JP2013194071A - Epoxy-modified silicone composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy-modified silicone composition having excellent storage stability under exposure to light such as sunlight when transported and stored.SOLUTION: An epoxy-modified silicone composition includes 0.0005-5 pts.mass of a light stabilizer based on 100 pts.mass of an epoxy-modified silicone represented by average composition formula (1), wherein Reach independently represents (A) a monovalent aliphatic organic group, (B) a monovalent aromatic organic group or (C) a monovalent organic group; Reach independently represents an organic group including an epoxy group; Y each independently represents a divalent organic group; Z represents a divalent hydrocarbon group bonding to Y; and a to n represent the number of moles of each siloxy unit present in 1 mole of the epoxy-modified silicone.

Description

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

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

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

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

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

  In the above Patent Documents 1 and 2, a cured product obtained using the epoxy-modified silicone has high heat resistance, high light resistance, or high adhesiveness, or a cured product containing the resulting epoxy-modified silicone. There is a description that the curable composition has high curability, but the storage stability of the epoxy-modified silicone itself containing a highly reactive epoxy group in the molecule is low, under light exposure conditions such as sunlight, or It could not be said that the storage stability under non-exposure conditions was still sufficient. Further, there is no description or suggestion regarding a composition in which a light stabilizer is blended with an epoxy-modified silicone, and an effect that is manifested by blending the light stabilizer.

Japanese Patent No. 3263177 JP 2005-171021 A

  An object of the present invention is to provide an epoxy-modified silicone composition having excellent storage stability under light exposure conditions such as sunlight during transportation and storage.

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

[1] At least one light stability selected from the group consisting of an ultraviolet absorber, a hindered amine light stabilizer, and an organic phosphorus light stabilizer with respect to 100 parts by mass of the epoxy-modified silicone represented by the following average composition formula (1) An epoxy-modified silicone composition comprising 0.0005 parts by mass or more and 5 parts by mass or less of an agent.

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

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

  The present invention can provide an epoxy-modified silicone composition having excellent storage stability under light exposure conditions such as sunlight during transportation and storage.

  The epoxy-modified silicone composition of the present invention is at least one selected from the group consisting of an epoxy-modified silicone represented by the following average composition formula (1), an ultraviolet absorber, a hindered amine light stabilizer, and an organic phosphorus light stabilizer. And a light stabilizer.

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.

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

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

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

Here, in the average composition formula (1), when j, k, l, m, and n simultaneously satisfy the following formulas (I) and (II), the above a, b, c, d, j , K, l, m, and n are numerical values selected from a range that satisfies Formula (III).
j + k + 1 + m> 0 Formula (I)
n> 0 Formula (II)
0 ≦ (b + c + d) ≦ a + (j + k + 1 + m) + 2n + 2 Formula (III)

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

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

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

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

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

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

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

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

Here, each R ⁴ independently has (D) a chain, branched or cyclic unsubstituted or substituted aliphatic hydrocarbon structure, having 1 to 8 carbon atoms and 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.
A specific example of R ⁴ will be described below.

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

R ³ in the above general formula has an aliphatic hydrocarbon structure in which R ² is a chain, branched or cyclic unsubstituted or substituted, has 4 to 24 carbon atoms and 1 oxygen atom. There is no particular limitation as long as it is a monovalent organic group containing 5 or more and containing an epoxy group, and for example, — (CH ₂ ) ₂ —O—, — (CH ₂ ) varies depending on the structure of the epoxy group. _{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 -, - 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) 14 -, - (CH 2) 15 -, - (CH 2) 16 - etc. An aliphatic hydrocarbon structure consisting of a chain or a branch can be exemplified.

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

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

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

Examples of such R ⁵ include — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, — (CH ₂ ) ₆ —, _{-CH (CH 3) -, -} CH 2 -CH (CH 3) -, - CH 2 -CH (CH 3) -CH 2 -, - CH 2 -CH (CH 3) - (CH 2) 2 -, _{-CH 2 -CH (CH 3) -} (CH 2) 3 -, - CH 2 -CH (CH 3) - (CH 2) 4 -, - CH 2 -CH (CH 3) - (CH 2) 5 - _{, -CH 2 -CH (CH 3)} - (CH 2) 6 -, - CH 2 -CH (CH 3) - (CH 2) 7 -, - CH 2 -CH (CH 3) -CH (CH 3) _{-CH 2 -, - CH 2 -CH} (CH 3) -CH 2 -CH (CH 3) -CH 2 -, - CH 2 -CH (CH 3) - (CH 2) 2 -CH (CH 3) - _{CH 2 -, - CH 2 -CH} (CH 3) - (C _{2) 3 -CH (CH 3)} -CH 2 -, - CH 2 -CH (CH 3) - (CH 2) 4 -CH (CH 3) -CH 2 -, - CH (CH 3) -CH 2 - _{, -CH (CH 3) - (} CH 2) 2 -, - CH (CH 3) - (CH 2) 3 -, - CH (CH 3) - (CH 2) 4 -, - CH (CH 3) - _{(CH 2) 5 -, -} CH (CH 3) - (CH 2) 6 -, - CH (CH 3) - (CH 2) 7 -, - CH (CH 3) - (CH 2) 8 -, - _{CH 2 -CH (CH 3) -CO} -O- (CH 2) 2 -, - CH 2 -CH (CH 3) -CO-O- (CH 2) 3 -, - CH 2 -CH (CH 3) _{-CO-O- (CH 2) 4} -, - CH 2 -CH (CH 3) -CO-O- (CH 2) 5 -, - CH 2 -CH (CH 3) -CO-O- (CH 2 ) _6- , — (CH ₂ ) ₂ —CO—O— (CH ₂ ) ₂ — , — (CH ₂ ) ₂ —CO—O— (CH ₂ ) ₃ —, — (CH ₂ ) ₂ —CO—O— (CH ₂ ) ₄ —, — (CH ₂ ) ₂ —CO—O— (CH ₂ ) ₅ —, — (CH ₂ ) ₂ —CO—O— (CH ₂ ) ₆ —, — (CH ₂ ) ₂ —CO—O— (CH ₂ ) ₇ —, and the like.

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

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

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

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

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

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

As the organic group R ² in the epoxy-modified silicone represented by the average composition formula (1) of the present invention, the curing rate when the silicone composition is cured is increased, or the 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) 14 -, - (CH 2) 15 -, - (CH 2) 16 - etc. chain Or more preferably an aliphatic hydrocarbon structure consisting of branched, represented by the general formula (2) to the general formula (5), and, R ³ is _{- (CH 2) 2 -,} - CH (CH 3 )-Is more preferable, represented by general formula (2) to general formula (5), and R ³ is particularly preferably — (CH ₂ ) ₂ —, represented by general formula (3). And R ³ is preferably — (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 ) —, the value of p is 2, and R ⁶ is -(CH ₂ ) ₂ — is particularly preferable, the value of p is 2, R ⁶ is — (CH ₂ ) ₂ —, and R ⁷ is preferably a methyl group.

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

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

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

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

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

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

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

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

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

<Method for measuring epoxy value>
A sample (eg, a resin sample) is dissolved in benzyl alcohol and 1-propanol. To this solution, an aqueous potassium iodide solution and a bromophenol blue indicator are added, followed by titration with 1N hydrochloric acid, and the point where the reaction system turns from blue to yellow is taken as the equivalent point. From the equivalent point, the epoxy value of the epoxy-modified silicone is calculated according to the following formula (IX).
Epoxy value (equivalent / 100 g) = (V × N × F) / (10 × W) Expression (IX)
[W, V, N, and F represent the following values, respectively.
W: weight of sample (g),
V: titer (mL)
N: Normality of hydrochloric acid used for titration (N),
F: Factor of hydrochloric acid used for titration]

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

Here, the number average molecular weight of the epoxy-modified silicone represented by the average composition formula (1) in the present invention will be described.
The number average molecular weight of the epoxy-modified silicone in the present invention refers to a value obtained by gel permeation chromatography (GPC) measurement using chloroform as an eluent and monodisperse polystyrene and styrene monomer as standard substances. Specifically, it refers to the number average molecular weight calculated using the above calibration curve from the elution time and detection intensity of the measurement sample solution prepared in advance from the elution time by RI detection.

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

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

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

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

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

  The reaction temperature at the time of hydrosilylation reaction is the type and molecular weight of the organohydrogen silicone used, the compound having a carbon-carbon double bond and an epoxy group, and, if necessary, the silicone having a carbon-carbon double bond. Furthermore, although it varies depending on the reaction mode such as batch, semi-batch, or continuous, the range of 0 ° C. or more and 250 ° C. or less is preferable from the viewpoint of increasing the reaction rate and efficiently completing the reaction. The range of 200 ° C. or lower is more preferable, the range of 20 ° C. or higher and 150 ° C. or lower is 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.

Next, the light stabilizer used in the present invention will be described.
In the epoxy-modified silicone composition of the present invention, at least one light stabilizer selected from the group consisting of an ultraviolet absorber, a hindered amine light stabilizer, and an organophosphorus light stabilizer is added to 100 parts by mass of the epoxy-modified silicone. It is necessary to contain 0005 parts by mass or more and 5 parts by mass or less. When the content of the light stabilizer is less than 0.0005 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone, it is not preferable because the storage stability of the epoxy-modified silicone under light exposure conditions such as sunlight is lowered. On the other hand, when the content of the light stabilizer exceeds 100 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone, the light stabilizer is not completely dissolved in the epoxy-modified silicone, and foreign matters remain in the epoxy-modified silicone. In some cases, the light resistance, crack resistance, adhesion and the like of a cured product obtained by curing the epoxy-modified silicone composition are not preferable.

  Since the storage stability of the epoxy-modified silicone of the present invention is further increased, the content of the light stabilizer with respect to 100 parts by mass of the epoxy-modified silicone is preferably 0.001 parts by mass or more, and 0.0015 parts by mass or more. It is more preferable that On the other hand, since the light resistance and moisture resistance of the cured product obtained by curing the epoxy-modified silicone composition of the present invention are enhanced, the content of the light stabilizer with respect to 100 parts by mass of the epoxy-modified silicone is 1 part by mass or less. It is preferable that it is 0.5 mass part or less, and it is still more preferable that it is 0.2 mass part or less.

  The light stabilizer used in the present invention is at least one light stabilizer selected from the group consisting of an ultraviolet absorber, a hindered amine light stabilizer, and an organic phosphorus light stabilizer.

    Examples of the ultraviolet absorber used in the present invention include (G-1) salicylic acids, (G-2) benzophenones, (G-3) benzotriazoles, (G-4) oxalic anilides, and the like. Can be mentioned. These can be used as one kind or a mixture of two or more kinds.

Specific examples of (G-1) salicylic acids include phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, and the like. These can be used as one kind or a mixture of two or more kinds.
Specific examples of (G-2) benzophenones include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone. 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, and the like. These can be used as one kind or a mixture of two or more kinds.
Specific examples of (G-3) benzotriazoles include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzo Triazole, 2- (2'-hydroxy-3 ', 5'-ditert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzotriazole,
2- (2′-hydroxy-3 ′, 5′-ditert-amylphenyl) benzotriazole, 2-{(2′-hydroxy-3 ′, 3 ″, 4 ″, 5 ″, 6 ″ -Tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole, and the like. These can be used as one kind or a mixture of two or more kinds.
Specific examples of (G-4) oxalic anilides include N- (2-ethylphenyl) -N ′-(2-ethoxy-5-t-butylphenyl) oxalic acid diamide, N- (2- Ethylphenyl) -N ′-(2-ethoxy-phenyl) oxalic acid diamide, 2-ethoxy-2′-ethyl-oxalic acid bisanilide, oxalic acid diamides having an aryl group optionally substituted on the nitrogen atom, etc. , Etc. These can be used as one kind or a mixture of two or more kinds.

The hindered amine light stabilizer used in the present invention is preferably a piperidine having a sterically hindered group, such as (H-1) an ester group-containing piperidine, (H-2) an ether group-containing piperidine, (H-3) Amido group-containing piperidines, (H-4) high molecular weight piperidine polycondensates, and the like. These can be used as one kind or a mixture of two or more kinds.
Specific examples of (H-1) ester group-containing piperidines include, for example, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine. 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, and the like. These can be used as one kind or a mixture of two or more kinds.
Specific examples of (H-2) ether group-containing piperidines include, for example, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine. 4-phenoxy-2,2,6,6-tetramethylpiperidine, and the like. These can be used as one kind or a mixture of two or more kinds.
Specific examples of (H-3) amide group-containing piperidines include, for example, 4- (phenylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl) -4-piperidyl) hexamethylene-1,6-dicarbamate, and the like. These can be used as one kind or a mixture of two or more kinds.
Specific examples of (H-4) high molecular weight piperidine polycondensates include, for example, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine heavy succinate. Examples include condensates, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol. These can be used as one kind or a mixture of two or more kinds.

  In addition, as the organic phosphorus light stabilizer used in the present invention, for example, (I-1) phosphite compounds having two benzene rings are preferably used.

  (H-1) Phosphite compounds having two benzene rings Specific examples of phosphite compounds include bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, Bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) propyl phosphite, bis (2,4-di- tert-butyl-6-methylphenyl) butyl phosphite, and the like.

  As the light stabilizer used in the present invention, since the storage stability of the epoxy-modified silicone composition of the present invention under light exposure conditions such as sunlight is further increased, it becomes an ultraviolet absorber, an organic phosphorus light stabilizer. More preferably, it is at least one selected from the group, more preferably at least one selected from the group consisting of (G-2) to (G-4) and (I-1), (G -2) to (G-4) is particularly preferably at least one selected from the group.

  In the present invention, 0.0005 parts by mass or more and 5 parts by mass of at least one light stabilizer selected from the group consisting of an ultraviolet absorber, a hindered amine-based light stabilizer, and an organic phosphorus-based light stabilizer with respect to 100 parts by mass of the epoxy-modified silicone. There is no particular limitation on the method for containing a part or less, for example,

(J-1) Cyclic organohydrogensilicone containing Si-H groups and / or organohydrogensilicone having a chain or branched structure, a compound having a carbon-carbon double bond and an epoxy group, and necessary Accordingly, a silicone having a carbon-carbon double bond is hydrosilylated in the presence of a transition metal catalyst for hydrosilylation reaction and a solvent to produce an epoxy-modified silicone, and then 100 parts by mass of the resulting epoxy-modified silicone is produced. In contrast, at least one light stabilizer selected from the group consisting of an ultraviolet absorber, a hindered amine light stabilizer, and an organic phosphorus light stabilizer is added in an amount of 0.0005 parts by mass to 5 parts by mass, and uniformly mixed and dissolved. A method of distilling off a solvent, a compound having an unreacted carbon-carbon double bond, and the like,
(J-2) In the above (J-1), with respect to 100 parts by mass of the epoxy-modified silicone produced, at least one selected from the group consisting of an ultraviolet absorber, a hindered amine light stabilizer, and an organic phosphorus light stabilizer. After adding 5 parts by mass or more of a light stabilizer and uniformly mixing and dissolving, when distilling off a solvent, a compound having an unreacted carbon-carbon double bond, etc., an ultraviolet absorber, a hindered amine light stabilizer , A part of at least one light stabilizer selected from the group consisting of organic phosphorus light stabilizers is distilled off, and the content of the light stabilizer is 0.0005 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone. A method of 5 parts by mass or less,
(J-3) At least one selected from the group consisting of an ultraviolet absorber, a hindered amine light stabilizer, and an organic phosphorus light stabilizer with respect to 100 parts by mass of the epoxy-modified silicone after dissolving the epoxy-modified silicone in a solvent. After adding 0.0005 parts by mass to 5 parts by mass of the light stabilizer and uniformly mixing and dissolving,
(J-4) After dissolving the epoxy-modified silicone in a solvent, with respect to 100 parts by mass of the epoxy-modified silicone, at least one selected from the group consisting of an ultraviolet absorber, a hindered amine light stabilizer, and an organic phosphorus light stabilizer After adding 5 parts by mass or more of the above light stabilizer and uniformly mixing and dissolving, the solvent and a part of the light stabilizer are distilled off, and the content of the light stabilizer is adjusted to 100 parts by mass of the epoxy-modified silicone. 0.0005 parts by mass or more and 5 parts by mass or less,
(J-5) 0.0005 parts by mass or more of at least one light stabilizer selected from the group consisting of an ultraviolet absorber, a hindered amine light stabilizer, and an organic phosphorus light stabilizer with respect to 100 parts by mass of the epoxy-modified silicone. A method of adding up to parts by mass and uniformly mixing and dissolving,
Etc. can be exemplified.

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

  In addition, after adding the light stabilizer in the above methods (J-1) to (J-5), the operation of uniformly mixing and dissolving is performed under light-shielding conditions, under sunlight exposure, or under non-sunlight exposure. Under the conditions. Of these, the operation is preferably performed under light-shielding conditions or under non-sunlight exposure conditions.

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

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

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

  The epoxy-modified silicone composition of the present invention is an epoxy in which the light stabilizer 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. A modified silicone is preferred. For example, the content of the epoxy-modified silicone in the epoxy-modified silicone composition of the present invention is preferably 95% by mass or more, more preferably 99% by mass or more, and 99.5% by mass or more. More preferably, it is particularly preferably 99.9% by mass or more, and more preferably 99.95% by mass or more.

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

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

  The epoxy-modified silicone composition of the present invention has excellent storage stability under light exposure conditions such as sunlight during transportation and storage, and is obtained by curing the epoxy-modified silicone composition. Since the cured product has good transparency and excellent light resistance, heat discoloration, and adhesion, it is used for light emitting element sealing materials, eyeglass lenses, optical equipment lenses, CD and DVD pickups. It is also suitably used as a lens material for lenses, automobile headlamp lenses, projector lenses and the like. Furthermore, it can also be used as various optical members such as optical fibers, optical waveguides, optical filters, optical adhesives, die bonding agents, underfill materials for optical semiconductor elements, optical disk substrates, display substrates, antireflection coatings and other coating materials. It is.

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

(1) Composition of block type organohydrogen silicone
Each component constituting 1 mol of the block type organohydrogen silicone represented by the average composition formula (11) by measurement methods of ²⁹ Si-NMR measurement, gel permeation chromatography (GPC) measurement, and ¹ H-NMR measurement. The number of moles of the unit was calculated.
(R ¹ ₃ SiO _1/2 ) _p (R ¹ ₂ HSiO _1/2 ) _q (R ¹ ₂ SiO _2/2 ) _r
(R ¹ HSiO _2/2 ) _s (R ¹ SiO _3/2 ) _t (HSiO _3/2 ) _u (SiO _4/2 ) _v (11)
Specifically, first, ²⁹ Si-NMR measurement of a block-type organohydrogensilicone was performed according to the method described below, and an integrated value calculated from the obtained spectrum pattern was analyzed to obtain a hydrogen alkylsiloxy unit, a dialkylsiloxy unit. The content such as units was calculated as a percentage.

Next, ¹ H-NMR measurement was performed according to the method described below, and the abundance of alkylsiloxy units having each organic group was calculated as a percentage based on the integrated value calculated from the obtained spectrum pattern.
Using the abundance ratio of each siloxy unit obtained from the above and the theoretical formula amount of each siloxy unit, the average formula amount of the siloxy unit was calculated.

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

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

^<29 Si-NMR measurement method>
0.15 g of epoxy-modified silicone was dissolved in 1 g of deuterated chloroform. To the solution obtained by adding 0.015 g of Cr (acac) ₃ to the solution, 10 μL of tetramethylsilane was further added to prepare an NMR measurement solution. Using this NMR measurement solution, measurement of ²⁹ Si-NMR under proton complete decoupling conditions was performed at an integration number of 4,000 times (apparatus: α-400 manufactured by JEOL Ltd.).

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

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

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

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

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

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

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

-D1-D1-D1-unit, -D1-D1-H1-unit, -H1-D1-H1-unit, -H1-H1-H1-unit, -H1-H1-D1-unit, -D1- Assuming that the integrated values of the peaks corresponding to the H1-D1-unit are A (D1D1D1), A (D1D1H1), A (H1D1H1), A (H1H1H1), A (H1H1D1), A (D1H1D1), dimethylsiloxy units The average chain length (γD1) and the average chain length (δD1) of hydrogen methylsiloxy units can be calculated by the following formulas (X) and (XI), respectively.
γD1 = 1 + A (D1D1D1) / {A (D1D1H1) + A (H1D1H1)} Expression (X)
δD1 = 1 + {A (H1H1H1) + A (H1H1D1)} / A (D1H1D1) Expression (XI)

(3) Composition of epoxy-modified silicone
It calculated using the result obtained by < ²⁹ > Si-NMR measurement, a gel permeation chromatography (GPC) measurement, and < ¹ > H-NMR measurement.
Specifically, first, ²⁹ Si-NMR measurement of the epoxy-modified silicone was performed according to the method described below, and the integrated value calculated from the obtained spectrum pattern was analyzed to obtain hydrogen alkylsiloxy units, dialkylsiloxy units, etc. 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 integrated value calculated from the obtained spectrum pattern.
Using the abundance ratio of each siloxy unit obtained from the above and the theoretical formula amount of each siloxy unit, the average formula amount of the siloxy unit was calculated.

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

なお、平均組成式（１）で表されるエポキシ変性シリコーン中に含有される全Ｓｉ数に対するＳｉＨ基の含有率（％）、並びに、平均組成式（１）で表されるエポキシ変性シリコーン中に含有される全Ｓｉ数に対する分岐鎖の含有率（％）は、下記式により算出した。
全Ｓｉ数に対するＳｉＨ基の含有率（％）＝［（ｃ＋ｉ＋ｍ）／（ａ＋ｂ＋ｃ＋ｄ＋ ｅ＋ｆ＋ｇ＋ｈ＋ｉ＋ｊ＋ｋ＋ｌ＋ｍ＋ｎ）×１００］
分岐鎖の含有率（％）＝［（ｊ＋ｋ＋ｌ＋ｍ＋２ｎ）／（ａ＋ｂ＋ｃ＋ｄ＋ｅ＋ｆ＋ ｇ＋ｈ＋ｉ＋ｊ＋ｋ＋ｌ＋ｍ＋ｎ）×１００］

In addition, in the epoxy-modified silicone represented by the average composition formula (1), the SiH group content (%) with respect to the total number of Si contained in the epoxy-modified silicone represented by the average composition formula (1). The branched chain content (%) relative to the total number of Si contained was calculated by the following formula.
SiH group content (%) with respect to the total number of Si = [(c + i + m) / (a + b + c + d + e + f + g + h + i + j + k + l + m + n) × 100]
Branched chain content (%) = [(j + k + l + m + 2n) / (a + b + c + d + e + f + g + h + i + j + k + l + m + n) × 100]

^<29 Si-NMR measurement method>
0.15 g of epoxy-modified silicone is dissolved in 1 g of deuterated chloroform. To the solution obtained by adding 0.015 g of Cr (acac) ₃ to the solution, 10 μL of tetramethylsilane was further added to prepare an NMR measurement solution. Using this NMR measurement solution, measurement of ²⁹ Si-NMR under proton complete decoupling conditions was performed at an integration number of 4,000 times (apparatus: α-400 manufactured by JEOL Ltd.).

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

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

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

(4) Measurement of low-boiling compound amount remaining in epoxy-modified silicone Using a gas chromatography analyzer GC-14B manufactured by Shimadzu Corporation, the amount was determined under the following conditions.
After weighing about 2 g of epoxy-modified silicone and 0.015 g of n-octane as an internal standard in a 5 mL volumetric flask, a solution diluted to 5 mL with chloroform was used as a measurement sample.
Column: DB-1 (registered trademark) manufactured by J & W Scientific,
Length 30m, inner diameter 0.25mm, liquid film 1μm
Carrier gas: Helium Detector: FID
Injection temperature: 250 ° C
Detector temperature: 300 ° C
Temperature raising condition: After holding at 50 ° C. for 5 min, the temperature was raised from 50 ° C. to 300 ° C. at 10 ° C./min.
From the obtained results, the content of each component contained in the epoxy-modified silicone was quantified and summed up using a separately prepared calibration curve by an internal standard method. In addition, a numerical value is represented with the mass fraction with respect to epoxy-modified silicone.

(5) Epoxy value Determined by the following procedure and calculation method.
Epoxy-modified silicone was dissolved in benzyl alcohol and 1-propanol. A potassium iodide aqueous solution and a bromophenol blue indicator were added to this solution, followed by titration with 1N hydrochloric acid, and the point where the reaction system turned from blue to yellow was defined as the equivalent point. From the equivalent point, the epoxy value of the epoxy-modified silicone was calculated according to the following formula.
Epoxy value (equivalent / 100 g) = (V × N × F) / (10 × W)
[W, V, N, and F represent the following values, respectively.
W: Weight of sample (g)
V: Titration volume (mL)
N: Normality of hydrochloric acid used for titration (N)
F: Factor of hydrochloric acid used for titration]

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

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

(8) Storage stability at the time of pseudo-sunlight irradiation The storage stability at the time of pseudo-sunlight irradiation of the epoxy-modified silicone composition was evaluated by a storage stability index α represented by the following formula (XII).
Storage stability index α = (storage viscosity) / (starting viscosity) Formula (XII)
The container containing the epoxy-modified silicone composition immediately after production was sealed under light-shielding conditions, and after adjusting the temperature at 25 ° C. for 2 hours, the viscosity at 25 ° C. was measured, and this was defined as “starting viscosity”.

  Furthermore, after putting 10 g of the epoxy-modified silicone composition in a transparent alkali-free glass container having an inner diameter of 25 mm and a glass thickness of 1 mm, the container is sealed with a polyolefin lid, and a Suga tester equipped with a 3 kW vertical metering lamp. Set the container on the Metalling Vertical Weather Meter (Model No .: MV3000) manufactured by Co., Ltd. and irradiate the metalling lamp for 8 hours at an illuminance of 0.53 kw / m2 under conditions of a temperature of 63 ° C and a humidity of 5% Rh The light corresponding to the wavelength of pseudo-sunlight is irradiated for 7 days, with a total of 12 hours of 4 hours after the ring lamp irradiation is stopped as one cycle. The viscosity at 25 ° C. of the epoxy-modified silicone composition after completion of the light irradiation test corresponding to the wavelength of the pseudo-sunlight was measured in the same manner as described above, and this was designated as “storage viscosity”.

When the storage stability index α is 1.2 or less, it is judged as having excellent storage stability, and ◎, and when the index α is more than 1.2 and 1.5 or less, it has storage stability. Judgment was made ◯, and when it exceeded 1.5, it was judged that there was no storage stability and x was given.
The viscosity was measured by the following measurement method.
A 0.4 ml resin composition sample was placed in a rotary E-type viscometer (manufactured by Toki Sangyo Co., Ltd., “TV-22 type”, rotor: 3 ° × R14), and the resin composition was measured at a temperature of 25 ° C. did.

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

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

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

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

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

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

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

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

As a result of molecular weight measurement, the number average molecular weight of the obtained block type organohydrogensilicone was 7,200. Further, 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 —] unit 2.3 mol%, hydrogen methylsiloxy unit 29.3 mol%, dimethylsiloxy unit 14.2 mol%, cyclohexylmethylsiloxy unit 54.2 mol%, dialkyl The average chain lengths of siloxy units and hydrogen methylsiloxy units were 40 and 4.3, respectively.

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

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

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

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

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

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

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

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

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

Moreover, the epoxy value of the epoxy-modified silicone (1a) was 0.214, the transition metal element contained was only platinum, and the content of the element was 5 ppm.
The above synthetic operation was repeated to obtain an epoxy-modified silicone (1a), and the following treatment was performed.

  1,000 g of epoxy-modified silicone (1a) and 0.01 g of 2-hydroxy-4-octoxybenzophenone as a light stabilizer [100 mass of epoxy-modified silicone (1a)] in a 2 liter stirring tank equipped with a stirring blade Is equivalent to 0.001 part by mass with respect to parts] A colorless and transparent epoxy-modified silicone prepared by mixing uniformly in a nitrogen atmosphere at 30 ° C. for 2 hours to uniformly dissolve 2-hydroxy-4-octoxybenzophenone A composition (1b) was obtained. The viscosity of the epoxy-modified silicone composition (1b) was 100,000 mPa · s or less. Table 1 shows the storage stability evaluation results of the epoxy-modified silicone composition (1b) during irradiation with pseudo sunlight.

[Example 2]
<Production of epoxy-modified silicone composition>
Example 1 was used except that 0.015 g of 2-hydroxy-4-octoxybenzophenone (equivalent to 0.0015 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone (1a)) was used as the light stabilizer. Thus, a transparent epoxy-modified silicone composition (2b) in which 2-hydroxy-4-octoxybenzophenone was uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (2b) was 100,000 mPa · s or less. Table 1 shows the storage stability evaluation results of the epoxy-modified silicone composition (2b) upon irradiation with pseudo sunlight.

[Example 3]
<Production of epoxy-modified silicone composition>
As in Example 1, except that 0.1 g of 2-hydroxy-4-octoxybenzophenone (corresponding to 0.01 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone (1a)) was used as the light stabilizer. Thus, a transparent epoxy-modified silicone composition (3b) in which 2-hydroxy-4-octoxybenzophenone was uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (3b) was 100,000 mPa · s or less. Table 1 shows the storage stability evaluation results of the epoxy-modified silicone composition (3b) during irradiation with pseudo sunlight.

[Example 4]
<Production of epoxy-modified silicone composition>
As in Example 1, except that 1 g of 2-hydroxy-4-octoxybenzophenone (equivalent to 0.1 part by mass with respect to 100 parts by mass of the epoxy-modified silicone (1a)) was used as the light stabilizer, A transparent epoxy-modified silicone composition (4b) in which 2-hydroxy-4-octoxybenzophenone was uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (4b) was 100,000 mPa · s or less. Table 1 shows the storage stability evaluation results of the epoxy-modified silicone composition (4b) during irradiation with pseudo sunlight.

[Example 5]
<Production of epoxy-modified silicone composition>
In the same manner as in Example 1, except that 40 g of 2-hydroxy-4-octoxybenzophenone (corresponding to 4 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone (1a)) was used as the light stabilizer, A transparent epoxy-modified silicone composition (5b) in which hydroxy-4-octoxybenzophenone was uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (5b) was 100,000 mPa · s or less. Table 1 shows the storage stability evaluation results of the epoxy-modified silicone composition (5b) upon irradiation with pseudo sunlight.

[Comparative Example 1]
<Production of epoxy-modified silicone composition>
As in Example 1, except that 0.001 g of 2-hydroxy-4-octoxybenzophenone (equivalent to 0.0001 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone (1a)) was used as the light stabilizer. Thus, a transparent epoxy-modified silicone composition (1c) in which 2-hydroxy-4-octoxybenzophenone was uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (1c) was 100,000 mPa · s or less. Table 1 shows the storage stability evaluation results of the epoxy-modified silicone composition (1c) during irradiation with pseudo sunlight.

[Comparative Example 2]
<Production of epoxy-modified silicone composition>
Photostabilization was performed in the same manner as in Example 1 except that 60 g of 2-hydroxy-4-octoxybenzophenone (corresponding to 6 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone (1a)) was used as the light stabilizer. An epoxy-modified silicone composition (2c) in which 2-hydroxy-4-octoxybenzophenone was mixed as an agent was produced. In the obtained epoxy-modified silicone composition (2c), undissolved dilauryl thiodipropionate remained, and the epoxy-modified silicone composition (2c) was cloudy and was not transparent. The viscosity of the epoxy-modified silicone composition (2c) was 100,000 mPa · s or less. Table 1 shows the storage stability evaluation results of the epoxy-modified silicone composition (2c) during irradiation with pseudo sunlight.

[Example 6]
<Production of epoxy-modified silicone composition>
Except for using 1 g of 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole (equivalent to 0.1 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone (1a)) as a light stabilizer. In the same manner as in Example 1, a transparent epoxy-modified silicone composition (6b) in which 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole was uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (6b) was 100,000 mPa · s or less. Table 2 shows the storage stability evaluation results of the epoxy-modified silicone composition (6b) during irradiation with pseudo sunlight.

[Example 7]
<Production of epoxy-modified silicone composition>
As in Example 1, except that 1 g of 2-ethoxy-2′-ethyl-oxalic acid bisanilide was used as the light stabilizer [corresponding to 0.1 part by mass with respect to 100 parts by mass of the epoxy-modified silicone (1a)]. Thus, a transparent epoxy-modified silicone composition (7b) in which 2-ethoxy-2′-ethyl-oxalic acid bisanilide was uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (7b) was 100,000 mPa · s or less. Table 2 shows the storage stability evaluation results of the epoxy-modified silicone composition (7b) during irradiation with pseudo sunlight.

[Example 8]
<Production of epoxy-modified silicone composition>
1 g of N- (2-ethylphenyl) -N ′-(2-ethoxy-phenyl) oxalic acid diamide as a light stabilizer [equivalent to 0.1 part by mass with respect to 100 parts by mass of the epoxy-modified silicone (1a)] Except that 0.05 g of dilauryl thiodipropionate (corresponding to 0.005 parts by mass with respect to 100 parts by mass of epoxy-modified silicone (1a)) was used as an antioxidant, the same as in Example 1, A transparent epoxy-modified silicone composition (8b) in which N- (2-ethylphenyl) -N ′-(2-ethoxy-phenyl) oxalic acid diamide and dilaurylthiodipropionate were uniformly dissolved was obtained. The viscosity of the epoxy-modified silicone composition (8b) was 100,000 mPa · s or less. Table 2 shows the storage stability evaluation results of the epoxy-modified silicone composition (8b) during pseudo-sunlight irradiation.

[Example 9]
<Production of epoxy-modified silicone composition>
1 g of bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene-1,6-dicarbamate as a light stabilizer [0.1 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone (1a) The bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene-1,6-dicarbamate was uniformly dissolved in the same manner as in Example 1 except that it was used. An epoxy-modified silicone composition (9b) was obtained. The viscosity of the epoxy-modified silicone composition (9b) was 100,000 mPa · s or less. Table 2 shows the storage stability evaluation results of the epoxy-modified silicone composition (9b) during pseudo-sunlight irradiation.

[Example 10]
<Production of epoxy-modified silicone composition>
As a light stabilizer, 1 g of bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite (equivalent to 0.1 part by mass with respect to 100 parts by mass of epoxy-modified silicone (1a)) and Tris ( Except for using 0.05 g of 2,4-di-tert-butylphenyl) phosphite [equivalent to 0.005 parts by mass with respect to 100 parts by mass of the epoxy-modified silicone (1a)], the same as in Example 1. Transparent epoxy-modified silicone composition in which bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite and tris (2,4-di-tert-butylphenyl) phosphite are uniformly dissolved (10b) was obtained. The viscosity of the epoxy-modified silicone composition (10b) was 100,000 mPa · s or less. Table 2 shows the storage stability evaluation results of the epoxy-modified silicone composition (10b) during pseudo-sunlight irradiation.

  It is possible to provide an epoxy-modified silicone composition having excellent storage stability under light exposure conditions such as sunlight during transportation and storage.

Claims (6)

At least one light stabilizer selected from the group consisting of an ultraviolet absorber, a hindered amine light stabilizer, and an organic phosphorus light stabilizer is added to 100 parts by mass of the epoxy-modified silicone represented by the following average composition formula (1). An epoxy-modified silicone composition containing 0005 parts by mass to 5 parts by mass.

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

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