 oxygen atoms. . ]   The silicone composition of any one of Claims 1-4 whose content rate of SiH group with respect to the total Si number in the said epoxy modified silicone is less than 2%.   The silicone composition according to any one of claims 1 to 5, wherein the viscosity at 25 ° C is 500,000 mPa · s or less.

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