JP2012041381A - Epoxy-modified silicone, method for producing the same and curable resin composition using the same, and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an epoxy-modified silicone excellent in transparency, heat resistance, crack resistance, adhesion, etc.; a curable resin composition for sealing light-emitting elements; and a light-emitting part.SOLUTION: The epoxy-modified silicone is represented by an average compositional formula (3) containing silicone compounds represented by general formula (2) or the like.

Description

  The present invention relates to an epoxy-modified silicone suitably used as a main component of a curable resin composition used for a sealing material for light emitting elements, a lens, and the like.

  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 and cooling cycle (hereinafter abbreviated as “adhesion”), and crack resistance during solder reflow performed at 250 ° C. or higher And a cured product having adhesiveness (hereinafter abbreviated as solder reflow resistance) is required, and the epoxy resin such as bisphenol A-based epoxy resin and bisphenol F-based epoxy resin which has been conventionally used as a main component. In the case of the composition, it is the actual situation that 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. It is attracting attention as a high-performance sealing material because it is expected to have both properties.

  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. However, the epoxy-modified silicone mainly composed of the T structure is brittle, and it is difficult to satisfy the crack resistance required for the light emitting device sealing material.

  In Patent Documents 2 and 3, 5 to 50% of the SiH bond of the organohydrogensilicon compound obtained by the reaction of an organohydrogencyclosiloxane and an organopolysiloxane having an aliphatic unsaturated group is allyl glycidyl ether or vinyl. Proposals have been made for organohydrogensiloxane compounds hydrosilylated with cyclohexyl epoxide and their use in cured coatings. A feature of this organohydrogensiloxane compound is that the SiH unit is partially hydrosilylated with an epoxy compound, and a part of the SiH unit remains unreacted. This unreacted SiH unit is used for further cross-linking reaction, and is used for a release coating material or the like. However, there is no description in these specifications for use in optical applications such as optical semiconductors.

  Patent Document 4 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 encapsulant. . Patent Document 5 proposes an epoxy resin composition containing a cyclic siloxane having at least one epoxycyclohexyl group in one molecule and its use for an optical semiconductor encapsulant. However, these resin compositions have insufficient light resistance, and crack resistance and adhesion are not at satisfactory levels.

Patent Document 6 discloses a siloxane having a cyclic structure and an organopolysiloxane having an epoxy group unit as a substituent. This publication describes that a cured product having high transparency, heat resistance, thermal shock resistance, and adhesion can be obtained by curing the organopolysiloxane, but the solder reflow resistance is not always satisfactory. It did not have the performance that can be done.
Patent Document 7 discloses an epoxy silicone resin in which a siloxane unit having at least an epoxy group bonded through a group containing an isocyanuric ring skeleton as a substituent is bonded from both ends of a divalent organic group. However, this resin composition has insufficient light resistance, and furthermore, the adhesiveness is not at a sufficiently satisfactory level.

  Patent Document 8 discloses an epoxy siloxane comprising a reaction product of vinyl silicone, silyl hydride functional silicone, and olefin epoxy compound. Patent Document 9 discloses an epoxy group-containing organopolysiloxane composed of a reaction product of a hydroxyl group-containing organopolysiloxane, an organohydropolysiloxane, and an epoxy group and alkenyl group-containing compound. These polysiloxanes are used as ultraviolet curable release coating compositions, and there is no description in the specification regarding the use for optical applications such as optical semiconductors.

  Patent Document 10 discloses a telechelic siloxane polymer having a plurality of terminal epoxy groups, which is obtained from the reaction of a polyorganosiloxane having a vinyl group at the end, an organosiloxane oligomer having an SiH unit, and an excess of an alkenyl group-containing epoxy compound. It is disclosed. Although the use of this polymer as a release coating material is also described, there is no description in these specifications for use in optical applications such as optical semiconductors.

  Moreover, although the structure of the epoxy modified silicone which has the cyclic structure which consists of a siloxane unit, and an epoxy unit in a molecule | numerator is disclosed in the said patent documents 2-10, there is no indication about a bicyclo structure, the description regarding the physical property, There is no suggestion.

  Patent Document 11 discloses a modified polysiloxane having at least two epoxy groups in one molecule containing components in a specific molecular weight range in a specific range, and a thermosetting composition containing the modified polysiloxane. Is disclosed. In this publication, there is a description that the glass transition temperature can be increased by adding a specific amount of a high molecular weight component, but there is no description or suggestion regarding solder reflow resistance.

  Furthermore, Patent Document 12 discloses an epoxy silicone containing a monocyclic and bicyclo ring structure siloxane component in a specific amount range. The epoxy silicone described in the publication is described as having light resistance, heat resistance, heat discoloration resistance, crack resistance and adhesion in a thermal cycle, but it cannot be said that the solder reflow resistance is necessarily satisfactory. It was.

Japanese Patent No. 3263177 JP 2005-523980 A JP 2005-529989 A JP 2005-171021 A Japanese Patent No. 4371111 International Publication No. 2007/46399 Pamphlet JP 2009-203258 A JP 7-216308 A Japanese Patent Laid-Open No. 10-182826 US Pat. No. 6,313,255 JP 2008-255295 A International Publication 2008/133108 Pamphlet

  The present invention has excellent transparency, light resistance, heat resistance, heat discoloration, crack resistance and adhesion in a thermal cycle, and epoxy-modified silicone having resistance to solder reflow, element and package material. An object of the present invention is to provide a curable resin composition for sealing a light-emitting element that has excellent adhesion and does not generate cracks and can suppress a decrease in luminance over a long period of time, and a light-emitting component formed using the resin composition. And

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

  In view of the above points, as a result of intensive studies on the siloxane skeleton structure, the present inventors have a monocyclic structure and a bicyclo structure composed of a siloxane skeleton at the same time, and have a specific range of molecular weight and a specific ratio of siloxane units of a specific skeleton. It has been found that the epoxy-modified silicone contained in can solve the above-mentioned problems, and the present invention has been completed.

That is, the present invention is as follows.
[1] An average comprising at least a compound represented by the following general formula (1) and a compound represented by the following general formula (2) and satisfying the following (a) to (e): Epoxy-modified silicone represented by composition formula (3).
(A) The content of the compound represented by the general formula (1) [WA] calculated from the peak intensity obtained when measured by matrix-assisted ionization time-of-flight mass spectrometry by the following formula (1) The ratio [WB] / [WA] of the content [WB] of the compound represented by the general formula (2) to 0.10 or more and 2.00 or less,

(B) The value of [g / (a + b + c + d + e + f + g + h + i + j)] is 0.020 or less,
(C) The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] is 0.25 or more and 0.35 or less,
(D) the content of components having a molecular weight of 800 or less is 20% or more and 40% or less,
(E) The content of components having a molecular weight of 10,000 or more is 10% or more and 25% or less

[Wherein R ¹ is each independently A) an unsubstituted or substituted carbon having an aliphatic hydrocarbon unit composed of one or more structures selected from a chain, branched and cyclic structure group A monovalent aliphatic organic group having a number of 1 to 24 and an oxygen number of 0 to 5, B) an unsubstituted or substituted aromatic hydrocarbon unit, which is unsubstituted or substituted as necessary A monovalent fragrance having an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of chain, branched and cyclic, having 6 to 24 carbon atoms and 0 to 5 oxygen atoms A group organic group, C) having an aliphatic and / or aromatic hydrocarbon unit composed of one or more structures selected from the group consisting of an unsubstituted or substituted chain, branched, and cyclic structure. 5 to 26, oxygen number 0 to 5, and silicon number 1 represents at least one organic group selected from the group consisting of a monovalent organic group which is 1.

R ² each independently has 4 or more carbon atoms having an aliphatic hydrocarbon unit having one or more types of structures selected from the group consisting of D) unsubstituted or substituted, chain, branched, and cyclic structures. And an organic group containing an epoxy group having an oxygen number of 1 or more and 5 or less.

R ³ each independently has A) an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of an unsubstituted or substituted chain, branched and cyclic structure, and having 1 or more carbon atoms A monovalent aliphatic organic group having 24 or less and an oxygen number of 0 or more and 5 or less, B) an unsubstituted or substituted aromatic hydrocarbon unit, which is optionally substituted or substituted, a chain, A monovalent aromatic organic group having 6 to 24 carbon atoms and 0 to 5 oxygen atoms, which has an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of branched and cyclic structures; C) having 5 or more and 26 or less carbon atoms, having an aliphatic and / or aromatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted, substituted, and chain-like, branched and cyclic structures 1 in which the oxygen number is 0 or more and 5 or less, and the silicon number is 1. A monovalent organic group, E) a monovalent structure comprising one or more structures selected from the group consisting of a chain-like and a branched-chain, unsubstituted or substituted, having 2 to 6 carbon atoms, including a carbon-carbon double bond It represents at least one organic group selected from the group consisting of aliphatic organic groups.

  X represents an unsubstituted or substituted divalent hydrocarbon group having one or more structures selected from the group consisting of a chain and a branch having 2 to 6 carbon atoms.

  Each Y independently represents a divalent hydrocarbon group having one or more structures selected from the group consisting of a chain and a branched group, which are unsubstituted or substituted with 2 to 6 carbon atoms.

  Furthermore, Z represents a bond with a divalent hydrocarbon group Y.

  In the formula, t each independently represents an integer of 0 or more, u represents each independently an integer of 3 or more, and v represents an integer of 0 or more.

A, b, c, d, e, f, g, h, i, j represent the number of moles of each structural unit present in 1 mol of the epoxy-modified silicone, and a, e, f exceeds 0. B, c, d, g, h, i, and j are values that are 0 or more and satisfy e = a + d + i. The chain in the general formulas (1) and (2) may be random or block. ]
[2] The epoxy-modified silicone according to [1], wherein an epoxy value of the epoxy-modified silicone represented by the average composition formula (3) is 0.20 or more and 0.40 or less.
[3] The epoxy-modified silicone according to [1] or [2] above, wherein the value of v in the general formula (2) is 0 or more and 9 or less.
[4] The value of [(h + i + j) / (a + b + c + d + e + f + g + h + i + j)] of the epoxy-modified silicone represented by the average composition formula (3) is in the range of 0.040 or less. [3] The epoxy-modified silicone according to any one of [3].
[5] A curable resin comprising 100 parts by mass of the epoxy-modified silicone according to any one of [1] to [4] and 1 part by mass or more and 200 parts by mass or less of a curing agent for epoxy resin. Composition.
[6] The curable resin composition according to the above [5], further comprising 0.001 part by mass or more and 10 parts by mass or less of a curing accelerator.
[7] A curable resin comprising 100 parts by mass of the epoxy-modified silicone according to any one of [1] to [4] and 0.001 to 10 parts by mass of a cationic polymerization catalyst. Composition.
[8] A sealing material for a light-emitting element comprising the curable resin composition according to any one of [5] to [7].
[9] A light-emitting component sealed with the light-emitting element sealing material according to [8].
[10] A lens comprising the curable resin composition according to any one of [5] to [7].

  According to the present invention, an epoxy-modified silicone having transparency, light resistance, heat resistance, heat discoloration resistance, crack resistance, adhesion, solder reflow resistance, and suitable for use as a light emitting device sealing material, the epoxy modified silicone And a curable resin composition for sealing a light-emitting element, as well as excellent adhesion to an element or a package material formed using the resin composition, without cracks, and with little decrease in luminance over a long period of time It is possible to provide a light emitting component such as an excellent light emitting diode.

  Furthermore, according to the present invention, it is possible to provide a curable resin composition suitable as a lens material that is suitable for injection molding, hard after curing, and excellent in dimensional stability.

It is sectional drawing which shows typically an example of the optical semiconductor light-emitting device using the sealing material for light emitting devices and the die-bonding material containing the epoxy modified silicone of this invention. It is sectional drawing which shows typically an example of the optical semiconductor light-emitting device using the sealing material for light emitting devices and the die-bonding material containing the epoxy modified silicone of this invention.

  The epoxy-modified silicone in the present invention is represented by an average composition formula (3) including at least a compound represented by the following general formula (1) and a compound represented by the following general formula (2).

[Wherein R ¹ is each independently A) an unsubstituted or substituted carbon having an aliphatic hydrocarbon unit composed of one or more structures selected from a chain, branched and cyclic structure group A monovalent aliphatic organic group having a number of 1 to 24 and an oxygen number of 0 to 5, B) an unsubstituted or substituted aromatic hydrocarbon unit, which is unsubstituted or substituted as necessary A monovalent fragrance having an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of chain, branched and cyclic, having 6 to 24 carbon atoms and 0 to 5 oxygen atoms A group organic group, C) having an aliphatic and / or aromatic hydrocarbon unit composed of one or more structures selected from the group consisting of an unsubstituted or substituted chain, branched, and cyclic structure. 5 to 26, oxygen number 0 to 5, and silicon number 1 represents at least one organic group selected from the group consisting of a monovalent organic group which is 1.

R ² each independently has 4 or more carbon atoms having an aliphatic hydrocarbon unit having one or more types of structures selected from the group consisting of D) unsubstituted or substituted, chain, branched, and cyclic structures. And an organic group containing an epoxy group having an oxygen number of 1 or more and 5 or less.

R ³ each independently has A) an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of an unsubstituted or substituted chain, branched and cyclic structure, and having 1 or more carbon atoms A monovalent aliphatic organic group having 24 or less and an oxygen number of 0 or more and 5 or less, B) an unsubstituted or substituted aromatic hydrocarbon unit, which is optionally substituted or substituted, a chain, A monovalent aromatic organic group having 6 to 24 carbon atoms and 0 to 5 oxygen atoms, which has an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of branched and cyclic structures; C) having 5 or more and 26 or less carbon atoms, having an aliphatic and / or aromatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted, substituted, and chain-like, branched and cyclic structures 1 in which the oxygen number is 0 or more and 5 or less, and the silicon number is 1. A monovalent organic group, E) a monovalent structure comprising one or more structures selected from the group consisting of a chain-like and a branched-chain, unsubstituted or substituted, having 2 to 6 carbon atoms, including a carbon-carbon double bond It represents at least one organic group selected from the group consisting of aliphatic organic groups.

  X represents an unsubstituted or substituted divalent hydrocarbon group having one or more structures selected from the group consisting of a chain and a branch having 2 to 6 carbon atoms.

  Each Y independently represents a divalent hydrocarbon group having one or more structures selected from the group consisting of a chain and a branched group, which are unsubstituted or substituted with 2 to 6 carbon atoms.

  Furthermore, Z represents a bond with a divalent hydrocarbon group Y.

In the formula, t each independently represents an integer of 0 or more, u represents each independently an integer of 3 or more, and v represents an integer of 0 or more. A, b, c, d, e, f, g, h, i, j represent the number of moles of each structural unit present in 1 mol of the epoxy-modified silicone, and a, e, f exceeds 0. B, c, d, g, h, i, and j are values that are 0 or more and satisfy e = a + d + i. The chain in the general formulas (1) and (2) may be random or block. ]
Here, in the average composition formula (3), when h, i, and j satisfy the following formulas (2) and (3), the above a, b, h, i, and j It is a numerical value selected from a range satisfying 4).

h + i ≠ 0 Formula (2)
j ≠ 0 Expression (3)
0 ≦ b ≦ a + (h + i) + 2j + 2 (4)
Moreover, when said h, i, j satisfy | fills following numerical formula (5) and numerical formula (6) simultaneously, said a and b are numerical values selected from the range which satisfies following formula (7). .

h + i = 0 Expression (5)
j = 0 Expression (6)
0 ≦ b ≦ a + 2 (7)
When h, i, and j satisfy the following expressions (2) and (6), respectively, a, b, h, and i are selected from a range that satisfies the following expression (8). It is a numerical value.

h + i ≠ 0 Formula (2)
j = 0 Expression (6)
0 ≦ b ≦ a + (h + i) +2 (8)
Further, when h, i, and j satisfy the following mathematical expressions (5) and (3), the above a, b, and j are numerical values selected from a range that satisfies the following mathematical expression (9). .

h + i = 0 Expression (5)
j ≠ 0 Expression (3)
0 ≦ b ≦ a + 2j + 2 (9)
The bicyclo structure represented by the general formula (2) is a component that plays an important role when the cured product obtained by curing the epoxy-modified silicone of the present invention exhibits excellent light resistance, crack resistance and adhesion. It is. With only the monocyclic structure represented by the general formula (1), it is difficult to obtain sufficient light resistance, crack resistance and adhesion after curing. In order to further improve the light resistance, crack resistance and adhesion of the cured product, the content of the compound having a monocyclic structure represented by the general formula (1) is set to [WA] and the general formula (2). When the content of the compound having a bicyclo structure represented by [WB] is [WB], the ratio [WB] / [WA] needs to be in the range of 0.10 or more and 2.00 or less. .

  In the present invention, matrix-assisted ionization time-of-flight mass spectrometry (hereinafter referred to as MALDI-) is used as a method for calculating the content ratio of the compound represented by the general formula (1) and the compound represented by the general formula (2). (TOF / MS) is used, and the peak intensity of the compounds of the general formula (1) and the general formula (2) obtained by measuring the epoxy-modified silicone of the present invention by MALDI-TOF / MS is used. ] / [WA] is calculated by the following mathematical formula (1).

  When the value of [WB] / [WA] is less than 0.10 or exceeds 2.00, light resistance, crack resistance, or adhesion tends to be insufficient. Since the cured product obtained by curing the resulting epoxy-modified silicone has improved light resistance, crack resistance and adhesion, and further has increased heat resistance, the value of [WB] / [WA] is 0. It is more preferably 25 or more and 1.50 or less, and further preferably 0.40 or more and 1.30 or less.

  In the above formula (I), the mass corresponding to each structure of the general formula (1) and the general formula (2) is an isotope of each element when the elements constituting the structure have isotopes. This is a value calculated using the mass of the isotope having the largest abundance among the masses of.

In the present invention, when there are a plurality of peaks corresponding to the general formulas (1) and (2), the value of [WB] / [WA] is a plurality of peak intensities corresponding to each structure. Calculate using the total value. However, in the present invention, 3% or less of the maximum intensity of the peak corresponding to the total mass of the mass corresponding to each structure of the general formula (1) and the general formula (2) and the mass 23 of sodium. Peaks having intensity are excluded from the calculation of the total peak intensity.
Below, the specific method of the measuring method by MALDI-TOF / MS is described.

  A solution in which 0.1 g of epoxy-modified silicone is dissolved in 100 mL of tetrahydrofuran at room temperature and a solution in which 10 mg of dithranol is dissolved in 1 mL of tetrahydrofuran are uniformly mixed at a volume ratio of 1: 1 at room temperature. To prepare solution a. Next, 1 μL of solution a was dropped on a sample plate on which 1 μL of 10 mg sodium iodide dissolved in 10 mL of acetone was placed, the solvent was evaporated at room temperature, and measurement was performed with MALDI-TOF / MS under the following measurement conditions. Do.

<Measurement conditions>
Equipment: Shimadzu AXIMA CFRplus
Laser: Nitrogen laser (337 nm)
Detector type: Linear mode Ion detection: Positive ion (positive mode)
Integration count: 500 times

The average composition formula (3) of the epoxy-modified silicone of the present invention will be described in detail below.
In the present invention, each R ¹ is independently a carbon having an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of A) unsubstituted or substituted, a chain, a branch, and a ring. A monovalent aliphatic organic group having a number of 1 to 24 and an oxygen number of 0 to 5, B) an unsubstituted or substituted aromatic hydrocarbon unit, which is unsubstituted or substituted as necessary A monovalent fragrance having an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of chain, branched and cyclic, having 6 to 24 carbon atoms and 0 to 5 oxygen atoms A group organic group, C) having an aliphatic and / or aromatic hydrocarbon unit composed of one or more structures selected from the group consisting of an unsubstituted or substituted chain, branched, and cyclic structure. 5 to 26, oxygen number of 0 to 5, and silica It represents at least one organic group selected from the group consisting of monovalent organic groups having a prime number of 1.

These may be organic groups in which one kind or two or more kinds are mixed.
The number of carbon atoms is 1 to 24 and the number of oxygens having an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of an unsubstituted or substituted chain, branched and cyclic structure of A) above Examples of the monovalent aliphatic organic group in which is from 0 to 5 include, for example,
(A-1) Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl A chain organic group comprising an aliphatic hydrocarbon such as a group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group,
(A-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, a norbornyl group,
(A-3) Organic groups containing an ether bond such as methoxyethyl, ethoxyethyl, propoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, and the like.

  From the one or more structures selected from the group consisting of chain, branched and cyclic, which are unsubstituted or substituted aromatic hydrocarbon units of the above B), which are unsubstituted or substituted as necessary Examples of the monovalent aromatic organic group having an aliphatic hydrocarbon unit and having 6 to 24 carbon atoms and 0 to 5 oxygen atoms include, for example, phenyl group, tolyl group, xylyl group, benzyl group, α -A methyl styryl group, 3-methyl styryl group, 4-methyl styryl group etc. are mentioned.

The number of carbon atoms is 5 or more, having an aliphatic and / or aromatic hydrocarbon unit composed of one or more kinds of structures selected from the group consisting of an unsubstituted or substituted chain, branched and cyclic structure of C) above Examples of the monovalent organic group having 26 or less, an oxygen number of 0 to 5 and a silicon number of 1 include organic groups represented by the following general formula (4) and general formula (5).
—CH ₂ —CH—SiR ⁴ ₃ (4)
—CH (CH ₃ ) —SiR ⁴ ₃ (5)
[Wherein R ⁴ is each independently F) an unsubstituted or substituted carbon number having one or more aliphatic hydrocarbon units selected from a chain, branched, or cyclic structure group. Is a monovalent aliphatic organic group having 1 to 8 and an oxygen number of 0 to 5 or G) an unsubstituted or substituted aromatic hydrocarbon unit, and optionally substituted or substituted, A monovalent aromatic organic compound having an aliphatic hydrocarbon unit composed of one or more kinds of structures selected from a chain, branched, and cyclic structure group, having 6 to 8 carbon atoms and 0 to 5 oxygen atoms Represents at least one organic group selected from the group consisting of groups. ]
A specific example of R ⁴ will be described below.

The number of carbon atoms having an aliphatic hydrocarbon unit having one or more kinds of structures selected from the group consisting of an unsubstituted or substituted chain, branched, and cyclic structure of F) is 1 to 8 and oxygen number is Examples of monovalent aliphatic organic groups of 0 or more and 5 or less include, for example:
(F-1) Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl A chain organic group comprising an aliphatic hydrocarbon such as a group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group,
(F-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, a norbornyl group,
(F-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.

  Further, from the above-mentioned G) unsubstituted or substituted aromatic hydrocarbon unit and, if necessary, one or more structures selected from the group consisting of a chain, a branched, and a cyclic, unsubstituted or substituted Examples of the monovalent aromatic organic group having 6 to 8 carbon atoms and an oxygen number of 0 to 5 having an aliphatic hydrocarbon unit include, for example, phenyl group, tolyl group, xylyl group, benzyl group, α- Examples thereof include organic groups composed of aromatic hydrocarbons such as a methylstyryl group, a 3-methylstyryl group, and a 4-methylstyryl group.

In the above R ¹ , the number of carbon and oxygen, and, if necessary, within the range of the number of silicon, the hydroxyl group, alkoxy unit, acyl unit, carboxyl unit, alkenyloxy unit, acyloxy unit as an organic group In addition, halogen atoms such as fluorine and chlorine, ester bonds, and hetero atoms such as nitrogen, phosphorus and sulfur other than oxygen atoms and silicon atoms may be contained. These may be organic groups in which one kind or two or more kinds are mixed.
Next, the organic group R ² in the present invention will be described.

R ² has 4 or more and 24 or less carbon atoms and 1 oxygen atom having an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of unsubstituted, substituted, and chain-like, branched, and cyclic structures. An organic group containing an epoxy group consisting of 5 or less, and examples thereof include the following general formulas (6) to (11). These may be organic groups in which one kind or two or more kinds are mixed.

The R ⁵ in the general formula above, for _{example, - (CH 2) 2 -O} -, - (CH 2) 3 -O -, - (CH 2) 4 -O -, - CH 2 -CH (CH _{3) -O -, - CH 2} -CH (CH 3) -CH 2 -O -, - CH 2 -CH 2 -CH (CH 3) -O -, - CH 2 -CH (CH 3) -COO- , —CH ₂ —CH ₂ —COO— and other structural units containing an ether bond or an ester bond, — (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 - linear and / or aliphatic hydrocarbon unit consisting of branched like.

  These may be organic groups in which one kind or two or more kinds are mixed. 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 R ³ in the present invention will be described.
R ³ each independently has A) an aliphatic hydrocarbon unit having one or more types of structures selected from the group consisting of an unsubstituted or substituted, chain, branched, and cyclic structure, and having 1 carbon atom. A monovalent aliphatic organic group having 24 or less and an oxygen number of 0 or more and 5 or less, B) an unsubstituted or substituted aromatic hydrocarbon unit, which is optionally substituted or substituted, in the form of a chain A monovalent aromatic organic group having 6 to 24 carbon atoms and 0 to 5 oxygen atoms, which has an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of branched and cyclic structures C) 5 or 26 carbon atoms having an aliphatic and / or aromatic hydrocarbon unit having one or more kinds of structures selected from the group consisting of an unsubstituted or substituted chain, branched, and cyclic structure. Hereinafter, the oxygen number is 0 or more and 5 or less, and the silicon number is 1. 1 which consists of a monovalent organic group, E) 1 or more types of structures chosen from the group which consists of the chain | strand shape and the branched form which are 2 or 6 carbon atoms containing a carbon-carbon double bond, and are unsubstituted or substituted. Represents at least one organic group selected from the group consisting of valent aliphatic organic groups. Here, the “carbon-carbon double bond” in the present invention will be described. The “carbon-carbon double bond” in the present invention refers to an aliphatic carbon-carbon double bond and does not include a double bond such as a benzene ring or a naphthalene ring.

In the above R ³ , A) an aliphatic hydrocarbon unit having one or more kinds of structures selected from the group consisting of unsubstituted, substituted, and chain, branched and cyclic structures, and having 1 to 24 carbon atoms A monovalent aliphatic organic group having 0 or less and 5 or less oxygen, B) an unsubstituted or substituted aromatic hydrocarbon unit, optionally substituted or substituted, chain or branched A monovalent aromatic organic group having 6 to 24 carbon atoms and 0 to 5 oxygen atoms, which has an aliphatic hydrocarbon unit composed of one or more structures selected from a structural group consisting of a ring and a ring, C ) Having 5 or more and 26 or less carbon atoms, having an aliphatic and / or aromatic hydrocarbon unit composed of one or more structures selected from the group consisting of unsubstituted, substituted, and chain-like, branched and cyclic structures; The oxygen number is 0 or more and 5 or less, and the silicon number is 1. The monovalent organic group is the same as described above.

  On the other hand, the monovalent | monohydric structure which consists of 1 or more types of structures chosen from the group which consists of the chain | strand shape and the branched form by which carbon number containing the carbon-carbon double bond of said E) is 2 or less 6 or less. Examples of the aliphatic organic group include a vinyl group, an allyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, and a hexenyl group. These may be organic groups in which one kind or two or more kinds are mixed.

In the above R ³ , the number of carbons and oxygen, and if necessary, within the range of the number of silicons, as an organic group, a hydroxyl unit, an alkoxy unit, an acyl unit, a carboxyl unit, an alkenyloxy unit, an acyloxy unit In addition, halogen atoms such as fluorine and chlorine, ester bonds, and hetero atoms such as nitrogen, phosphorus and sulfur other than oxygen atoms and silicon atoms may be contained. These may be organic groups in which one kind or two or more kinds are mixed.
Next, the organic groups X, Y, and Z in the present invention will be described.

The organic groups X and Y are linking groups generated by hydrosilylation during the production of the epoxy-modified silicone of the present invention described later, and are unsubstituted or substituted having 2 to 6 carbon atoms, chained and branched. A divalent hydrocarbon group having at least one structure selected from the group consisting of: Specifically, for example, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, — (CH ₂ ) ₆ —, —CH ( CH ₃ ) —, —CH ₂ —CH (CH ₃ ) —, —CH (CH ₃ ) —CH ₂ — and the like can be exemplified. These may be organic groups in which one kind or two or more kinds are mixed.

  Z represents a bond with a divalent hydrocarbon group Y, specifically, a Si—Y—Z—Si structure, and the —X— hydrocarbon group described above.

As the organic groups R ¹ and R ^{3 in the} average composition formula (3) including the general formula (1) and the general formula (2) of the present invention, the light resistance of the epoxy-modified silicone of the present invention is improved or stored. Since the stability at the time tends to increase, the hydroxyl unit, alkoxy unit, acyl unit, carboxyl unit, alkenyloxy unit with respect to the total number of moles of all Si units of the epoxy-modified silicone represented by the average composition formula (3), The total number of moles of silicon atoms bonded to an acyloxy unit, a halogen atom such as fluorine or chlorine, or an ester bond, and further an organic group containing a hetero atom such as nitrogen, phosphorus or sulfur excluding an oxygen atom or silicon atom, It is preferably 10% or less, more preferably 1% or less, and still more preferably not contained at all.

  On the other hand, when producing a cured product using the epoxy-modified silicone of the present invention, the epoxy-modified silicone represented by the average composition formula (3) 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 epoxy-modified silicone of the present invention tends to have good light resistance and improved heat discoloration, the average composition formula (3) including the general formula (1) and the general formula (2) in the present invention. The organic groups R ¹ and R ³ are selected from the group consisting of C) in which (A-1), (A-2) and R ⁵ are (F-1) and (F-2). Is more preferable, and is more preferably an organic group selected from the group consisting of 1 to 8 carbon atoms and 0 oxygen number in (A-1) and (A-2). A-2 is more preferably an unsubstituted chain organic group selected from the group consisting of 1 to 8 carbon atoms and 0 oxygen number, and particularly preferably a methyl group.

As the organic group R ² in the epoxy-modified silicone represented by the average composition formula (3) including the compound represented by the general formula (1) and the compound represented by the general formula (2) of the present invention, an epoxy obtained Since the curing rate at the time of curing the modified silicone is increased or the light resistance of the cured product obtained by using the epoxy-modified silicone tends to be increased, aliphatic carbonization in which R ⁵ is a chain and / or a branched chain formula is a hydrogen unit (7) is preferably one represented by - (11), ^{R 5} is - _{(CH 2) 2} - are more preferable those represented by the general formula (7) to (11) is , ^{R 5} is - _{(CH 2) 2} - formula (8) to (11) in those represented more preferably, ^{R 5} is - Table at a is the formula (9) - _{(CH 2) 2} Are particularly preferred.

The divalent hydrocarbon group X in the present invention tends to increase the light resistance and heat discoloration of a cured product obtained using the epoxy-modified silicone of the present invention, and therefore-(CH ₂ ) _2- , -CH One or more structures selected from the group consisting of (CH ₃ ) — are preferable, and — (CH ₂ ) ₂ — is more preferable.

  The values of t and u in the general formulas (1) and (2) represent the number of chains, and the chains may be random or block. In the present invention, t is each independently an integer of 0 or more, and u is each independently an integer of 3 or more.

  In the present invention, the viscosity of the epoxy-modified silicone is reduced to increase the handleability, or the heat-discoloration property of the cured product obtained using the epoxy-modified silicone tends to be improved. Therefore, the general formula (1) and the general formula The value of (t + u) in the formula (2) is preferably 10 or less, more preferably 1 or less, and u is preferably 3 or more and 7 or less, t is 0, and u is 3 or more and 7 or less. More preferably, t is 0, and u is particularly preferably 3 or more and 5 or less.

The values of t and u in the above general formulas (1) and (2) can be calculated by the MALDI-TOF / MS measurement.
In the present invention, v is an integer of 0 or more. The heat resistance of the cured product obtained using the epoxy-modified silicone of the present invention is improved, the compatibility with the curing agent is good, and a transparent and uniform cured product is obtained. The value of is preferably 0 or more and 9 or less, more preferably 0 or more and 6 or less, still more preferably 0 or more and 3 or less, and particularly preferably 0.

  In the average composition formula (3) of the present invention, a, b, c, d, e, f, g, h, i, and j represent the number of moles of each structural unit present in 1 mole of the epoxy-modified silicone, a, e, and f are values exceeding 0, and b, c, d, g, h, i, and j are values that are 0 or more and satisfy e = a + d + i.

  The epoxy-modified silicone of the present invention does not show a modification reaction or a change in viscosity during storage, exhibits excellent storage stability, and at the same time exhibits excellent crack resistance after curing. The value of [g / (a + b + c + d + e + f + g + h + i + j)] representing the remaining amount of unreacted SiH groups to be required must be 0.020 or less, preferably 0.015 or less, and preferably 0.010 or less. Is more preferable, and it is still more preferable that it is 0.005 or less.

  In order for the epoxy-modified silicone of the present invention to exhibit solder reflow resistance in addition to crack resistance and adhesion, the abundance of M structure present in the epoxy-modified silicone represented by the average composition formula (3) The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] is within the range of 0.25 to 0.35, and the content of components having a molecular weight of 800 or less in the epoxy-modified silicone represented by the average composition formula (3) That the content of the component having a molecular weight of 10,000 or more in the epoxy-modified silicone represented by the average composition formula (3) is 10% or more and 25% or less. It is necessary to be satisfied at the same time.

  In addition to the crack resistance and adhesion of the epoxy-modified silicone of the present invention, it represents the abundance of the M structure present in the epoxy-modified silicone represented by the average composition formula (3) in order to further increase the solder reflow resistance [ The value of (a + b) / (a + b + c + d + e + f + g + h + i + j)] is preferably in the range of 0.26 to 0.34, and more preferably in the range of 0.27 to 0.33. The content of the component having a molecular weight of 800 or less in the epoxy-modified silicone represented by the average composition formula (3) is preferably in the range of 23% to 37%, and in the range of 25% to 35%. It is more preferable that Furthermore, the content of the component having a molecular weight of 10,000 or more in the epoxy-modified silicone represented by the average composition formula (3) is preferably in the range of 12% or more and 22% or less, and 12% or more and 20% or less. More preferably, it is the range.

  The value of [(h + i + j) / (a + b + c + d + e + f + g + h + i + j)] representing the branched chain content improves the handleability of the epoxy-modified silicone, and further improves the compatibility with the curing agent and the curing accelerator, and the uniform mixing property. Since crack resistance tends to be good after curing, it is preferably 0.040 or less, more preferably 0.010 or less, and even more preferably 0.

  In the present invention, f tends to be less sticky on the surface of the cured product obtained using epoxy-modified silicone, and therefore f is preferably 1 or more, more preferably 1.5 or more. .

  Since the heat resistance of the cured product obtained using the epoxy-modified silicone of the present invention tends to increase, the epoxy value of the epoxy-modified silicone is preferably 0.20 or more, more preferably 0.23 or more. And more preferably 0.25 or more. On the other hand, since the light resistance and heat discoloration of a cured product obtained using epoxy-modified silicone tend to increase, the epoxy value of epoxy-modified silicone is preferably 0.40 or less, and is 0.37 or less. Is more preferable, and it is still more preferable that it is 0.35 or less.

  The epoxy-modified silicone represented by the average composition formula (3) of the present invention has a number average molecular weight of 400 or more and 1,000 from the viewpoint of improving handleability and processability due to fluidity and the like. Is preferably in the range of 500 to 100,000, more preferably in the range of 500 to 100,000, still more preferably in the range of 500 to 50,000, and more preferably in the range of 500 to 10,000. The following ranges are particularly preferred.

  Here, [g / (a + b + c + d + e + f + g + h + i + j)], [(a + b) / (a + b + c + d + e + f + g + h + i + j)], [(h + i + j) / (a + b + c, +++), and (+) ++ A method for calculating f will be described.

[G / (a + b + c + d + e + f + g + h + i + j)] and [(h + i + j) / (a + b + c + d + e + f + g + h + i + j)] in the epoxy-modified silicone represented by the average composition formula (3) of the present invention are obtained by performing ²⁹ Si-NMR measurement by the method described below. This is a value obtained by calculating the abundance ratio of each structural unit corresponding to g, (a + b), and (h + i + j) with respect to the total Si based on the integrated value calculated from the obtained spectrum pattern.

  On the other hand, f is calculated by the following mathematical formula (10) using the number average molecular weight obtained by gel permeation chromatography (GPC) measurement described later, and the epoxy value obtained by measuring epoxy value described later. Value.

f = (number average molecular weight) / (100 / epoxy value) Formula (10)
<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.

  Next, the number average molecular weight of the epoxy-modified silicone represented by the average composition formula (3) in the present invention, the content of components having a molecular weight of 800 or less in the epoxy-modified silicone represented by the average composition formula (3), and The content of components having a molecular weight of 10,000 or more in the epoxy-modified silicone represented by the average composition formula (3) will be described.

  The molecular weight in the epoxy-modified silicone represented by the average composition formula (3) is a value obtained by gel permeation chromatography (GPC) measurement using chloroform as an eluent and monodisperse polystyrene and styrene monomers as standard substances. is there. Specifically, it refers to the number average molecular weight calculated using the above calibration curve from the elution time and detection intensity of the measurement sample solution prepared in advance from the elution time by RI detection.

  On the other hand, the content of components having a molecular weight of 800 or less in the epoxy-modified silicone represented by the average composition formula (3) is the elution start point and elution end point of the epoxy-modified silicone in the elution curve obtained by the GPC measurement. A numerical value expressed as a percentage of the peak area (peak area 2) corresponding to a molecular weight of 800 or less with respect to the elution peak area (peak area 1) obtained by linking [[(peak area 2) / (peak area] 1) Numerical value represented by x100 (%)].

  The content of components having a molecular weight of 10,000 or more in the epoxy-modified silicone represented by the average composition formula (3) is the elution start point and elution of the epoxy-modified silicone in the elution curve obtained by the above GPC measurement. A numerical value representing the ratio of the peak area (peak area 3) corresponding to a molecular weight of 10,000 or more to the elution peak area (peak area 1) obtained by linking the end points [ie, (peak area 3) / (Peak area 1) × a numerical value represented by 100 (%)].

Next, 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>
The 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 (11).

Epoxy value (equivalent / 100 g) = (V × N × F) / (10 × W) Formula (11)
[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]

Next, the specific example of the manufacturing method of the epoxy modified silicone of this invention is demonstrated.
The epoxy-modified silicone of the present invention needs to contain at least the compounds represented by the above general formula (1) and general formula (2). As long as the epoxy-modified silicone of the present invention satisfies the requirements of the present invention, the production method is not limited. For example, (a-1) a cyclic organohydrogen silicone containing a Si—H group, and if necessary, A compound having a chain-branched organohydrogen silicone is subjected to a hydrosilylation reaction to form a compound having a carbon-carbon double bond and an epoxy group, and a silicone having two or more carbon-carbon double bonds. (A-2) An organosilicone containing a condensation-reactive group such as an organohalosilane or an organoalkoxysilane as a substrate, hydrolyzed as necessary, and then subjected to a condensation reaction. A method of introducing an organic group having a cyclic structure having (a-3) an organic group containing an epoxy unit as a substituent A method of ring-opening polymerization of luganosilicone in the presence of linear and / or branched siloxanes, containing or not containing Si-H groups in the molecule as required, (a-4) It can be produced by a method of synthesizing a modified polysiloxane obtained by the methods described in 1), (a-2) and (a-3) by re-equilibration reaction. In addition, a method of mixing the epoxy-modified silicones obtained by the above-described method, an epoxy-modified silicone obtained by the above-mentioned method, the general formula (1), the general formula (2), and other molecules at least The epoxy-modified silicone represented by the average composition formula (3) of the present invention is produced by a method of mixing at least one epoxy-modified silicone selected from the group consisting of epoxy-modified silicones having one or more epoxy groups. It is also possible.

  Among these, the method (a-1) can simultaneously form the general formula (1) and the general formula (2) of the present invention, and the general formula (1) and the general formula (2) It is a method preferably used because it is possible to produce an epoxy-modified silicone represented by the average composition formula (3). Further, subsequently, the epoxy-modified silicone obtained by the method (a-1) and the epoxy-modified silicone having at least one epoxy group in the general formula (1), the general formula (2), and other molecules. The method of mixing at least one epoxy-modified silicone selected from the group consisting of silicones, or the method of mixing the epoxy-modified silicones obtained by the method (a-1) is a requirement of the present invention by a simple operation. This is a preferable method because an epoxy-modified silicone satisfying the above can be produced.

Hereinafter, the method (a-1) will be described.
The method of (a-1) is an average composition containing at least an organohydrogensilicon represented by the following general formula (12) and a silicone having a carbon-carbon double bond represented by the general formula (13). Epoxy-modified silicone by adding a silicone having a carbon-carbon double bond represented by formula (14) and a vinyl compound <B> containing a compound <A> having a carbon-carbon double bond and an epoxy group It is a method of manufacturing.

[Wherein R ¹ is the same as described above, and each R ⁶ is independently an unsubstituted or substituted chain or branched chain having 2 to 6 carbon atoms including a carbon-carbon double bond. Represents a monovalent aliphatic organic group having at least one structure selected from the group consisting of:

  T, u, and v in the formula are the same as above, and k, l, m, n, o, p, and q are the number of moles of each structural unit present in 1 mole of silicone having a carbon-carbon double bond. K is a value exceeding 0, and l, m, n, o, p, q are each a value of 0 or more.

The chain in general formula (12) may be random or block. ]
In the average composition formula (14), when o, p, and q simultaneously satisfy the following formulas (12) and (13), the above k, l, o, p, and q It is a numerical value selected from a range that satisfies (14).
o + p ≠ 0 Formula (12)
q ≠ 0 Formula (13)
0 ≦ k + l ≦ o + p + 2q + 2 (14)
Further, when the above o, p, and q simultaneously satisfy the following formulas (15) and (16), k and l are numerical values selected from a range that satisfies the following formula (17). It is.

o + p = 0 Formula (15)
q = 0 ... Formula (16)
0 ≦ k + l ≦ 2 (17)
Further, when the above o, p, and q satisfy the following equations (12) and (16) respectively, the above k, l, o, and p are within the range that satisfies the following equation (18). The number to be selected.

o + p ≠ 0 Formula (12)
q = 0 ... Formula (16)
0 ≦ k + l ≦ o + p + 2 Formula (18)
Further, when o, p, and q satisfy the following equations (15) and (13), respectively, k, l, and q are numerical values selected from a range that satisfies the following equation (19). It is.

o + p = 0 Formula (15)
q ≠ 0 Formula (13)
0 ≦ k + l ≦ 2q + 2 (19)
The method for producing the silicone represented by the organohydrogen silicone represented by the general formula (12), the general formula (13), and the average composition formula (14) used in the present invention is not particularly limited, and is conventionally known. It is possible to utilize the compound produced by the method.

  In the present invention, the silicone having a carbon-carbon double bond represented by the average composition formula (14) is a silicone in which a part of the silicone has a carbon-carbon double bond represented by the general formula (13). The silicone having a carbon-carbon double bond represented by the average composition formula (14) may be a silicone having a carbon-carbon double bond represented by the general formula (13). . When a part of the silicone having a carbon-carbon double bond represented by the average composition formula (14) is a silicone having a carbon-carbon double bond represented by the general formula (13), the average composition formula (14 In addition to the silicone having a carbon-carbon double bond represented by the general formula (13), the silicone having a carbon-carbon double bond represented by) is linear, cyclic, branched, ladder-like, Silicone having a carbon-carbon double bond of any structure such as a cage may be included.

As the compound of the general formula (12) that can be used in the present invention, t is independently an integer of 0 or more, u is independently an integer of 3 or more, and R ¹ is as described above. If it is an organic group, there will be no limitation in particular, It can be used as a 1 type, or 2 or more types of mixture.

Since the light resistance of the epoxy-modified silicone of the present invention tends to be good, the organohydrogensilicone represented by the general formula (12) is a linear or branched chain in which R ¹ is unsubstituted or substituted. And a compound having a monovalent aliphatic organic group having 1 to 24 carbon atoms and having an aliphatic hydrocarbon unit consisting of one or more structures selected from the group consisting of cyclic structures, such as Examples of the compound include 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3 , 5,7,9,11-hexamethylcyclohexasiloxane, 1,3,5,7,9,11,13-heptamethylcycloheptasiloxane, 1,3,5,7,9, 11,13,15-octamethylcyclooctasiloxane, 1,3,5,7,9,11,13,15,17-nonamethylcyclononasiloxane, 1,3,5,7,9,11,13, 15,17,19-decamethylcyclodecasiloxane, 1,3,5,7,9,11,13,15,17,19,21-dodecamethylcyclodecasiloxane, 1,1,3,5-tetramethyl Cyclotrisiloxane, 1,1,3,5,5,7-hexamethylcyclotetrasiloxane, 1,3,5,7-tetraethylcyclotetrasiloxane, 1,3,5,7,9-pentaethylcyclopentasiloxane 1,3,5,7,9,11-hexaethylcyclohexasiloxane, 1,3,5,7,9,11,13-heptaethylcycloheptasiloxane and the like.

Among the above, the viscosity of the epoxy-modified silicone of the present invention is reduced to increase the handleability, or the heat discoloration and crack resistance of the cured product obtained using the epoxy-modified silicone of the present invention tend to be improved. Therefore, it is preferable to use a compound having a value of (t + u) of 10 or less in general formula (12), more preferably a compound having t of 1 or less and u of 3 or more and 7 or less. It is more preferable to use a compound having 0 and u is 3 or more and 7 or less, even more preferable to use a compound having t is 0 and u is 3 or more and 5 or less, and t is 0 and u is 3 It is particularly preferable to use a compound having 5 or less and R ¹ is a methyl group, and most preferably 1,3,5,7-tetramethylcyclotetrasiloxane.

In the compound of the general formula (13) in the present invention, R ¹ is the same as described above, and R ⁶ is an unsubstituted or substituted chain having 2 to 6 carbon atoms including a carbon-carbon double bond, It is a compound having a monovalent aliphatic organic group having at least one structure selected from the group consisting of branched groups. Examples of the organic group for R ⁶ include a vinyl group, an allyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, and a hexenyl group. These may be organic groups in which one kind or two or more kinds are mixed.

In the above R ¹ , the number of carbon and oxygen, and, if necessary, within the range of the number of silicon, the hydroxyl group, alkoxy unit, acyl unit, carboxyl unit, alkenyloxy unit, acyloxy unit as an organic group In addition, halogen atoms such as fluorine and chlorine, ester bonds, and hetero atoms such as nitrogen, phosphorus and sulfur other than oxygen atoms and silicon atoms may be contained.

As the compound of the general formula (13), a compound having a vinyl group is preferable as R ⁶ because it has a high reactivity and tends to perform a hydrosilylation reaction with high reproducibility.

  On the other hand, as the compound of the general formula (13), the epoxy-modified silicone of the present invention has good light resistance and heat discoloration, or the stability during storage tends to increase. Hydroxyl unit, alkoxy unit, acyl unit, carboxyl unit, alkenyloxy unit, acyloxy unit, halogen atom such as fluorine or chlorine, ester bond, oxygen atom or silicon The total number of moles of silicon atoms bonded to organic groups containing heteroatoms such as nitrogen, phosphorus and sulfur excluding atoms is preferably 10% or less, more preferably 1% or less, and no inclusion Is more preferable.

Further, R ¹ has an aliphatic hydrocarbon unit having one or more kinds of structures selected from the above-mentioned unsubstituted or substituted structure group consisting of a chain, a branched chain and a cyclic structure of A), It is preferably selected from the group consisting of (A-1) and (A-2) in a monovalent aliphatic organic group having 1 to 24 and an oxygen number of 0 to 5; It is more preferable that it is an organic group selected from the group consisting of 1 to 8 carbon atoms and 0 oxygen number in (A-2), and the number of carbon atoms in (A-1) and (A-2) is More preferably, it is an unsubstituted chain organic group selected from the group consisting of 1 to 8 and oxygen number 0. Examples of such compounds include dimethylvinylsiloxy-terminated polydimethylsiloxane, dimethylvinylsiloxy-terminated dimethylsiloxane-methylethylsiloxane copolymer, dimethylvinylsiloxy-terminated dimethylsiloxane-methyloctylsiloxane copolymer, and the like. Furthermore, as the compound of the general formula (13) in the present invention, it is particularly preferable R ¹ is a methyl group.

  In the present invention, v in the general formula (13) is an integer of 0 or more. Since the heat resistance of the cured product obtained by using the epoxy-modified silicone of the present invention is improved, the compatibility with the curing agent is good, a transparent and uniform cured product is obtained, and the adhesion tends to be good. The value of is preferably 0 or more and 9 or less, more preferably 0 or more and 6 or less, still more preferably 0 or more and 3 or less, and particularly preferably 0.

  Preferred examples of the compound of the general formula (13) in the present invention include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane when v = 0, and 1,5 when v = 1. -Divinyl-1,1,3,3,5,5-hexamethyltrisiloxane, dimethylvinylsiloxy-terminated polydimethylsiloxane having a value of v of 9 or less, and 1,3-divinyl-1,1,3 , 3-tetramethyldisiloxane is particularly preferred.

Organic groups R ¹ and R of silicone having a carbon-carbon double bond represented by an average composition formula (14) including at least a silicone having a carbon-carbon double bond represented by the general formula (13) in the present invention. ⁶ is the same as described above. In addition, R ¹ of the silicone having a carbon-carbon double bond represented by the average composition formula (14) may be organic as long as it is within the range of the number of carbons and oxygen, and, if necessary, the number of silicons. As a group, hydroxyl unit, alkoxy unit, acyl unit, carboxyl unit, alkenyloxy unit, acyloxy unit, halogen atom such as fluorine or chlorine, ester bond, nitrogen, phosphorus, sulfur other than oxygen atom or silicon atom, etc. Of heteroatoms.

  Since the light resistance of the epoxy-modified silicone of the present invention tends to be good or stability during storage tends to increase, an average containing at least a silicone having a carbon-carbon double bond represented by the general formula (13) Hydroxyl unit, alkoxy unit, acyl unit, carboxyl unit, alkenyloxy unit, acyloxy unit, fluorine and chlorine with respect to the total number of moles of all Si units in the silicone having a carbon-carbon double bond represented by the composition formula (14) The total number of moles of silicon atoms bonded to organic atoms containing hetero atoms such as nitrogen atoms, phosphorus bonds and sulfur atoms other than halogen atoms such as halogen atoms, ester bonds, and oxygen atoms and silicon atoms is 10% or less. Is preferably 1% or less, and more preferably not contained at all.

Further, R ¹ has an aliphatic hydrocarbon unit composed of one or more structures selected from the structural group consisting of a chain, a branched chain and a ring, which is unsubstituted or substituted in the above A), and has 1 or more carbon atoms It is preferably selected from the group consisting of (A-1) and (A-2) in a monovalent aliphatic organic group having 24 or less and an oxygen number of 0 or more and 5 or less, and (A-1) and (A -2) It is more preferably an organic group selected from the group consisting of 1 to 8 carbon atoms and 0 oxygen number, and (A-1) and (A-2) have 1 to 8 carbon atoms. Hereinafter, an unsubstituted chain organic group selected from the group having 0 oxygen is more preferable, and a methyl group is particularly preferable.

  The silicone having a carbon-carbon double bond represented by the average composition formula (14) including at least the silicone having a carbon-carbon double bond represented by the general formula (13) of the present invention is the epoxy-modified of the present invention. The heat resistance of the cured product obtained using silicone is improved, the compatibility with the curing agent is good, a transparent and uniform cured product is obtained, and the adhesion tends to be good, so the number average molecular weight is 180. Preferably, it is 1,000 or less, more preferably 180 or more and 800 or less, and further preferably 180 or more and 600 or less.

  Moreover, 1 mol of the silicone which has a carbon-carbon double bond represented by the average composition formula (14) including at least the silicone having a carbon-carbon double bond represented by the general formula (13) of the present invention is constituted. The number of moles of each unit is such that the value of [q / (k + l + m + o + p + q)] is 0.040 from the viewpoint of allowing the hydrosilylation reaction in producing the epoxy-modified silicone of the present invention to proceed stably and with good reproducibility. It is preferable that q is 0, and the value of [(o + p) / (k + l + m + o + p + q)] is more preferably 0.010 or less, and the value of [(o + p + q) / (k + l + m + o + p + q)] is 0. More preferably it is.

  On the other hand, since the stickiness of the surface of the cured product obtained using the epoxy-modified silicone produced by the production method of the present invention tends to be suppressed, it has a carbon-carbon double bond represented by the general formula (13). The value of (k + n + p) of the silicone having a carbon-carbon double bond represented by the average composition formula (14) containing at least silicone is preferably 1 or more, more preferably 1.5 or more. More preferably, it is 8 or more.

  Here, a calculation method of k to q in the silicone having a carbon-carbon double bond represented by the average composition formula (14) including at least the silicone having a carbon-carbon double bond represented by the general formula (13). Will be described.

Calculation of k to q of the silicone having a carbon-carbon double bond represented by the average composition formula (14) including at least the silicone having a carbon-carbon double bond represented by the general formula (13) is ²⁹ Si -NMR measurement, GPC measurement, and, if necessary, calculated using results obtained by ¹ H-NMR measurement. Specifically, first, ²⁹ Si-NMR measurement and ¹ H-NMR measurement of silicone represented by the average composition formula (14) are performed, and each component is based on an integral value calculated from the obtained spectrum pattern. Calculate the abundance of units as a percentage.

  Next, an average formula amount of the structural unit is calculated using the obtained abundance ratio of each structural unit and the theoretical formula amount of each structural unit.

  Furthermore, the number average molecular weight obtained by GPC measurement of the silicone represented by the average composition formula (14) is defined as an average considering the abundance of each structural unit calculated above as the molecular weight per mole of the silicone. Dividing by the formula amount, the total number of moles of each unit constituting the silicone represented by the average composition formula (14) is calculated. From the total number of moles of each unit constituting the silicone represented by the obtained average composition formula (14) and the abundance of each unit, one mole of silicone represented by the average composition formula (14) is constructed. The number of moles of each unit can be calculated.

  In the present invention, the silicone having a carbon-carbon double bond represented by the average composition formula (14) is a silicone having a carbon-carbon double bond represented by the general formula (13). Preferably, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,5-divinyl-1,1,3,3,5,5-hexamethyltrisiloxane, value of v Is more preferably 9 or less, more preferably 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

  In the present invention, a part of the vinyl compound <B> may be a compound <A> having a carbon-carbon double bond and an epoxy group, and the entire vinyl compound <B> is a carbon-carbon double bond and an epoxy. It may be a compound <A> having a group.

  The compound <A> having a carbon-carbon double bond and an epoxy group that can be used in the present invention is not particularly limited as long as the epoxy-modified silicone of the present invention can be produced, and an epoxy group and a carbon-carbon double bond are essential. The number of carbon atoms having an aliphatic hydrocarbon unit having at least one structure selected from the group consisting of a chain, a branched, and a cyclic structure, which is a non-substituted or substituted structural unit, is 4 to 24 and oxygen A compound having a number of 1 or more and 5 or less can be used. Specific examples of such compounds include compounds represented by the following general formula (15) to general formula (20).

Examples of R ^{7 in} the general formula (15) to the general formula (20) include CH ₂ ═CH—O—, CH ₂ ═CH—CH ₂ —O—, and CH ₂ ═CH—CH ₂ —CH. _{2 -O-, CH 2 = C (} CH 3) -O-, CH 2 = C (CH 3) -CH 2 -O-, CH 2 = CH 2 -CH (CH 3) -O-, CH 2 = Structural units containing an ether bond or ester bond such as C (CH ₃ ) —COO—, CH ₂ ═CH—COO—, CH ₂ ═CH—, CH ₂ ═CH—CH ₂ —, CH ₂ ═C (CH _{3) -, CH 2 = CH-} (CH 2) 2 -, CH 2 = CH- (CH 2) 3 -, CH 2 = CH- (CH 2) 4 -, CH 2 = CH- (CH 2) 5 _{-, CH 2 = CH- (CH} 2) 6 -, CH 2 = CH- (CH 2) 7 -, CH 2 = CH- ( _{H 2) 8 -, CH 2} = CH- (CH 2) 9 -, CH 2 = CH- (CH 2) 10 -, CH 2 = CH- (CH 2) 11 -, CH 2 = CH- (CH 2 _{) 12 -, CH 2 = CH-} (CH 2) 13 -, CH 2 = CH- (CH 2) 14 - linear and / or aliphatic hydrocarbon unit consisting of branched like. These may be organic groups in which one kind or two or more kinds are mixed. Furthermore, when an optical isomer exists, it may be an organic group mixed alone or in combination of two or more optical isomers.

As the compound <A> has a tendency to increase the curing speed when curing the resulting epoxy-modified silicone, or the light resistance and heat discoloration of the cured product obtained using the epoxy-modified silicone tend to increase, R ⁷ Has a carbon-carbon double bond as an essential constituent unit, and is a general formula composed of one or more aliphatic hydrocarbon units selected from the group consisting of a chain and a branch, which are unsubstituted or substituted (16) - (20) are preferred, the general formula ^{R 7} is a vinyl group (16) to (20) are more preferable, the general formula ^{R 7} is a vinyl group (17) to more preferably (20), A compound of the general formula (18) in which R ⁷ is a vinyl group, that is, 4-vinylcyclohexene oxide is particularly preferable.

  As a compound used as a vinyl compound <B> other than the compound <A> having a carbon-carbon double bond and an epoxy group, for example, (a) an epoxy group is not contained and a carbon-carbon double bond is an essential component. The unit has an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of unsubstituted, substituted, and chain-like, branched, and cyclic structures, having 3 to 24 carbon atoms and an oxygen number of 0 or more and 5 or less compounds, (I) a carbon-carbon double bond as an essential constituent unit, an unsubstituted or substituted aromatic hydrocarbon unit, and an optionally substituted or substituted chain A compound having an aliphatic hydrocarbon unit consisting of one or more structures selected from a structural group consisting of branched, cyclic, and having 8 to 24 carbon atoms and 0 to 5 oxygen atoms, (c) Expressed by equation (21) 1 or more carbon atoms in the molecule that - include silane containing a carbon double bond.

^{_{CH 2 = CH-SiR 5 3}} ··· (21)
[Wherein R ⁵ is independently the same as described above. ]
The above compounds (a) to (c) can be used as one kind or a mixture of two or more kinds. In addition, these compounds have a hydroxyl unit, an alkoxy unit, an acyl unit, a carboxyl unit, an alkenyloxy unit, an acyloxy unit, a halogen atom such as fluorine or chlorine, or the like, as long as the carbon number and the oxygen number are within the ranges described above. Further, it may contain an ester bond and a heteroatom such as nitrogen, phosphorus or sulfur excluding an oxygen atom or a silicon atom.

  (A) one or more selected from the group consisting of an unsubstituted or substituted chain, branched, and cyclic structure that does not contain an epoxy group and has a carbon-carbon double bond as an essential constituent unit Specific examples of the compound having an aliphatic hydrocarbon unit having a structure of 3 to 24 carbon atoms and 0 to 5 oxygen atoms include propylene, 1-butene, 1-pentene, 1-hexene and 1-heptene. 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, cyclopentene, methylsiluro Carbon-carbon double bonds such as pentene, cyclohexene, methylcyclohexene, norbornene, vinylcyclohexane, vinyldecahydronaphthalene Compound consisting of a hydrocarbon, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, allyl methyl ether, allyl ethyl ether, carbon atoms such as allyl propyl ether - a compound having a carbon double bond and an ether bond, and the like. These can be used as one kind or a mixture of two or more kinds.

  (A) It has a carbon-carbon double bond as an essential constituent unit, and is composed of an unsubstituted or substituted aromatic hydrocarbon unit, and an unsubstituted or substituted chain, branched or cyclic as necessary. Specific examples of the compound having an aliphatic hydrocarbon unit having one or more structures selected from the structural group and having 8 to 24 carbon atoms and 0 to 5 oxygen atoms include, for example, styrene, 3 -Methylstyrene, 4-methylstyrene, α-methylstyrene and the like. These can be used as one kind or a mixture of two or more kinds.

  (C) Specific examples of silanes containing one or more carbon-carbon double bonds in the molecule include carbon-carbons such as vinyltrimethylsilane, vinylethyldimethylsilane, vinyldiethylmethylsilane, and vinyltriethylsilane. Vinyl alkylsilane having a double bond, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, vinyltriisopropoxysilane, vinyltri-t- Aromatics having carbon-carbon double bonds such as butoxysilane, aliphatic vinylalkoxysilanes having carbon-carbon double bonds, vinylphenylmethylmethoxysilane, vinylphenyldiethoxysilane, vinyldiphenylethoxysilane, etc. Vinyl arylsilanes having a carbon-carbon double bond such as vinylalkoxysilane, vinylphenyldimethylsilane, vinylphenyldiethylsilane, vinylaralkylsilanes having a carbon-carbon double bond such as vinylbenzyldimethylsilane, vinylbenzyldiethylsilane, etc. Is mentioned. Silanes containing a carbon-carbon double bond in these molecules can be used as one kind or a mixture of two or more kinds.

  Among these, since there exists a tendency for the light resistance of the hardened | cured material obtained using the epoxy-modified silicone obtained after hydrosilylation reaction to increase, vinyl compounds other than the compound <A> which has a carbon-carbon double bond and an epoxy group < B> is a hydroxyl unit, an alkoxy unit, an acyl unit, a carboxyl unit, an alkenyloxy unit, an acyloxy unit, a halogen atom such as fluorine or chlorine, an ester bond, or nitrogen or phosphorus other than an oxygen atom or a silicon atom. It is preferable that no organic group containing a hetero atom such as sulfur is contained. Furthermore, a) one or more kinds selected from the structural group consisting of an unsubstituted or substituted, chain, branched, and cyclic structure that does not contain an epoxy group and has a carbon-carbon double bond as an essential constituent unit. Selected from the group consisting of a compound having an aliphatic hydrocarbon unit having a structure of 3 to 24 carbon atoms and an oxygen number of 0 to 5 and the above-mentioned c) vinylalkylsilane having a carbon-carbon double bond. More preferably.

  Specific examples of the compound (a) are preferably 1-hexene, 1-heptene, 1-octene, 1 because it tends to increase the handleability of vinyl compounds or to facilitate the removal of excess compounds. -Nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, cyclopentene, cyclohexene, methylcyclohexene, norbornene, vinylcyclohexane Is mentioned. On the other hand, specific examples of the preferred compound (c) include vinyltrimethylsilane, vinylethyldimethylsilane, vinyldiethylmethylsilane, and vinyltriethylsilane, because the excess compound tends to be easily distilled off. Preferably, a vinyl trimethylsilane is mentioned.

  Next, carbon represented by an average composition formula (14) including at least an organohydrogensilicon represented by the general formula (12) and a silicone having a carbon-carbon double bond represented by the general formula (13). Example of specific method for producing epoxy-modified silicone by adding silicone having carbon double bond and vinyl compound <B> including compound <A> having carbon-carbon double bond and epoxy group explain.

  The epoxy-modified silicone of the present invention is a silicone having a carbon-carbon double bond represented by the general formula (13) with respect to the SiH unit of the organohydrogen silicone represented by the general formula (12). A silicone having a carbon-carbon double bond represented by the above average composition formula (14) and a vinyl compound <B> including a compound <A> having a carbon-carbon double bond and an epoxy group; It can manufacture by adding by the method of the following [manufacturing method 1] or [manufacturing method 2].

[Production Method 1]
Average composition formula containing at least a silicone having a carbon-carbon double bond represented by general formula (13) with respect to the SiH unit of the organohydrogensilicon represented by general formula (12) in the presence of a hydrosilylation catalyst. One step of simultaneously adding a mixture of a silicone having a carbon-carbon double bond represented by (14) and a vinyl compound <B> containing a compound <A> having a carbon-carbon double bond and an epoxy group A method comprising the steps of:

[Production Method 2]
In the presence of a hydrosilylation catalyst, a vinyl compound <B> containing a compound <A> having a carbon-carbon double bond and an epoxy group is added to the SiH unit of the organohydrogensilicon represented by the general formula (12). And then adding a silicone having a carbon-carbon double bond represented by the average composition formula (14) including at least a silicone having a carbon-carbon double bond represented by the general formula (13) And a second step. The method comprises two steps.

  The epoxy-modified silicone of the present invention can be produced by any of the above [Production Method 1] and [Production Method 2]. In the case of [Production Method 2], the first step and the second step may be performed continuously, and after the additional product obtained in the first step is separated and recovered, the second step is performed. Also good.

  As described above, in the epoxy-modified silicone of the present invention, the ratio of the content [WB] of the compound represented by the general formula (2) to the content [WA] of the compound represented by the general formula (1) [ The value of [WB] / [WA] is preferably 0.5 or more and 6.00 or less. The value of [WB] / [WA] has a carbon-carbon double bond represented by the general formula (13) added to the SiH unit of the organohydrogensilicon represented by the general formula (12). It is obtained by controlling the amount of the carbon-carbon double bond of silicone and the amount of the carbon-carbon double bond of the compound <A> having a carbon-carbon double bond and an epoxy group within the ranges described below. be able to.

  In [Production Method 1], in the presence of a hydrosilylation catalyst, the carbon represented by the general formula (13) with respect to the number of moles (r1) of the SiH unit of the organohydrogensilicon represented by the general formula (12). -The number of moles (r2) of the carbon-carbon double bond of the silicone having a carbon double bond and the average composition formula (14) other than the silicone having a carbon-carbon double bond represented by the general formula (13) The number of moles (r3) of the carbon-carbon double bond of the silicone having a carbon-carbon double bond represented, and the carbon-carbon double bond of the compound <A> having a carbon-carbon double bond and an epoxy group The number of moles (r4) and the number of moles of carbon-carbon double bonds (r5) of the vinyl compound <B> other than the compound <A> having a carbon-carbon double bond and an epoxy group are represented by the following formula (A1). ~ Simultaneously satisfies formula (A5) As the circumference, preferably an addition reaction coexist Each compound to the reaction system.

0.05 ≦ r2 / r1 ≦ 0.75 Formula (A1)
0.15 ≦ r4 / r1 Formula (A2)
0 ≦ r3 Formula (A3)
0 ≦ r5 Formula (A4)
1 ≦ (r2 + r3 + r4 + r5) / r1 ≦ 5 Formula (A5)
When the value of [r2 / r1] is less than 0.05 or exceeds 0.75, or when the value of [r4 / r1] is less than 0.15, the value of [WB] / [WA] May be less than 0.10 or may exceed 2.00, which is not preferable because the cured product obtained by using the epoxy-modified silicone of the present invention tends to have insufficient crack resistance or adhesion. .

  In addition, when the value of [(r2 + r3 + r4 + r5) / r1] is less than 1, a part of the SiH unit of the organohydrogensilicon represented by the general formula (12) remains unreacted and the epoxy group is opened. An epoxy-modified silicone containing a high molecular weight is generated in the ring, making it impossible to produce the epoxy-modified silicone stably and with good reproducibility. Epoxy-modified silicone undergoes a modification reaction and a viscosity change during storage, so that the storage stability When the epoxy-modified silicone is cured, there is a possibility that inconveniences such as a decrease in crack resistance may occur.

  On the other hand, when the value of [(r2 + r3 + r4 + r5) / r1] exceeds 5, the hydrosilylation reaction catalyst may be stabilized and the hydrosilylation reaction rate may be reduced. The epoxy-modified silicone obtained by the method of the present invention may be reduced. This is not preferable because the load of the process of separating and recovering the epoxy-modified silicone from the reaction mixture is increased.

  Further, a silicone having a carbon-carbon double bond represented by an average composition formula (14) other than a silicone having a carbon-carbon double bond represented by the general formula (13), a carbon-carbon double bond, and The vinyl compound <B> other than the compound <A> having an epoxy group is a compound that can be used as necessary, and the number of moles (r3) and (r5) of the carbon-carbon double bond is 0. It is the above numerical value.

From the viewpoint of producing an epoxy-modified silicone having excellent reproducibility, transparency, light resistance, heat resistance, crack resistance and adhesion, r1 to r5 are represented by the following formulas (A3), (A4), and It is preferable that the formulas (A6) to (A8) are simultaneously satisfied,
0.10 ≦ r2 / r1 ≦ 0.70 Formula (A6)
0.20 ≦ r4 / r1 Formula (A7)
0 ≦ r3 Formula (A3)
0 ≦ r5 Formula (A4)
1 ≦ (r2 + r3 + r4 + r5) / r1 ≦ 2 Formula (A8)

More preferably, r1 to r5 simultaneously satisfy the following formula (A3), formula (A4), and formula (A9) to formula (A11),
0.15 ≦ r2 / r1 ≦ 0.65 Formula (A9)
0.25 ≦ r4 / r1 Formula (A10)
0 ≦ r3 Formula (A3)
0 ≦ r5 Formula (A4)
1 ≦ (r2 + r3 + r4 + r5) /r1≦1.8 Formula (A11)

More preferably, r1 to r5 simultaneously satisfy the following formula (A9), formula (A10), and the following formula (A12) to formula (A14).
0.15 ≦ r2 / r1 ≦ 0.65 Formula (A9)
0.25 ≦ r4 / r1 Formula (A10)
r3 = 0 Formula (A12)
r5 = 0 Formula (A13)
1 ≦ (r2 + r4) /r1≦1.5 Formula (A14)

  In [Production Method 2], in the first step in the presence of a hydrosilylation catalyst, carbon-carbon 2 is used relative to the number of moles of SiH units (s1) of the organohydrogensilicone represented by the general formula (12). The number of moles of carbon-carbon double bond (s2) of compound <A> having a heavy bond and an epoxy group, and the carbon of vinyl compound <B> other than compound <A> having a carbon-carbon double bond and an epoxy group -The number of moles of carbon double bonds (s3) and the compounds satisfy the following formulas (B1) to (B3) at the same time, the compounds are added together in the reaction system, and then in the second step, The number of moles (s4) of the carbon-carbon double bond of the silicone having a carbon-carbon double bond represented by (s1) to (s3) and the general formula (5), and the general formula (5) Silicone having carbon-carbon double bond The number of moles (s5) of the carbon-carbon double bond of the silicone having a carbon-carbon double bond represented by the other average composition formula (6) satisfies the following formulas (B4) to (B6) at the same time. It is preferable to add each compound in the reaction system in such a range.

0 ≦ s3 Formula (B1)
0.25 ≦ s2 / s1 ≦ 0.95 (formula (B2))
0.25 ≦ (s2 + s3) /s1≦0.95 Expression (B3)
0 ≦ s5 Formula (B4)
0.05 ≦ s4 / s1 Formula (B5)
1.0 ≦ (s4 + s5) / [s1− (s2 + s3)] ≦ 3.0 Formula (B6)
When the value of [s2 / s1] is less than 0.25 or exceeds 0.95, or when the value of [(s2 + s3) / s1] is less than 0.25 or exceeds 0.95, or When the value of [s4 / s1] is less than 0.05, the value of [WB] / [WA] may be less than 0.10 or may exceed 2.00. It is not preferable because the cured product obtained by use tends to have insufficient crack resistance or adhesion.

  When the value of {(s4 + s5) / [s1- (s2 + s3)]} is less than 1.0, a part of the SiH unit of the organohydrogensilicon represented by the general formula (4) is unreacted. As a result, an epoxy-modified silicone containing a high molecular weight product is generated by ring opening of an epoxy group, and it becomes impossible to stably produce the epoxy-modified silicone with good reproducibility. In addition, there is a possibility that inconveniences such as a decrease in storage stability due to a change in viscosity and a decrease in crack resistance when epoxy-modified silicone is cured are not preferable. On the other hand, when the value of {(s4 + s5) / [s1- (s2 + s3)]} exceeds 3, the hydrosilylation reaction catalyst may be stabilized and the hydrosilylation reaction rate may be reduced. Since the load of the process of separating and recovering the epoxy-modified silicone from the reaction mixture containing the resulting epoxy-modified silicone tends to increase, it is not preferable.

  Here, an average composition formula other than a vinyl compound <B> other than the compound <A> having a carbon-carbon double bond and an epoxy group, and a silicone having a carbon-carbon double bond represented by the general formula (13) The silicone having a carbon-carbon double bond represented by (14) is a compound that can be used as necessary, and the number of moles (s3) and (s5) of the carbon-carbon double bond is 0. It is the above numerical value.

From the viewpoint of producing an epoxy-modified silicone having excellent reproducibility, transparency, light resistance, heat resistance, crack resistance, and adhesion, s1 to s5 are represented by the following formulas (B1), (B4), and It is preferable that the formulas (B7) to (B10) are satisfied at the same time,
0 ≦ s3 Formula (B1)
0.30 ≦ s2 / s1 ≦ 0.90 (formula (B7))
0.30 ≦ (s2 + s3) /s1≦0.90 Formula (B8)
0 ≦ s5 Formula (B4)
0.10 ≦ s4 / s1 Formula (B9)
1.0 ≦ (s4 + s5) / [s1− (s2 + s3)] ≦ 2.0 Formula (B10)
It is more preferable that s1 to s5 satisfy the following formula (B1), formula (B4), and formula (B11) to formula (B14) at the same time,
0 ≦ s3 Formula (B1)
0.35 ≦ s2 / s1 ≦ 0.85 Formula (B11)
0.35 ≦ (s2 + s3) /s1≦0.85 Formula (B12)
0 ≦ s5 Formula (B4)
0.15 ≦ s4 / s1 Formula (B13)
1.0 ≦ (s4 + s5) / [s1− (s2 + s3)] ≦ 1.8 Formula (B14)
More preferably, s1 to s5 satisfy the following formula (B11) and formulas (B15) to (B18) at the same time.

s3 = 0 Formula (B15)
0.35 ≦ s2 / s1 ≦ 0.85 Formula (B11)
s5 = 0 Formula (B16)
0.15 ≦ s4 / s1 ≦ 0.97 (formula (B17))
1.0 ≦ s4 / (s1-s2) ≦ 1.5 Formula (B18)
In the absence of a hydrosilylation catalyst, the hydrosilylation reaction between the SiH unit of the organohydrogensilicon represented by the general formula (4) and the compound having a carbon-carbon double bond does not proceed. In the production method, a hydrosilylation catalyst is used.

  As the hydrosilylation catalyst that can be used in the present invention, a conventionally known catalyst can be used. Examples of such a hydrosilylation catalyst include a simple substance of Group 8 metal, a metal solid supported on a support such as alumina, silica, and carbon black, a salt of the metal, Examples include complexes. Of these, platinum, rhodium, and ruthenium, which are metals of Group 8 of the periodic table, which have high hydrosilylation reaction activity and are unlikely 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 number of moles in terms of metal atom of the catalyst used in the hydrosilylation reaction is the same as that before 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 total number of SiH units of the organohydrogensilicone is preferably 1 / 1,200 times or less, more preferably 1 / 6,000 times or less, and 1 / 25,000 times or less. More preferably. On the other hand, from the viewpoint of performing the hydrosilylation reaction at a reproducible rate, the number of moles in terms of metal atom of the catalyst used when the hydrosilylation reaction is performed is the total number of SiH units of the organohydrogensilicone before the hydrosilylation reaction. On the other hand, it is preferably 1 / 5,000,000 times or more, more preferably 1 / 1,000,000 times or more, and further preferably 1 / 800,000 times or more.

  It is represented by an average composition formula (14) including at least a silicone having a carbon-carbon double bond represented by the general formula (13) with respect to the SiH unit of the organohydrogen silicone represented by the general formula (12). The amount of the hydrosilylation catalyst used when adding the silicone having a carbon-carbon double bond and the vinyl compound <B> containing the compound <A> having a carbon-carbon double bond and an epoxy group is as described above. If it is in the range, it is not necessary to be constant, and it may be changed at the initial stage of the reaction or during the reaction.

  In the present invention, the reaction temperature for the hydrosilylation reaction is represented by an average composition formula (14) including at least the organohydrogensilicone used and the silicone having a carbon-carbon double bond represented by the general formula (13). Type and molecular weight of silicone having carbon-carbon double bond, or type of vinyl compound <B> including compound <A> having carbon-carbon double bond and epoxy group, further batch type, semi Although it varies depending on the reaction mode such as batch type or continuous type, the range of 0 ° C. or higher and 250 ° C. or lower is preferable and the range of 10 ° C. or higher and 200 ° C. or lower is more preferable in terms of increasing the reaction rate and completing the reaction efficiently. The range of 20 ° C. or higher and 150 ° C. or lower is 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.

  In carrying out the hydrosilylation reaction in the present invention, it is possible to remove the reaction heat by the hydrosilylation reaction, 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 to use a solvent.

  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 solvent used is an organohydrogen silicone, a silicone having a carbon-carbon double bond represented by an average composition formula (13) containing at least a silicone having a carbon-carbon double bond represented by the general formula (13). Depending on the type and molecular weight, or the type of vinyl compound <B> including the compound <A> having a carbon-carbon double bond and an epoxy group, and further, the reaction mode such as batch, semi-batch, or continuous However, in general, in the hydrosilylation reaction, the mass of the solvent relative to the total mass of the mixture is in the range of 0.1% by mass to 99.9% by mass, preferably in the range of 10% by mass to 95% by mass. More preferably, it is the range of 20 mass% or more and 90 mass% or less.

  In the present invention, the hydrosilylation reaction is preferably performed in an inert gas atmosphere such as nitrogen, helium, or argon.

  In the present invention, the reaction method for carrying out the hydrosilylation reaction is not particularly limited. For example, an organohydrogen silicone used in the present invention and a silicone having a carbon-carbon double bond represented by the general formula (13) are used. At least one or more kinds consisting of a silicone having a carbon-carbon double bond represented by at least an average composition formula (14) and a vinyl compound <B> containing a compound <A> having a carbon-carbon double bond and an epoxy group Examples thereof include a method in which the compound is reacted sequentially, continuously or all at once by a method of one or a combination of two or more selected from the group consisting of batch, semi-batch and continuous.

  As a method for adding the hydrosilylation catalyst, in the case of following the [Production Method 1], an organohydrogen silicone of the general formula (12) and a silicone having a carbon-carbon double bond represented by the general formula (13) are used. A vinyl compound <B> including a compound <A> having at least a silicone having a carbon-carbon double bond and a carbon-carbon double bond and an epoxy group represented by the average composition formula (14) including at least It is preferred to premix the solvent and finally add the hydrosilylation catalyst. In the case of following [Production Method 2], a vinyl compound <B> containing an organohydrogensilicone of general formula (12), a compound <A> having a carbon-carbon double bond and an epoxy group, and further if necessary The solvent is premixed, and finally the hydrosilylation catalyst is added to carry out the first step, followed by the average composition formula including at least the silicone having a carbon-carbon double bond represented by the general formula (13) ( It is preferable to carry out the second step by adding a silicone having a carbon-carbon double bond represented by 14). In the second step, a hydrosilylation catalyst can be additionally added. In that case, the average composition formula (14) including at least a silicone having a carbon-carbon double bond represented by the general formula (13) is used. It is preferable to add a hydrosilylation catalyst after adding the silicone having the carbon-carbon double bond represented. Thus, the method of adding the hydrosilylation catalyst to the reaction system at the end is a preferable method because it may be effective in preventing the reaction system from gelling due to side reactions.

  A vinyl compound <B> containing a compound <A> having a carbon-carbon double bond and an epoxy group and a carbon-carbon double bond represented by the general formula (13) with respect to the SiH unit of the organohydrogensilicone When the silicone having a carbon-carbon double bond represented by the average composition formula (14) including at least the silicone having is added by a hydrosilylation reaction, the moisture in the system may affect. 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, particularly preferably 0.05% by mass or less, and most preferably 0.01% by mass or less.

  Prior to separating and collecting the epoxy-modified silicone from the reaction mixture, the following post-treatment operation is performed from the viewpoint of suppressing the modification of the epoxy-modified silicone when separating and collecting the epoxy-modified silicone from the reaction mixture. It is a method preferably used. That is, a) the alcohol is brought into contact with or mixed with the reaction mixture to reduce or eliminate the unreacted SiH units, and b) a conventionally known hydrosilylation catalyst deactivator or deactivator is reacted with the reaction mixture. C) deactivating or deactivating the catalyst by contacting or mixing, and c) contacting, mixing, or circulating the reaction mixture with the adsorbent to remove a metal component such as a hydrosilylation catalyst or a coloring component. Examples of post-processing methods include a process of removing or reducing adsorption, or d) a process of a combination of these.

  Examples of the alcohols used in a) include at least one alcohol having a structure selected from a chain, branched or cyclic structure group having 1 to 4 carbon atoms. Examples of the deactivator and deactivator of the hydrosilylation catalyst used in b) include sulfur-containing compounds such as dodecyl mercaptan and 2-mercaptobenzothiazole, acetonitrile, acrylonitrile, 2-pentenylolyl, 3-pentenenitrile, Nitriles such as benzonitrile, 1-heptin, 1-octyne, 1-decyne, 3-methyl-1-pentyne, 2-propyn-1-ol, 3-butyn-1-ol, 2-pentyn-1-ol, 4-pentyn-1-ol, 4-pentyn-2-ol, 2-methyl-3-butyn-1-ol, 3-methyl-1-pentyn-3-ol, 3-methyl-1-hexyn-3-ol 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, 1-ethynyl-1-cyclohe Sanol, 2,5-dimethyl-3-hexyne-2,5-diol, 1,1-dimethyl-2-propynylamine, 3-methyl-3- (trimethylsiloxy) -1-butyne, dimethyl-bis (1,1 -Dimethyl-2-propinoxy) -silane, 3-methyl-3- (trimethylsiloxy) -1-pentyne, 3,5-dimethyl-3- (trimethylsiloxy) -1-hexyne, 3-ethyl-3- (trimethyl And acetylene compounds such as (siloxy) -1-pentyne, methylpropionate, and ethylpropionate. Moreover, as an adsorbent which adsorbs, removes, or reduces metal components such as hydrosilylation catalyst used in c) and coloring components, for example, activated carbon, celite, silica gel, alumina powder, ion exchange resin, and the like can be given.

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

Moreover, the temperature at the time of performing these post-treatments is preferably in the range of 0 ° C. or higher and 200 ° C. or lower, more preferably in the range of 5 ° C. or higher and 150 ° C. or lower, more preferably 10 from the viewpoint of suppressing the modification of the epoxy-modified silicone. It is in the range of not less than 100 ° C and particularly preferably not less than 15 ° C and not more than 100 ° C. If it is in the said range, it is not necessary to be constant temperature, and it is also possible to change temperature on the way.
The mixture containing the epoxy-modified silicone obtained by the post-treatment is subjected to a step of separating the epoxy-modified silicone, and the epoxy-modified silicone of the present invention is recovered.

  Hereinafter, in the method for producing an epoxy-modified silicone of the present invention, the compound having a carbon-carbon double bond and the deactivator or deactivator of the hydrosilylation catalyst used as necessary are collectively referred to as a low boiling point compound. The solvents used as necessary and the alcohols used as necessary in the treatment operation for reducing or eliminating unreacted SiH units are collectively referred to as volatile compounds.

  Next, a method for separating the epoxy-modified silicone from the mixture containing the epoxy-modified silicone will be described.

  The method for separating the epoxy-modified silicone from the mixture containing the epoxy-modified silicone is not particularly limited. For example, the low-boiling compound and the volatile compound are distilled off from the mixture containing the epoxy-modified silicone to recover the epoxy-modified silicone. In the case where the epoxy-modified silicone is a compound having high volatility, a method of separating and recovering the epoxy-modified silicone by distillation, and the like can be mentioned.

  The temperature at which the epoxy-modified silicone is separated from the mixture containing the epoxy-modified silicone varies depending on the types of the epoxy-modified silicone, the low-boiling compound and the volatile compound, preferably from the viewpoint of suppressing the modification of the epoxy-modified silicone. The range is from 0 ° C to 200 ° C, more preferably from 5 ° C to 150 ° C, still more preferably from 10 ° C to 140 ° C, and particularly preferably from 15 ° C to 130 ° C. If it is in the said range, the temperature at the time of isolate | separating an epoxy-modified silicone from the mixture containing an epoxy-modified silicone does not need to be a fixed temperature, and it is also possible to change temperature on the way.

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

  The process of separating the epoxy-modified silicone from the mixture containing the epoxy-modified silicone is effective even when the viscosity of the mixture containing the epoxy-modified silicone is increased by reducing the content of low-boiling compounds and volatile compounds. It is preferable to use an apparatus capable of separating a boiling compound and a volatile compound. Examples of such devices 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 obtained by the production method of the present invention is derived from the vinyl compound <B> including the compound <A> having a carbon-carbon double bond and an epoxy group, which was used when the epoxy-modified silicone was produced. In some cases, a low boiling point compound such as a compound having a carbon-carbon double bond or a solvent and / or a volatile compound may remain.

  Here, the “compound having a carbon-carbon double bond” in the present invention will be described. The compound having a carbon-carbon double bond in the present invention refers to a compound other than silicone and having one or more carbon-carbon double bonds in the molecule. Therefore, vinyl silicone and epoxy-modified silicone are not included even if they have a carbon-carbon double bond in the molecule.

As a compound having such a carbon-carbon double bond, for example,
(I) excess or unreacted vinyl compound added to be subjected to hydrosilylation reaction,
(Ii) Impurities having a carbon-carbon double bond contained in the vinyl compound added for use in the hydrosilylation reaction,
(Iii) The by-product etc. which the carbon-carbon double bond in the vinyl compound added in order to use for hydrosilylation reaction produced | generated internal rearrangement in hydrosilylation reaction, etc. are mentioned.

  As a specific example of the impurity having a carbon-carbon double bond contained in the vinyl compound added for use in the (ii) hydrosilylation reaction, it may be contained in, for example, 4-vinylcyclohexene oxide. 4-epoxyethylcyclohexene etc. are mentioned.

  The (iii) by-product produced by the internal rearrangement of the carbon-carbon double bond in the vinyl compound added to be used for the hydrosilylation reaction during the hydrosilylation reaction includes the type of vinyl compound used, Although depending on the hydrosilylation reaction conditions, for example, as a by-product when 1-hexene is used as the vinyl compound, 2-hexene, 3-hexene, etc. are used, and, for example, vinylcyclohexane is used as the vinyl compound. Examples of by-products include ethylidenylcyclohexane.

  Furthermore, as the vinyl compound, for example, (a-1) 4-vinylcyclohexene oxide, (a-2) 1-methyl-4-isopropenylcyclohexene oxide, (a-3) 1,4-dimethyl-4-vinyl When epoxycycloalkanes having a vinyl group such as cyclohexene oxide and (a-4) vinyl norbornene oxide are used, by-products corresponding to (a-1) to (a-4) are respectively (b- 1) 4-ethylidenylcyclohexene oxide, (b-2) 1-methyl-4-isoproperenyl cyclohexene oxide, (b-3) 1,4-dimethyl-4-ethylidenylcyclohexene oxide, (b- 4) Ethylidenyl norbornene oxide and the like. Further, for example, when (a-5) 1,2-epoxy-5-hexene is used as a compound having a carbon-carbon double bond and an epoxy group, carbon in the vinyl compound corresponding to (a-5) -By-products generated by internal rearrangement of the carbon double bond during the hydrosilylation reaction include 1,2-epoxy-4-hexene, 1,2-epoxy-3-hexene, 1,2-epoxy- 2-hexene and the like can be mentioned.

  Since the heat-resistant discoloration and light resistance of the cured product using the epoxy-modified silicone obtained by the production method of the present invention tend to be improved, the total amount of low-boiling compounds remaining in the epoxy-modified silicone is 2% by mass or less. Preferably, it is 1.5% by mass or less, more preferably 1% by mass or less, still more preferably 0.75% by mass or less, and 0.5% by mass or less. It is particularly preferable that it is 0.3% by mass or less.

  In the present invention, when the low-boiling compound is composed of two or more components, the total amount of low-boiling compounds remaining in the epoxy-modified silicone in the present invention is the total value of each component remaining in the epoxy-modified silicone. Means.

  The total amount of low-boiling compounds remaining in the epoxy-modified silicone should be small, but reducing the total amount of low-boiling compounds to 0 reduces coloring and discoloration compared to the time and labor required. The effect to do is small. Therefore, from the viewpoint of cost effectiveness, it is realistic that the total amount of low boiling point compounds remaining in the epoxy-modified silicone is reduced to about 0.003% by mass.

  Of the low boiling point compounds remaining in the epoxy-modified silicone, the residual amount of the compound having a carbon-carbon double bond is based on the epoxy-modified silicone from the viewpoint of coloring or reducing discoloration of the cured product by light or heat. It is preferably 1.5% by mass or less, more preferably 1% by mass or less, still more preferably 0.75% by mass or less, still more preferably 0.5% by mass or less, It is particularly preferably 0.3% by mass or less, and most preferably 0.1% by mass or less.

In the present invention, when the compound having a carbon-carbon double bond is composed of two or more components, the residual amount of the compound having a carbon-carbon double bond remaining in the epoxy-modified silicone in the present invention is: It means the total value of each component remaining in the epoxy-modified silicone.
Of the compounds having a carbon-carbon double bond remaining in the epoxy-modified silicone, the residual amount of the compound having an epoxy group is the same as that of the epoxy-modified silicone from the viewpoint of coloring or reducing discoloration of the cured product by light or heat. It is preferably 1% by mass or less, more preferably 0.6% by mass or less, still more preferably 0.3% by mass or less, and even more preferably 0.1% by mass or less. Preferably, it is particularly preferably 0.05% by mass or less.
Here, when there are two or more compounds having a carbon-carbon double bond and an epoxy group remaining in the epoxy-modified silicone, the residual amount of the compound having a carbon-carbon double bond and an epoxy group is: It means the total amount of each remaining component.

  Further, among the compounds having a carbon-carbon double bond remaining in the epoxy-modified silicone, the carbon-carbon 2 of the compound <A> having a carbon-carbon double bond and an epoxy group added for use in the hydrosilylation reaction. The residual amount of the by-product generated by causing internal dislocations in the double bond is preferably 0.5% by mass or less based on the epoxy-modified silicone from the viewpoint of reducing the coloration or discoloration of the cured product due to light or heat. It is more preferably 0.3% by mass or less, further preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less.

  Here, the carbon-carbon double bond of the compound <A> having a carbon-carbon double bond and an epoxy group, which was added to be used for the hydrosilylation reaction remaining in the epoxy-modified silicone, was generated due to internal rearrangement. When there are two or more by-products, the residual amount of by-products generated by the internal rearrangement of the carbon-carbon double bond of the vinyl compound having an epoxy group added for use in the hydrosilylation reaction Means the total amount of each remaining component.

  In addition, in the compound <A> having a carbon-carbon double bond and an epoxy group added for use in the hydrosilylation reaction, the carbon-carbon 2 between the compounds already having the carbon-carbon double bond and the epoxy group is included. When a compound having a different heavy bond position is contained, the compound having a different carbon-carbon double bond position is a compound having a carbon-carbon double bond and an epoxy group in the present invention <A>. Of carbon-carbon double bonds are not included in by-products generated by internal rearrangement.

  Further, in the present invention, when the hydrosilylation catalyst deactivator or deactivator is brought into contact with or mixed with the reaction mixture to deactivate or deactivate the catalyst, the hydrosilylation used in the treatment is used. The residual amount of the catalyst deactivator or deactivator is preferably 0.5% by mass or less based on the epoxy-modified silicone from the viewpoint of reducing coloring or discoloration of the cured product due to light or heat. It is more preferably 3% by mass or less, still more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less.

  In the present invention, when the hydrosilylation catalyst deactivator or deactivator comprises two or more components, the hydrosilylation catalyst deactivator or deactivator remaining in the epoxy-modified silicone of the present invention The residual amount of means the total value of each component remaining in the epoxy-modified silicone.

  The epoxy-modified silicone obtained in the present invention is used for processing to reduce or eliminate unreacted SiH units by contacting or mixing the solvent or reaction mixture used in producing the epoxy-modified silicone with alcohols. Volatile compounds may remain. When making the epoxy-modified silicone of the present invention a cured product, from the viewpoint of suppressing the generation of bubbles in the cured product, the total amount of volatile compounds remaining in the epoxy-modified silicone of the present invention is 1% by mass or less. Preferably, it is 0.1 mass% or less, more preferably 0.05 mass% or less, and particularly preferably 0.005 mass% or less.

  In the present invention, when the volatile compound is composed of two or more components, the total amount of the volatile compound remaining in the epoxy-modified silicone in the present invention is the total of each component remaining in the epoxy-modified silicone. Mean value.

  The total amount of volatile compounds remaining in the epoxy-modified silicone should be small, but reducing the total amount of remaining volatile compounds to 0 reduces the coloration and discoloration compared to the time and labor required. The effect to do is small. Therefore, from the viewpoint of cost effectiveness, it is realistic that the total amount of volatile compounds remaining in the epoxy-modified silicone is reduced to about 0.001% by mass.

  The epoxy-modified silicone obtained by the present invention may contain a residue of a catalyst such as a hydrosilylation catalyst used when producing the epoxy-modified silicone, or a metal component eluted from the reaction apparatus. For example, when SUS316 alloy is used, metal elements such as Fe, Ni, Cr, and Mo may be eluted. These metals, especially transition metal components, may affect the light resistance of the cured product when the epoxy-modified silicone obtained by the present invention is cured. From the viewpoint of maintaining the light resistance of the cured product at a high level, the total amount of transition metal components corresponding to Groups 3 to 11 of the periodic table contained in the epoxy-modified silicone of the present invention is 20 ppm in terms of elements. Is preferably 10 ppm or less, more preferably 7 ppm or less.

  When it is necessary to reduce the content of the transition metal component, the method includes, for example, passing the reaction solution after the hydrosilylation reaction through an adsorbent such as activated carbon, silica gel, alumina powder, ion exchange resin, etc. An example of the method for adsorbing and removing is used. Also, for example, considering the amount of the transition metal element eluted from the reaction apparatus in the step of producing the epoxy-modified silicone of the present invention, the total amount of transition metal components contained in the epoxy-modified silicone of the present invention is below the above range. As a preferable method, a method of reducing the amount of the catalyst used for the hydrosilylation reaction is also exemplified.

  When producing the epoxy-modified silicone of the present invention, the epoxy-modified silicone having at least one epoxy group in the molecule that can be mixed with the epoxy-modified silicone obtained by the method (a-1). The silicone is an epoxy-modified silicone represented by the average composition formula (22).

[Wherein R ² is the same as described above. Each R ⁸ independently represents hydrogen, H) an unsubstituted or substituted aliphatic hydrocarbon unit having one or more types of structures selected from the group consisting of chain, branched and cyclic structures. A monovalent aliphatic organic group having a number of 1 to 24 and an oxygen number of 0 to 5, I) an unsubstituted or substituted aromatic hydrocarbon unit, which is unsubstituted or substituted as necessary A monovalent fragrance having an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of chain, branched and cyclic, having 6 to 24 carbon atoms and 0 to 5 oxygen atoms A group organic group, J) having an aliphatic and / or aromatic hydrocarbon unit composed of one or more structures selected from the group consisting of an unsubstituted or substituted chain, branched, and cyclic structure. 5 or more and 26 or less, oxygen number is 0 or more and 5 or less, and silicon number is 1 Represents at least one organic group selected from the group consisting of a monovalent organic group. ]

  In addition, W1-W10 in average composition formula (22) can be mixed with the epoxy-modified silicone obtained by the method (a-1), and has at least one epoxy group in the molecule. The number of moles of each structural unit present in 1 mole of the modified silicone is represented, w1 to w10 each have a value of 0 or more, and the value of (w2 + w3 + w4 + w6 + w7 + w9) is at least 1 or more.

Moreover, when said w1-w10 each satisfy | fills following numerical formula (12)-numerical formula (14) simultaneously, said w1-w4 and w8-w10 are selected from the range which satisfy | fills numerical formula (15).
w5 + w6 + w7 ≠ 0 (12)
w8 + w9 ≠ 0 (13)
w10 ≠ 0 Expression (14)
0 ≦ w1 + w2 + w3 + w4 ≦ w8 + w9 + 2 × w10 + 2 Expression (15)

Furthermore, when said w8-w10 each satisfy | fills following numerical formula (16) and numerical formula (17) simultaneously, said w1-w4 is selected from the range which satisfy | fills numerical formula (18).
w8 + w9 = 0 Formula (16)
w10 = 0 Formula (17)
0 ≦ w1 + w2 + w3 + w4 ≦ 2 (18)

Moreover, when said w8-w10 each satisfy | fills following Numerical formula (13) and Numerical formula (17) simultaneously, said w1-w4, w8, and w9 are selected from the range which satisfy | fills Numerical formula (19).
w8 + w9 ≠ 0 (13)
w10 = 0 Formula (17)
0 ≦ w1 + w2 + w3 + w4 ≦ w8 + w9 + 2 Formula (19)

Furthermore, when said w8-w10 each satisfy | fills following numerical formula (16) and numerical formula (14) simultaneously, said w1-w4 and w10 are selected from the range which satisfy | fills numerical formula (20).
w8 + w9 = 0 Formula (16)
w10 ≠ 0 Expression (14)
0 ≦ w1 + w2 + w3 + w4 ≦ 2 × w10 + 2 (20)

  The structure of the epoxy-modified silicone having at least one epoxy group in the molecule that can be mixed with the epoxy-modified silicone obtained by the method (a-1) used in the present invention is not particularly limited. Any structure such as linear, branched, cyclic, ladder-like, and cage-like, or a mixture of two or more of these may be used. Further, each structural unit may have a block-like chain structure, may be randomly dispersed, or a mixture thereof.

In the present invention, each R ⁸ independently has hydrogen, H) an unsubstituted or substituted aliphatic hydrocarbon unit composed of one or more structures selected from a chain, branched and cyclic structure group. A monovalent aliphatic organic group having 1 to 24 carbon atoms and 0 to 5 oxygen atoms, I) an unsubstituted or substituted aromatic hydrocarbon unit, which is unsubstituted or substituted as necessary A monovalent valence having 6 to 24 carbon atoms and 0 to 5 oxygen atoms, which has an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of chain, branched and cyclic structures. An aromatic organic group, J) an unsubstituted or substituted carbon having an aliphatic and / or aromatic hydrocarbon unit composed of one or more structures selected from the group consisting of chain, branched and cyclic structures The number is from 5 to 26, the oxygen number is from 0 to 5, and It represents at least one organic group selected from the group consisting of monovalent organic groups having 1 silicon.
These may be organic groups in which one kind or two or more kinds are mixed.

H) an aliphatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted, substituted, and chain-like, branched, and cyclic structures, having 1 to 24 carbon atoms and an oxygen number Examples of the monovalent aliphatic organic group in which is from 0 to 5 include, for example,
(H-1) Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl A chain organic group comprising an aliphatic hydrocarbon such as a group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group,
(H-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, a norbornyl group,
(H-3) Organic groups containing an ether bond such as methoxyethyl, ethoxyethyl, propoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, and the like.

From the one or more structures selected from the group consisting of a chain, a branch and a ring, which are unsubstituted or substituted aromatic hydrocarbon units of the above I), which are unsubstituted or substituted as necessary Examples of the monovalent aromatic organic group having an aliphatic hydrocarbon unit and having 6 to 24 carbon atoms and 0 to 5 oxygen atoms include, for example, phenyl group, tolyl group, xylyl group, benzyl group, α -A methyl styryl group, 3-methyl styryl group, 4-methyl styryl group etc. are mentioned.
The number of carbon atoms is 5 or more, having an aliphatic and / or aromatic hydrocarbon unit having one or more types of structures selected from the group consisting of an unsubstituted or substituted chain, branched and cyclic structure of J) above Examples of the monovalent organic group having 26 or less, an oxygen number of 0 or more and 5 or less, and a silicon number of 1 include organic groups represented by the following general formula (23) and general formula (24).
—CH ₂ —CH—SiR ⁴ ₃ (23)
—CH (CH ₃ ) —SiR ⁴ ₃ (24)
[Wherein R ⁴ is the same as described above. ]
In the above R ⁸ , as long as it is within the range of the carbon number and oxygen number, and if necessary, the silicon number, an organic group is a hydroxyl unit, an alkoxy unit, an acyl unit, a carboxyl unit, an alkenyloxy unit, an acyloxy unit. In addition, halogen atoms such as fluorine and chlorine, ester bonds, and hetero atoms such as nitrogen, phosphorus and sulfur other than oxygen atoms and silicon atoms may be contained. These may be organic groups in which one kind or two or more kinds are mixed.

Epoxy having at least one epoxy group in the molecule represented by the average composition formula (22), which can be mixed with the epoxy-modified silicone obtained by the method (a-1) used in the present invention. As the modified silicone, the epoxy-modified silicone of the present invention does not exhibit a modification reaction or viscosity change during storage, exhibits excellent storage stability, and at the same time exhibits excellent crack resistance after curing. The total molar amount of each structural unit having hydrogen as R ⁸ is preferably 2% or less, more preferably 1.5% or less, relative to the total molar amount of the structural units (w1 + w2 + w3 + w4 + w5 + w6 + w7 + w8 + w9 + w10). It is more preferably 1% or less, and particularly preferably 0.5% or less.

On the other hand, at least one epoxy group in the molecule represented by the average composition formula (22) that can be mixed with the epoxy-modified silicone obtained by the method (a-1) used in the present invention. The epoxy-modified silicone R ⁸ has an epoxy-modified silicone represented by the average composition formula (22) because the epoxy-modified silicone of the present invention tends to have good light resistance or increase stability during storage. Hydroxyl unit, alkoxy unit, acyl unit, carboxyl unit, alkenyloxy unit, acyloxy unit, halogen atom such as fluorine or chlorine, ester bond, oxygen atom or silicon relative to the total number of moles of all Si units in silicone The total number of moles of silicon atoms bonded to organic groups containing heteroatoms such as nitrogen, phosphorus, and sulfur, excluding atoms, is It is preferably 10% or less, more preferably 1% or less, and still more preferably not contained at all.

Similarly, the light resistance of the epoxy-modified silicone represented by the average composition formula (3) containing at least the compounds represented by the general formula (1) and the general formula (2) of the present invention is improved, and heat discoloration is achieved. In the molecule represented by the average composition formula (22), which can be mixed with the epoxy-modified silicone obtained by the method (a-1) used in the present invention. R ⁸ of the epoxy-modified silicone having one or more epoxy groups is preferably selected from the group consisting of (H-1) and (H-2), and (H-1) and (H-2). ) Is more preferably an organic group selected from the group consisting of 1 to 8 carbon atoms and 0 oxygen atoms, and (H-1) and (H-2) have 1 to 8 carbon atoms. , Selected from the group consisting of oxygen number 0 A substituted chain organic group is more preferred, and a methyl group is particularly preferred.

  Epoxy having at least one epoxy group in the molecule represented by the average composition formula (22), which can be mixed with the epoxy-modified silicone obtained by the method (a-1) used in the present invention. The molecular weight of the modified silicone is particularly limited as long as it can satisfy the requirements of the epoxy-modified silicone represented by the average composition formula (3) including at least the compound represented by the general formula (1) and the general formula (2) of the present invention. However, the number average molecular weight of the epoxy-modified silicone is preferably in the range of 400 or more and 1,000,000 or less, and 500 or more and 500,000 or less from the viewpoint of improving the handleability and processability due to fluidity and the like. The range of 500 to 100,000 is more preferable, and the range of 500 to 50,000 is more preferable. Preferably, and particularly preferably from 500 to 10,000.

  In the present invention, the epoxy-modified silicone obtained by the method of (a-1), the general formula (1), the general formula (2), and an epoxy modified having at least one epoxy group in other molecules About each weight ratio at the time of mixing the epoxy modified silicone obtained by the method of (a-1) with at least 1 sort (s) or more of epoxy modified silicone selected from the group which consists of silicone, this invention There is no particular limitation as long as the requirements of the epoxy-modified silicone represented by the average composition formula (3) including at least the compound represented by the general formula (1) and the general formula (2) can be satisfied.

  In the present invention, the epoxy-modified silicone obtained by the method of (a-1), the general formula (1), the general formula (2), and an epoxy modified having at least one epoxy group in other molecules The method of mixing at least one epoxy-modified silicone selected from the group consisting of silicones, or the method of mixing the epoxy-modified silicones obtained by the method (a-1) may be uniformly mixed. There is no particular limitation as long as it is possible, and a method in which the compound to be mixed is uniformly mixed using a solvent in which the compound is mixed, if necessary, and then the solvent is distilled off, or a method in which the compound to be mixed in a bulk is uniformly mixed Alternatively, a method based on a combination of these can be used. Among these, it is preferable to use a method of uniformly mixing in bulk because the labor and energy for removing volatile components such as solvents can be reduced.

  Prior to the mixing operation, reducing the low-boiling compounds remaining in the compound to be mixed in advance is represented by the general formula (1) and the general formula (2) of the present invention stably and with good reproducibility. Since the light resistance and heat discoloration resistance of the epoxy-modified silicone represented by the average composition formula (3) containing at least the compound can be enhanced, it is used as a preferred method. The total amount of the low boiling compounds remaining in the compound to be mixed is preferably reduced to 2% by mass or less, more preferably 1.5% by mass or less, and 1% by mass or less. Is more preferably 0.75% by mass or less, particularly preferably 0.5% by mass or less, and most preferably reduced to 0.3% by mass or less.

  As a device that can be used for mixing, a conventionally known vertical or horizontal mixer, stirrer, extruder, in-line mixer, or the like can be used. Examples of such devices include vertical stirring tanks, surface renewal stirring tanks, surface renewal twin screw kneaders, single or biaxial horizontal stirrers, short or twin screw extruders, and spiral slant mixers. , A container rotating and shaking mixer, a container rotating mixer, and the like.

  In the present invention, the epoxy-modified silicone obtained by the method of (a-1), the general formula (1), the general formula (2), and an epoxy modified having at least one epoxy group in other molecules The temperature at which the operation of mixing at least one epoxy-modified silicone selected from the group consisting of silicones or mixing the epoxy-modified silicones obtained by the method (a-1) is the kind of the compound used. Although it varies depending on the case, it is preferably in the range of −20 ° C. to 200 ° C., preferably in the range of 0 ° C. to 150 ° C., more preferably in the range of 10 ° C. to 100 ° C. More preferably, it is the range of 10 degreeC or more and 80 degrees C or less. If it is in the said range, the temperature at the time of performing mixing operation does not need to be a fixed temperature, and it is also possible to change temperature in the middle.

  In the present invention, the epoxy-modified silicone obtained by the method of (a-1), the general formula (1), the general formula (2), and an epoxy modified having at least one epoxy group in other molecules The atmosphere when performing the operation of mixing at least one epoxy-modified silicone selected from the group consisting of silicones, or mixing the epoxy-modified silicones obtained by the method of (a-1) is air, or Inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide, lower saturated hydrocarbon gas having 1 to 4 carbon atoms, gas atmosphere selected from the group consisting of air, distribution and reduced pressure Alternatively, it can be performed under pressure, bubbling, or a combination of these. These gases can be used as one kind or a mixture of two or more kinds. Among these, a preferable gas is air, or the above-mentioned inert gas, a lower saturated hydrocarbon gas having 1 to 4 carbon atoms, more preferably air or the above-mentioned inert gas, and more preferably a dew point. Is dry air of −30 ° C. or lower, or nitrogen.

  In the present invention, the epoxy-modified silicone obtained by the method of (a-1), the general formula (1), the general formula (2), and an epoxy modified having at least one epoxy group in other molecules The time for performing the operation of mixing at least one epoxy-modified silicone selected from the group consisting of silicones or mixing the epoxy-modified silicones obtained by the method (a-1) is the type of compound used. Although it varies depending on the molecular weight, it is usually in the range of 0.1 second to 24 hours, preferably 1 second to 10 hours, more preferably 1 minute to 1 hour in order to suppress the modification of the epoxy-modified silicone. .

The epoxy-modified silicone obtained by the present invention has excellent transparency that can be used in applications requiring transparency, and also has excellent light resistance, heat resistance, heat discoloration, and crack resistance, adhesion. Since it has solder reflow resistance, it is preferably used as a sealing material for light emitting elements. In addition, since the epoxy-modified silicone of the present invention gives a hardened product having excellent dimensional stability, it is a spectacle lens, a lens for optical equipment, a lens for picking up CDs or DVDs, a lens for automobile headlamps, a lens for projectors. It is also suitably used as a lens material. Furthermore, it can also be used as various optical members such as optical fibers, optical waveguides, optical filters, optical adhesives, die bonding agents, underfill materials for optical semiconductor elements, optical disk substrates, display substrates, antireflection coatings and other coating materials. It is.
When used in the above-mentioned applications, the epoxy-modified silicone obtained by the present invention is an epoxy resin and / or a curing agent for epoxy resin, a curing accelerator, a cationic polymerization catalyst, a modifying agent, an antioxidant, and a thermal stability as necessary. It is used as a curable resin composition appropriately mixed with conventionally known additives such as an agent, a silane coupling agent, an antifoaming agent, a colorant, a phosphor, a light diffusing agent, an inorganic filler, and a heat conductive filler.

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

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

The hydrogenation reaction of the aromatic ring of the aromatic glycidyl ether can be carried out by a conventionally known method using, for example, a ruthenium-based catalyst or a rhodium-based catalyst.
Examples of the alicyclic epoxy resins include conventionally known compounds such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate and 2,2-bis (hydroxymethyl) -1-butanol. , 2-epoxy-4- (2-oxiranyl) cyclohexane adduct, bis (3,4-epoxycyclohexylmethyl) adipate, and the like.

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

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

  The amount of the epoxy resin used is preferably 0.1 to 100 parts by weight, more preferably 1 to 100 parts by weight, and still more preferably 1 to 80 parts by weight with respect to 100 parts by weight of the epoxy-modified silicone obtained by the present invention. It is.

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

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

  The amount of the epoxy resin curing agent used is preferably in the range of 0.1 to 3 equivalents, more preferably 0.5 to 2 equivalents with respect to the epoxy groups of the epoxy-modified silicone obtained by the present invention. Preferably it is 1 mass part-200 mass parts with respect to 100 mass parts, More preferably, it is 10 mass parts-150 mass parts, More preferably, it is the range of 20 mass parts-100 mass parts.

  The curable resin composition obtained by using the epoxy-modified silicone obtained by the present invention may contain a curing accelerator as necessary. Examples of the curing accelerator used include imidazole compounds, quaternary ammonium salts, phosphonium salts, amine compounds, aluminum chelate compounds, organic phosphine compounds, metal carboxylates and acetylacetone chelate compounds. These curing accelerators can be used as one kind or a mixture of two or more kinds.

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

  The blending amount of these curing accelerators is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, from the viewpoint of increasing the curing rate with respect to 100 parts by mass of the epoxy-modified silicone. It is especially preferable that it is 0.1 mass part or more. On the other hand, from the viewpoint of moisture resistance and coloration of the cured product, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, and 1 part by mass or less. It is particularly preferred.

  The epoxy-modified silicone of the present invention can be made into a curable resin composition by blending a conventionally known cationic polymerization catalyst.

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

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

  The blending amount of these cationic polymerization catalysts is usually preferably 0.001 parts by mass or more and more preferably 0.005 parts by mass or more from the viewpoint of increasing the curing rate with respect to 100 parts by mass of the epoxy-modified silicone. Preferably, it is 0.01 mass part or more. On the other hand, from the viewpoint of moisture resistance and coloration of the cured product, it is preferably 10 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.5 parts by mass or less, and 0.2 It is particularly preferable that the amount is not more than part by mass.

  As a curing agent and a curing catalyst suitably used for the epoxy-modified silicone of the present invention, in addition to the above, for example, aluminum trisacetyl as described in JP-A-4-84444 and JP-A-2005-93569 A combination of an aluminum compound having an organic group such as acetonate and a compound having an OH group or an alkoxy group directly bonded to Si, such as diphenylsilanediol and diphenyldiethoxysilane.

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

The blending amount of the polyols containing two or more hydroxyl groups in one molecule is preferably 0.1 parts by mass or more from the viewpoint of improving the adhesion with respect to 100 parts by mass of the epoxy-modified silicone, and has heat resistance and moisture resistance. From this viewpoint, it is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, still more preferably 3 to 20 parts by weight, and particularly preferably 3 to 10 parts by weight.
In the curable resin composition of the present invention, various silane coupling agents can be used for the purpose of improving physical properties such as adhesion. Suitable silane coupling agents for the present invention include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldisilane. Ethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Ethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, N- (2-aminoethyl) aminomethyltrimethoxysilane N- (2-aminoethyl) (3-aminopropyl) trimethoxysilane, N- (2-aminoethyl) (3-aminopropyl) triethoxysilane, N- (2-aminoethyl) (3-aminopropyl) Methyldimethoxysilane, N- [N ′-(2-aminoethyl) (2-aminoethyl)] (3-aminopropyl) trimethoxysilane, 2- (2-aminoethyl) thioethyltriethoxysilane, 2- ( 2-aminoethyl) thioethylmethyldiethoxysilane, 3- (N-phenylamino) propyltrimethoxysilane, 3- (N-cyclohexylamino) propyltrimethoxysilane, (N-phenylaminomethyl) trimethoxysilane, ( N-phenylaminomethyl) methyldimethoxysilane, (N-cyclohexylaminomethyl) triet Sisilane, (N-cyclohexylaminomethyl) methyldiethoxysilane, piperazinomethyltrimethoxysilane, piperazinomethyltriethoxysilane, 3-piperazinopropyltrimethoxysilane, 3-piperazinopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3 -Mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3- (trimethoxysilyl) propyl succinic anhydride, 3- (triethoxy Ryl) propyl succinic anhydride, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, vinyltrimethoxysilane , Vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylvinyldimethoxysilane, Methylvinyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylcyclo Hexyldimethoxysilane, methylcyclohexyldiethoxysilane, methylcyclopentyldimethoxysilane, methylcyclopentyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3 -Methacryloxypropyltriethoxysilane and the like. Moreover, the partial condensate of these silane coupling agents can also be used.

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

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

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

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

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

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

The method for laminating the semiconductor material on the substrate is not particularly limited, but for example, MOCVD method, HDVPE method, liquid phase growth method and the like are used.
Examples of the structure of the light emitting element include a homojunction having a MIS junction, a PN junction, and a PIN junction, a heterojunction, and a double heterostructure. A single or multiple quantum well structure may also be used.

  A light emitting diode can be manufactured by sealing a light emitting element using the light emitting element sealing material which consists of curable resin composition containing the epoxy modified silicone of this invention. In this case, the light-emitting element can be sealed only with the light-emitting element sealing material, but it is also possible to use another sealing material in combination. When other sealing materials are used in combination, after sealing with the light emitting device sealing material obtained using the epoxy-modified silicone obtained by the present invention, the periphery is sealed with other sealing materials, or other It is also possible to seal the periphery with a light emitting element sealing material obtained by using the epoxy-modified silicone obtained by the present invention. Examples of the other sealing material include an epoxy resin, a silicone resin, an acrylic resin, a urea resin, an imide resin, and glass.

  As a method of sealing a light emitting element with a light emitting element sealing material obtained by using the epoxy-modified silicone of the present invention, for example, a light emitting element sealing material is previously injected into a mold mold, and the light emitting element is fixed thereto. Examples include a method of curing after immersing the prepared lead frame and the like, a method of injecting a light emitting element sealing material into a mold having the light emitting element inserted therein, and a method of curing. At this time, examples of the method for injecting the light-emitting element sealing material include injection by a dispenser, transfer molding, injection molding, and the like. Other sealing methods include a method in which a light emitting device sealing material is dropped onto the light emitting device, and stencil printing, screen printing, or a method of applying and curing through a mask, a cup in which the light emitting device is disposed in the lower part, etc. For example, a method of injecting a light-emitting element sealing material with a dispenser or the like and curing it.

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

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

  The light-emitting diode obtained by using the epoxy-modified silicone of the present invention includes, for example, a backlight such as a liquid crystal display, illumination, various sensors, a light source such as a printer and a copying machine, an instrument light source for vehicles, a signal lamp, a display lamp, and a display It is useful as a light source for a planar light emitter, a display, a decoration, various lights, and the like.

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

(1) Calculation of content ratio of compound represented by general formula (1) and compound represented by general formula (2) ([WB] / [WA]) [WA] and [WB] in the present invention The values correspond to the structures of general formula (1) and general formula (2) obtained by measuring with epoxy-modified silicone matrix-assisted ionization time-of-flight mass spectrometry (hereinafter, MALDI-TOF / MS). The intensity of the peak corresponding to the total mass of the mass to be added and the mass 23 of sodium is expressed.

  In addition, the mass corresponding to each structure of the general formula (1) and the general formula (2) is the mass of the isotope of each element when the elements constituting the structure have isotopes. The value calculated using the mass of the isotope having the highest abundance.

  In the present invention, when a plurality of peaks corresponding to the general formulas (1) and (2) are present, the content [WA] of the compound having the structure of the general formula (1) and the general formula (2) The content [WB] of the compound represented by the formula was the total peak intensity corresponding to each structure.

However, the peak having an intensity of 3% or less with respect to the maximum intensity of the peak corresponding to the total mass of the mass corresponding to each structure of the general formula (1) and the general formula (2) and the mass 23 of sodium. The intensity of was excluded from the calculation of the total peak intensity.
The measurement method of MALDI-TOF / MS was performed by the following method.

<Measurement method of MALDI-TOF / MS>
A solution in which 0.1 g of epoxy-modified silicone is dissolved in 100 mL of tetrahydrofuran at room temperature and a solution in which 10 mg of dithranol is dissolved in 1 mL of tetrahydrofuran are uniformly mixed at a volume ratio of 1: 1 at room temperature. Thus, solution a was prepared. Next, 1 μL of solution a was dropped on a sample plate on which 1 μL of 10 mg sodium iodide dissolved in 10 mL of acetone was placed, the solvent was evaporated at room temperature, and measurement was performed with MALDI-TOF / MS under the following measurement conditions. went.

(Measurement condition)
Equipment: Shimadzu AXIMA CFRplus
Laser: Nitrogen laser (337 nm)
Detector type: Linear mode Ion detection: Positive ion (positive mode)
Integration count: 500 times

(2) 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 is performed according to the method described below, and the integrated value calculated from the obtained spectrum pattern is analyzed to contain hydrogen alkyl units, dialkylsiloxy units, and the like. The fraction was calculated as a percentage.
Next, ¹ H-NMR measurement was performed according to the method described below, and the abundance of alkylsiloxy units having each organic group was calculated as a percentage based on the integral value calculated from the obtained spectrum pattern.

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

  Subsequently, gel permeation chromatography (GPC) measurement of the epoxy-modified silicone was performed according to the method described below, and the number average molecular weight obtained was the molecular weight per mole of the epoxy-modified silicone represented by the average composition formula (3). The total number of moles of each unit constituting the epoxy-modified silicone represented by the average composition formula (3) 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 (3) and the abundance of each unit, the epoxy-modified silicone 1 represented by the average composition formula (3) The number of moles of each unit constituting the mole was calculated.

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

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

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

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

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

(3) Content of component having molecular weight of 800 or less and content of component having molecular weight of 10,000 or more in epoxy-modified silicone Calculated by analyzing the elution curve obtained by the above-mentioned gel permeation chromatography (GPC) measurement. .
Specifically, in the elution curve, the ratio of the peak area (peak area 2) corresponding to a molecular weight of 800 or less to the total area (peak area 1) surrounded by the peak based on the epoxy-modified silicone and the baseline is expressed as follows. It was expressed by a numerical value expressed as a percentage [that is, a numerical value represented by (peak area 2) / (peak area 1) × 100 (%)].

  The content of components having a molecular weight of 10,000 or more in the epoxy-modified silicone represented by the average composition formula (3) is the elution start point and elution of the epoxy-modified silicone in the elution curve obtained by the above GPC measurement. A numerical value representing the ratio of the peak area (peak area 3) corresponding to a molecular weight of 10,000 or more to the elution peak area (peak area 1) obtained by linking the end points [ie, (peak area 3) / (Peak area 1) × 100 (%))].

(4) Measurement of amount of low boiling point compound and amount of volatile compound 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 measuring about 0.5 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) Metal Element Content The platinum content was analyzed using a quadrupole ICP mass spectrometer (manufactured by Thermo Elemental: X7-ICP-MS).

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

(8) Heat resistance Tg of the pulverized cured product was measured with a DSC220C manufactured by Seiko Instruments Inc. under a temperature rising rate of 10 ° C / min, and used as an index of heat resistance. Tg of the cured product was 120 ° C. or more, ◯, 100 ° C. or more and less than 120 ° C., and less than 100 ° C.

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

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

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

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

In addition, the adhesion is evaluated by the number of occurrences of peeling between the cured resin and the polyphthalamide resin mold, and ◎ indicates that peeling did not occur for 40 cycles or more, and peeling occurred for 20 cycles or more and less than 40 cycles. The case where peeling occurred in less than 5 cycles was evaluated as x.
In addition, it was set as xx when the crack has already generate | occur | produced at the time of completion | finish of hardening and evaluation is impossible.

(12) Resistance to solder reflow The produced optical semiconductor elements (20 pieces) were left at 85 ° C. and 85 RH% for 24 hours, and the absorbed optical semiconductor elements were subjected to a solder reflow oven (preheat 150 ° C. × 100 seconds + reflow [maximum temperature 260 C]]), and the number of cracks, housing materials, optical semiconductor elements, or elements peeled off from the lead electrode after passing twice (a moisture absorption reflow test) was confirmed. Solder reflow resistance was evaluated based on the number of cracks, housing agent, or cracks. 1 or less was evaluated as ◎, 2 or more and 4 or less as ○, and 5 or more as ×.

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

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

At the start of the reaction, the ratio between the total number of SiH units (r1) of the organohydrogensilicone and the number of moles (r2) of the carbon-carbon double bonds of the silicone having a coexisting carbon-carbon double bond ( The value of r2 / r1) is 0.62, the total number of SiH units of the organohydrogensilicone (r1), and the carbon-carbon 2 of the compound <A> having a coexisting carbon-carbon double bond and epoxy group. The value of the ratio (r4 / r1) to the number of moles of heavy bonds (r4) is 0.49, and the total number of carbon-carbon double bonds in the added compound relative to the total number of moles of SiH units in the organohydrogensilicone. The number of moles was 1.11 times.
In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms was 1 / 259,459 times the total number of moles of SiH units in the organohydrogensilicone before the hydrosilylation reaction. .

  After the cooling was completed, 954 g of acetonitrile (reagent manufactured by Wako Pure Chemical Industries, Ltd.) dehydrated and purified under dry nitrogen was added to the reaction solution, and the mixture was stirred for 2 hours under an atmospheric pressure dry nitrogen atmosphere, and then the stirring was stopped. . Next, 790 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd .: granular) heated and dried at 150 ° C. for 3 hours under a dry nitrogen stream was added, and activated carbon treatment was performed for 48 hours under a dry nitrogen atmosphere.

  After the activated carbon treatment was completed, the activated carbon was filtered using a PTFE membrane filter having a pore size of 1 μm to collect the filtrate. Furthermore, the activated carbon separated by the above operation was washed with 1500 g of 1,4-dioxane (reagent manufactured by Wako Pure Chemical Industries, Ltd.) purified by dehydration distillation under nitrogen, and the activated carbon was similarly filtered using a membrane filter. The washing liquid was collected and mixed with the previously obtained filtrate. 1,4-dioxane and acetonitrile were distilled off from the collected liquid mixture using an evaporator at a heating temperature of 40 ° C. under reduced pressure to obtain an epoxy-modified silicone-containing component.

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

The obtained [epoxy-modified silicone 1a] had a structure represented by the following average composition formula (H-1) having a number average molecular weight of 2,100.
(Me ₂ YSiO _1/2 ) _7.91 (MeZSiO _2/2 ) _7.91 (Me [VCHO] SiO _2/2 ) _4.83 (H-1)
[Wherein Y in the average composition formula (H-1) represents a divalent organic group represented by —CH ₂ —CH ₂ —, and Z represents a bond with a divalent hydrocarbon group Y. In addition, (Me [VCHO] SiO _2/2 ) represents a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit by an anti-markovnikov by a hydrosilylation reaction. ]

Since no unreacted SiH unit was detected, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.
The compound represented by the general formula (1) contained in the [epoxy-modified silicone 1a] is a compound represented by the following chemical formula (25) (total mass number 759 with the mass of sodium), while the general formula The compound represented by (2) is a compound represented by the following chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 2.10, average composition The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in formula (3) was 0.383. The content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 1a] was 20.4%, and the content of components having a molecular weight of 10,000 or more was 26.5%. Furthermore, the epoxy value of [epoxy-modified silicone 1a] was 0.23, the transition metal component contained was only platinum, and the content of this component was 0.5 ppm in terms of platinum element.

As the volatile compound remaining in the [epoxy-modified silicone 1a], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.001 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.
[Epoxy-modified silicone 1a] was not observed to increase in molecular weight even when stored at 25 ° C. for 1 week.

[Production Example 2 of Epoxy-Modified Silicone]
2 L reactor was used, 40 g of 1,3,5,7-tetramethylcyclotetrasiloxane purified by dehydration distillation was used, 1,3-divinyltetramethyldisiloxane was not used, dehydration distillation purification 108 g of the prepared 4-vinylcyclohexene oxide, 590 g of 1,4-dioxane purified by dehydration distillation, 1,4-diplatinum tetramethyldisilicone complex containing 500 ppm platinum in terms of platinum element After adding 1 g of dioxane solution and heating in an oil bath heated to 70 ° C. while stirring under an atmospheric pressure dry nitrogen atmosphere, the temperature of the inner solution exceeded 65 ° C., and then 500 ppm of platinum in terms of platinum element was added. 1 g of 1,4-dioxane solution of platinum divinyltetramethyldisilicone complex contained was added, Except that the reaction time is 5 hours, in the same manner as Production Example of the epoxy-modified silicone 1], was carried out hydrosilylation reaction.

  At this time, the temperature of the reaction solution was between 65 ° C and 100 ° C. After the reaction for 5 hours, the hydrosilylation reaction proceeded quantitatively, and no unreacted SiH unit was detected. Subsequently, the heating of the reaction solution was stopped and the mixture was allowed to cool to room temperature.

  After cooling was completed, 590 g of acetonitrile (reagent manufactured by Wako Pure Chemical Industries, Ltd.) purified by dehydration distillation under dry nitrogen was added to the reaction solution, and the mixture was stirred for 2 hours under an atmospheric pressure dry nitrogen atmosphere, and then the stirring was stopped. . Next, 800 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd .: granular) heated and dried at 150 ° C. for 3 hours under a dry nitrogen stream was added, and activated carbon treatment was performed for 48 hours under a dry nitrogen atmosphere.

  After the activated carbon treatment was completed, the activated carbon was filtered using a PTFE membrane filter having a pore size of 1 μm to collect the filtrate. Furthermore, the activated carbon separated by the above operation was washed with 900 g of 1,4-dioxane (reagent manufactured by Wako Pure Chemical Industries, Ltd.) purified by dehydration distillation under nitrogen, and the activated carbon was similarly filtered using a membrane filter. The washing liquid was collected and mixed with the previously obtained filtrate. 1,4-dioxane and acetonitrile were distilled off from the collected liquid mixture using an evaporator at a heating temperature of 40 ° C. under reduced pressure to obtain an epoxy-modified silicone-containing component.

  A part of the 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 40 ° C. and a pressure of 0.2 kPa at a flow rate of 10 ml / min in terms of atmospheric pressure inside. Epoxy-modified silicone with reduced low-boiling compounds by reducing the low-boiling compounds by reducing the low-boiling compounds by introducing heat treatment under reduced pressure for 24 hours, and then stopping the introduction of dry nitrogen and subsequently heating to 280 ° C. to 300 ° C. at a pressure of 20 Pa Got. This operation was repeated for the remaining epoxy-modified silicone obtained by distilling off 1,4-dioxane and acetonitrile obtained above to obtain 50 g of [epoxy-modified silicone 2a] with reduced low boiling point compounds.

  [Epoxy-modified silicone 2a] thus obtained had a structure represented by the following chemical formula (H-2). Moreover, the epoxy value was 0.54, the transition metal component contained was only platinum, and the content of the component was 0.5 ppm in terms of platinum element.

As the volatile compound remaining in the [epoxy-modified silicone 2a], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.001 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.
[Epoxy-modified silicone 2a] was not observed to increase in molecular weight even when stored at 25 ° C. for 1 week.

[Production Example 3 of Epoxy-Modified Silicone]
In the hydrosilylation reaction, 84 g of 1,3-divinyltetramethyldisiloxane purified by dehydration distillation was used, 69.31 g of 4-vinylcyclohexene oxide purified by dehydration distillation was used, [Epoxy-modified silicone production example 1], except that 930 g of dioxane was used, the hydrosilylation reaction was performed for 110 hours, and the solution was cooled after the hydrosilylation reaction, and then added to 930 g of acetonitrile. Thus, 187 g of [epoxy-modified silicone 3a] with reduced low boiling point compounds was obtained.

  When sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction progressed quantitatively, and no unreacted SiH unit was detected.

At the start of the reaction, the ratio between the total number of SiH units (r1) of the organohydrogensilicone and the number of moles (r2) of the carbon-carbon double bonds of the silicone having a coexisting carbon-carbon double bond ( The value of r2 / r1) is 0.68, and the total number of SiH units of the organohydrogensilicone (r1) and the carbon-carbon 2 of the compound <A> having a coexisting carbon-carbon double bond and epoxy group. The ratio (r4 / r1) to the number of moles of heavy bonds (r4) is 0.42, and the total number of carbon-carbon double bonds in the added compound with respect to the total number of moles of SiH units in the organohydrogensilicone. The number of moles was 1.10 times.
Further, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms was 1 / 259,459 times the total number of moles of SiH units of the organohydrogensilicone before the hydrosilylation reaction. It was.

[Epoxy-modified silicone 3a] obtained had a structure represented by the following average composition formula (H-3) having a number average molecular weight of 2,400.
(Me ₂ YSiO _1/2 ) _9.97 (MeZSiO _2/2 ) _9.97 (Me [VCHO] SiO _2/2 ) _4.75 (H-3)
Here, in the average composition formula (H-3), Y represents a divalent organic group represented by —CH ₂ —CH ₂ —, and Z represents a bond with a divalent hydrocarbon group Y. In addition, (Me [VCHO] SiO _2/2 ) represents a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit by an anti-markovnikov by a hydrosilylation reaction. ]

Since no unreacted SiH unit was detected, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.
The compound represented by the general formula (1) contained in the [epoxy-modified silicone 3a] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 3.03, The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.400. The content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 1a] was 17.0%, and the content of components having a molecular weight of 10,000 or more was 34.9%. Furthermore, the epoxy value of [epoxy-modified silicone 3a] was 0.20, the transition metal component contained was only platinum, and the content of this component was 0.5 ppm in terms of platinum element.

As the volatile compound remaining in [epoxy-modified silicone 3a], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.002 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.
[Epoxy-modified silicone 3a] was not observed to increase in molecular weight even when stored at 25 ° C. for 1 week.

[Production Example 4 of Epoxy-Modified Silicone]
Use of 1.5 L reactor, 80 g of 1,3-divinyltetramethyldisiloxane purified by dehydration distillation during hydrosilylation reaction, 76.24 g of 4-vinylcyclohexene oxide purified by dehydration distillation 860 g of 1,4-dioxane purified by dehydration and distillation, 1 g of 1,4-dioxane solution of platinum divinyltetramethyldisilicone complex containing 500 ppm of platinum in terms of platinum element, hydrosilylation The hydrosilylation reaction was carried out in the same manner as in [Epoxy-modified silicone production example 1] except that the reaction time was 100 hours.

  At the start of the reaction, the ratio between the total number of SiH units (r1) of the organohydrogensilicone and the number of moles (r2) of the carbon-carbon double bonds of the silicone having a coexisting carbon-carbon double bond ( The value of r2 / r1) is 0.65, the total number of SiH units of the organohydrogensilicone (r1), and the carbon-carbon 2 of the compound <A> having a coexisting carbon-carbon double bond and epoxy group. The value of the ratio (r4 / r1) to the number of moles of heavy bonds (r4) is 0.46, and the total number of carbon-carbon double bonds in the added compound with respect to the total number of moles of SiH units of the organohydrogensilicone. The number of moles was 1.11 times.

  Further, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms was 1 / 235,872 times the total number of moles of SiH units of the organohydrogensilicone before the hydrosilylation reaction. . Further, when sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction proceeded quantitatively, and unreacted SiH units were not detected.

  After completion of the hydrosilylation reaction, 86 g of benzonitrile (reagent manufactured by Wako Pure Chemical Industries, Ltd.) purified by dehydration distillation under dry nitrogen was added to the reaction solution while maintaining the heating temperature, and the reaction solution was kept under an atmospheric pressure dry nitrogen atmosphere for 2 hours. After stirring, stirring was stopped and cooled to room temperature.

  Next, 300 g of activated carbon (manufactured by Wako Pure Chemical Industries, Ltd .: granular) heated and dried at 150 ° C. for 3 hours under a dry nitrogen stream was added, and the activated carbon treatment was performed for 48 hours under a dry nitrogen atmosphere. After the activated carbon treatment was completed, the activated carbon was filtered using a PTFE membrane filter having a pore size of 1 μm to collect the filtrate. Furthermore, the activated carbon separated by the above operation was washed with 1500 g of 1,4-dioxane (reagent manufactured by Wako Pure Chemical Industries, Ltd.) purified by dehydration distillation under nitrogen, and the activated carbon was similarly filtered using a membrane filter. The washing liquid was collected and mixed with the previously obtained filtrate. 1,4-dioxane was distilled off from the recovered mixture using an evaporator at a heating temperature of 40 ° C. under reduced pressure to obtain an epoxy-modified silicone-containing component.

The obtained epoxy-modified silicone-containing component was introduced into the inside at a flow rate of 10 mL / min in terms of atmospheric pressure, while the temperature was 40 ° C. and the pressure was 0. The low boiling compound was distilled off in a glass tube oven at 2 kPa to obtain an epoxy-modified silicone-containing component with reduced low boiling compound. This operation was repeated for the remaining epoxy-modified silicone obtained by distilling off the 1,4-dioxane obtained above to obtain 208 g of [epoxy-modified silicone 4a] with reduced low boiling point compounds.
[Epoxy-modified silicone 4a] obtained had a structure represented by the following average composition formula (H-4) having a number average molecular weight of 2,300.

(Me ₂ YSiO _1/2 ) _9.05 (MeZSiO _2/2 ) _9.05 (Me [VCHO] SiO _2/2 ) _4.98 (H-4)
[Wherein Y in the average composition formula (H-4) represents a divalent organic group represented by —CH ₂ —CH ₂ —, and Z represents a bond with a divalent hydrocarbon group Y. In addition, (Me [VCHO] SiO _2/2 ) represents a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit by an anti-markovnikov by a hydrosilylation reaction. ]

Since no unreacted SiH unit was detected, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.
The compound represented by the general formula (1) contained in the [epoxy-modified silicone 4a] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 2.44. The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.39. The content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 4a] was 17.7%, and the content of components having a molecular weight of 10,000 or more was 30.7%. Furthermore, the epoxy value of [epoxy modified silicone 4a] was 0.22, and the transition metal component contained was only platinum, and the content of the component was 0.5 ppm in terms of platinum element.

As the volatile compound remaining in [epoxy-modified silicone 4a], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.002 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.
[Epoxy-modified silicone 4a] showed no increase in molecular weight even when stored at 25 ° C. for 1 week.

[Production Example 5 of Epoxy-Modified Silicone]
A 2.5 L reactor with reflux condenser, thermometer and stirrer is replaced with dry nitrogen. Under dry nitrogen conditions, 80 g of 1,3,5,7-tetramethylcyclotetrasiloxane (reagent manufactured by Shin-Etsu Chemical Co., Ltd.) purified by dehydration distillation under dry nitrogen in the above apparatus, dehydration distillation purification under dry nitrogen After charging 104.5 g of 4-vinylcyclohexene oxide (reagent manufactured by Aldrich) and 855 g of 1,4-dioxane (reagent manufactured by Wako Pure Chemical Industries, Ltd.) purified by dehydration distillation under nitrogen, the reaction was performed under an atmospheric pressure dry nitrogen atmosphere. The mixture was heated in an oil bath heated to 70 ° C. with stirring.
After the temperature of the inner solution exceeds 65 ° C., 2.5 g of a 1,4-dioxane solution of platinum divinyltetramethyldisilicone complex containing 500 ppm of platinum in terms of platinum element is added to the solution under dry nitrogen. The hydrosilylation reaction was carried out for 4 hours. At this time, the temperature of the reaction solution was between 65 ° C and 100 ° C. After the reaction for 4 hours, 4-vinylcyclohexene oxide was not detected in the reaction solution. Thereafter, 50 g of 1,3-divinyltetramethyldisiloxane (reagent manufactured by Shin-Etsu Chemical Co., Ltd.), which was subsequently purified by dehydration and distillation under dry nitrogen, was added to the reaction solution, followed by stirring at 70 ° C. while stirring in an atmospheric pressure dry nitrogen atmosphere. The hydrosilylation reaction was performed for 36 hours by heating in an oil bath, and the reaction liquid was stopped from heating and allowed to cool to room temperature. At this time, the temperature of the reaction solution was between 65 ° C and 75 ° C. As a result of analyzing the solution before stopping the heating, the hydrosilylation reaction progressed quantitatively, and unreacted SiH units were not detected.

  In this production example, no vinyl compound <B> other than the compound <A> having a carbon-carbon double bond and an epoxy group is used, and the total number of SiH units of organohydrogensilicone at the start of the reaction (s1 ) And the number of moles of carbon-carbon double bonds (s2) of the compound <A> having a carbon-carbon double bond and an epoxy group (s2 / s1) is 0.63, at the start of the reaction Of the silicone having a carbon-carbon double bond added after the reaction of the total number of SiH units (s1) of the organohydrogensilicone with the compound <A> having a carbon-carbon double bond and an epoxy group is completed. The value of the ratio (s4 / s1) to the number of moles of carbon-carbon double bonds (s4) (s4 / s1) was 0.40, and the value of [s4 / (s1-s2)] was 1.10.

  In addition, the number of moles of the catalyst used to start the hydrosilylation reaction in terms of metal atoms was 1 / 207,568 times the total number of moles of SiH units in the organohydrogensilicone before the hydrosilylation reaction. It was.

  After the cooling was completed, the reaction solution was treated in the same glass tube oven as [Epoxy-modified silicone production example 1], except that 855 g of acetonitrile dehydrated and purified under dry nitrogen was used. 200 g of [epoxy-modified silicone 5a] with reduced low boiling point compounds was obtained.

The obtained [epoxy-modified silicone 5a] had a structure represented by the following average composition formula (H-5) having a number average molecular weight of 1,200.
(Me ₂ YSiO _1/2 ) _2.82 (MeZSiO _2/2 ) _2.82 (Me [VCHO] SiO _2/2 ) _4.18 (H-5)
Here, in the average composition formula (H-5), Y represents a divalent organic group represented by —CH ₂ —CH ₂ —, and Z represents a bond with a divalent hydrocarbon group Y. In addition, (Me [VCHO] SiO _2/2 ) represents a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit by an anti-markovnikov by a hydrosilylation reaction. ]

Since no unreacted SiH unit was detected, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.
The compound represented by the general formula (1) contained in the [epoxy-modified silicone 5a] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is a compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 0.66, The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.29. The content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 5a] was 31.8%, and the content of components having a molecular weight of 10,000 or more was 10.8%. Furthermore, the epoxy value of [epoxy-modified silicone 5a] was 0.35, the transition metal component contained was only platinum, and the content of this component was 0.5 ppm in terms of platinum element.

As the volatile compound remaining in [epoxy-modified silicone 5a], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.001 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.
[Epoxy-modified silicone 5a] showed no increase in molecular weight even when stored at 25 ° C. for 1 week.

[Production Example 6 of Epoxy-Modified Silicone]
Use of 1.5 L reactor, 72 g of 1,3-divinyltetramethyldisiloxane purified by dehydration distillation during hydrosilylation reaction, 90.1 g of 4-vinylcyclohexene oxide purified by dehydration distillation 850 g of 1,4-dioxane purified by dehydration and distillation, 2 g of 1,4-dioxane solution of platinum divinyltetramethyldisilicone complex containing 500 ppm platinum in terms of platinum element, hydrosilylation The hydrosilylation reaction was carried out in the same manner as in [Epoxy-modified silicone production example 1] except that the reaction time was 90 hours.

  At the start of the reaction, the ratio between the total number of SiH units (r1) of the organohydrogensilicone and the number of moles (r2) of the carbon-carbon double bonds of the silicone having a coexisting carbon-carbon double bond ( The value of r2 / r1) is 0.58, the total number of moles of SiH units in the organohydrogen silicone (r1), and the carbon-carbon 2 of the compound <A> having a coexisting carbon-carbon double bond and epoxy group. The ratio (r4 / r1) to the number of moles of heavy bonds (r4) is 0.55, and the total number of carbon-carbon double bonds in the added compound relative to the total number of moles of SiH units in the organohydrogensilicone. The number of moles was 1.13 times.

  In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms was 1 / 259,459 times the total number of moles of SiH units in the organohydrogensilicone before the hydrosilylation reaction. . Further, when sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction proceeded quantitatively, and unreacted SiH units were not detected.

  After completion of the hydrosilylation reaction, 43 g of benzonitrile (reagent manufactured by Wako Pure Chemical Industries, Ltd.) purified by dehydration distillation under dry nitrogen was added to the reaction solution while maintaining the heating temperature, and the reaction solution was kept under an atmospheric pressure dry nitrogen atmosphere for 2 hours. After stirring, stirring was stopped and cooled to room temperature.

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

  The obtained epoxy-modified silicone-containing component was introduced into the inside at a flow rate of 10 mL / min in terms of atmospheric pressure, while the temperature was 40 ° C. and the pressure was 0. 0, as in “Epoxy-modified silicone production example 1”. The low boiling compound was distilled off in a glass tube oven at 2 kPa to obtain an epoxy-modified silicone-containing component with reduced low boiling compound. This operation was repeated for the remaining epoxy-modified silicone obtained by distilling off 1,4-dioxane obtained above to obtain 210 g of [epoxy-modified silicone 6a] with reduced low boiling point compounds.

The obtained [epoxy-modified silicone 6a] had a structure represented by the following average composition formula (H-6) having a number average molecular weight of 1,900.
(Me ₂ YSiO _1/2 ) _6.65 (MeZSiO _2/2 ) _6.65 (Me [VCHO] SiO _2/2 ) _4.80 (H-6)
Here, Y in the average composition formula (H-6) represents a divalent organic group represented by —CH ₂ —CH ₂ —, and Z represents a bond with a divalent hydrocarbon group Y. In addition, (Me [VCHO] SiO _2/2 ) represents a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit by an anti-markovnikov by a hydrosilylation reaction. ]

Since no unreacted SiH unit was detected, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.
The compound represented by the general formula (1) contained in the [epoxy-modified silicone 6a] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is a compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 1.56, The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.37. In [Epoxy-modified silicone 6a], the content of components having a molecular weight of 800 or less was 23.4%, and the content of components having a molecular weight of 10,000 or more was 20.9%. Furthermore, the epoxy value of [epoxy-modified silicone 6a] was 0.25, the transition metal component contained was only platinum, and the content of this component was 5 ppm in terms of platinum element.

As the volatile compound remaining in [epoxy-modified silicone 6a], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.002 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.
[Epoxy-modified silicone 6a] did not increase in molecular weight even when stored at 25 ° C. for 1 week.

[Production Example 7 of Epoxy-Modified Silicone]
(1) Synthesis of Si-H containing silicone In a 0.5 liter reactor equipped with a reflux condenser, a thermometer and a stirrer bar, octamethylcyclotetrasiloxane (reagent made by Azmax) purified by distillation under nitrogen was added. 80 g, 31.04 g of 1,1,3,3-tetramethyldisiloxane (Azmax reagent) purified by distillation under nitrogen, activated clay (Tonsil Optimum 230FF) dried at 110 ° C. for 5 hours under vacuum: 0.6 g of Zude Chemie) was charged, and the reaction was carried out for 20 hours under stirring at 65 ° C. under nitrogen. The obtained reaction solution is passed through a 1 μm filter to remove the catalyst, and dissolved in 330 g of hexane (special grade Wako Pure Chemicals reagent). The solution is neutralized and washed with 650 g of an aqueous solution containing 0.012 g of sodium hydrogen carbonate (special grade product manufactured by Wako Pure Chemical Industries, Ltd.), and then the aqueous phase is separated. The obtained n-hexane solution is washed with 330 g of pure water, and the aqueous phase separation is repeated until the aqueous phase becomes neutral. Next, 25 g of anhydrous sodium sulfate (special grade product manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the n-hexane phase was dehydrated by standing at 20 ° C. for 12 hours to obtain an n-hexane solution of Si—H containing silicone. . Next, from the n-hexane solution of the Si—H-containing silicone after washing with water, the solvent was distilled off at 65 ° C. and 26 kPa for 1 hour, and then the pressure was reduced to 670 Pa over 0.5 hour. Under the conditions, the low molecular weight oligomer was removed over 1.5 hours to obtain 70 g of a dimethylsiloxane polymer [Si-H containing silicone 7a] having SiH bonds at both ends. The number average molecular weight of the dimethylsiloxane polymer having SiH bonds at both ends was 870.

(2) Production of epoxy-modified silicone In the hydrosilylation reaction, 1,3,5,7-tetramethylcyclotetrasiloxane purified by dehydration distillation and 1,3-divinyltetramethyldisiloxane purified by dehydration distillation (1) above 70 g of [Si—H-containing silicone 7a] obtained in the above), 30 g of dehydrated and purified 4-vinylcyclohexene oxide, 400 g of dehydrated and purified 1,4-dioxane, Except that 2 g of a 1,4-dioxane solution of a platinum divinyltetramethyldisilicone complex containing 500 ppm of platinum in terms of platinum element was added, and that the hydrosilylation reaction time was 5 hours, [Manufacturing of epoxy-modified silicone] The hydrosilylation reaction was performed as in Example 1].

  At the start of the reaction, the ratio between the total number of SiH units (r1) of the organohydrogensilicone and the number of moles (r2) of the carbon-carbon double bonds of the silicone having a coexisting carbon-carbon double bond ( The value of r2 / r1) is 0, the total number of SiH units of the organohydrogen silicone (r1), and the carbon-carbon double bond of the compound <A> having a coexisting carbon-carbon double bond and epoxy group. The ratio (r4 / r1) to the number of moles of (r4) is 1.51, and the total number of carbon-carbon double bonds in the added compound with respect to the total number of SiH units of the organohydrogensilicone Was 1.51 times.

  Further, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms was 1 / 31,236 times the total number of moles of SiH units of the organohydrogensilicone before the hydrosilylation reaction. . Further, when sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction proceeded quantitatively, and unreacted SiH units were not detected.

  At this time, the temperature of the reaction solution was between 65 ° C and 100 ° C. After the reaction for 5 hours, the hydrosilylation reaction proceeded quantitatively, and no unreacted SiH unit was detected. Subsequently, the heating of the reaction solution was stopped and the mixture was allowed to cool to room temperature.

  After cooling was completed, 400 g of acetonitrile dehydrated and purified under dry nitrogen was added to the reaction solution, and the mixture was stirred for 2 hours under an atmospheric pressure dry nitrogen atmosphere, and then the stirring was stopped. Next, 330 g of activated carbon heated and dried at 150 ° C. for 3 hours under a dry nitrogen stream was added, and the activated carbon treatment was performed for 48 hours under a dry nitrogen atmosphere. After the activated carbon treatment was completed, the activated carbon was filtered using a PTFE membrane filter having a pore size of 1 μm to collect the filtrate. Furthermore, the activated carbon separated by the above operation was washed with 900 g of 1,4-dioxane purified by dehydration distillation under nitrogen, and the activated carbon was similarly filtered using a membrane filter to recover the washing solution. The resulting filtrate was mixed. 1,4-dioxane and acetonitrile were distilled off from the collected liquid mixture using an evaporator at a heating temperature of 40 ° C. under reduced pressure to obtain an epoxy-modified silicone-containing component.

  The obtained epoxy-modified silicone-containing component was introduced with dry nitrogen at a flow rate of 10 mL / min in terms of atmospheric pressure, similarly to “Epoxy-modified silicone production example 1” except that the treatment time was 3 hours. However, the low-boiling compound was distilled off in a glass tube oven at a temperature of 40 ° C. and a pressure of 0.2 kPa to obtain an epoxy-modified silicone-containing component in which the low-boiling compound was reduced. This operation was repeated for the remaining epoxy-modified silicone obtained by distilling off the 1,4-dioxane obtained above to obtain 75 g of [epoxy-modified silicone 7a] in which the low boiling point compound was reduced.

The obtained [Epoxy-modified silicone 7a] had a structure represented by the following average composition formula (H-7) having a number average molecular weight of 1,100.
(Me ₂ [VCHO] SiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₁₀ (H-7)
[Here, (Me ₂ [VCHO] SiO _2/2 ) in the average composition formula (H-7) represents a unit in which vinylcyclohexene oxide is added to a dimethylhydrogensiloxy unit by an anti-Markovnikov by a hydrosilylation reaction. ]

Since no unreacted SiH unit was detected, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.
Further, the [epoxy-modified silicone 7a] did not contain the compounds represented by the general formulas (1) and (2). In addition, the value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.167. In [Epoxy-modified silicone 7a], the content of components having a molecular weight of 800 or less was 20%, and the content of components having a molecular weight of 10,000 or more was 15%. Furthermore, the epoxy value of [epoxy modified silicone 7a] was 0.18, the transition metal component contained was only platinum, and the content of this component was 0.8 ppm in terms of platinum element.

As the volatile compound remaining in [epoxy-modified silicone 7a], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.001 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.
[Epoxy-modified silicone 7a] was not observed to increase in molecular weight even when stored at 25 ° C. for 1 week.

[Production Example 8 of Epoxy-Modified Silicone]
During the hydrosilylation reaction, 37 g of 1,3-divinyltetramethyldisiloxane purified by dehydration distillation was used, 150.7 g of 4-vinylcyclohexene oxide purified by dehydration distillation was used, and the hydrosilylation reaction time was 20 hours. Except for this, the hydrosilylation reaction was carried out in the same manner as in [Production Example 6 of Epoxy-Modified Silicone].

  At the start of the reaction, the ratio between the total number of SiH units (r1) of the organohydrogensilicone and the number of moles (r2) of the carbon-carbon double bonds of the silicone having a coexisting carbon-carbon double bond ( The value of r2 / r1) is 0.298, the total number of SiH units of the organohydrogen silicone (r1), and the carbon-carbon 2 of the compound <A> having a coexisting carbon-carbon double bond and epoxy group. The value of the ratio (r4 / r1) to the number of moles of heavy bonds (r4) is 0.912, and the total number of carbon-carbon double bonds in the added compound with respect to the total number of moles of SiH units of the organohydrogensilicone. The number of moles was 1.21 times.

  In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms was 1 / 259,459 times the total number of moles of SiH units in the organohydrogensilicone before the hydrosilylation reaction. . Further, when sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction proceeded quantitatively, and unreacted SiH units were not detected.

  After completion of the hydrosilylation reaction, 43 g of benzonitrile purified by dehydration and distillation under dry nitrogen was added to the reaction solution while maintaining the heating temperature. After stirring for 2 hours under an atmospheric pressure dry nitrogen atmosphere, the stirring was stopped. And cooled to room temperature.

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

  The obtained epoxy-modified silicone-containing component was introduced at a temperature of 40 ° C. and a pressure of 0. The low boiling compound was distilled off in a glass tube oven at 2 kPa to obtain an epoxy-modified silicone-containing component with reduced low boiling compound. This operation was repeated with respect to the remaining epoxy-modified silicone obtained by distilling off 1,4-dioxane obtained above to obtain 220 g of [epoxy-modified silicone 8a] in which low boiling point compounds were reduced.

The obtained [epoxy-modified silicone 8a] had a structure represented by the following average composition formula (H-8) having a number average molecular weight of 1,000.
(Me ₂ YSiO _1/2 ) _1.71 (MeZSiO _2/2 ) _1.71 (Me [VCHO] SiO _2/2 ) _4.02 (H-8)
Here, Y in the average composition formula (H-8) represents a divalent organic group represented by —CH ₂ —CH ₂ —, and Z represents a bond with a divalent hydrocarbon group Y. In addition, (Me [VCHO] SiO _2/2 ) represents a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit by an anti-markovnikov by a hydrosilylation reaction. ]

Since no unreacted SiH unit was detected, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.
The compound represented by the general formula (1) contained in the [epoxy-modified silicone 8a] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 0.42. The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.23. The content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 8a] was 37.1%, and the content of components having a molecular weight of 10,000 or more was 9.2%. Furthermore, the epoxy value of [epoxy modified silicone 8a] was 0.40, the transition metal component contained was only platinum, and the content of the component was 4 ppm in terms of platinum element.

As the volatile compound remaining in [epoxy-modified silicone 8a], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.001 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.
[Epoxy-modified silicone 8a] was not observed to increase in molecular weight even when stored at 25 ° C. for 1 week.

[Production Example 9 of Epoxy-Modified Silicone]
During hydrosilylation reaction, 75 g of 1,3-divinyltetramethyldisiloxane purified by dehydration distillation was used, 84.9 g of 4-vinylcyclohexene oxide purified by dehydration distillation was used, and 500 ppm of platinum in terms of platinum element was used. Except that 2.2 g of 1,4-dioxane solution of platinum divinyltetramethyldisilicone complex contained was added and that the hydrosilylation reaction time was 90 hours, the same as [Production Example 6 of Epoxy-Modified Silicone] The hydrosilylation reaction was carried out.

  At the start of the reaction, the ratio between the total number of SiH units (r1) of the organohydrogensilicone and the number of moles (r2) of the carbon-carbon double bonds of the silicone having a coexisting carbon-carbon double bond ( The value of r2 / r1) is 0.605, the total number of moles of SiH units of organohydrogensilicone (r1), and the carbon-carbon 2 of the compound <A> having a coexisting carbon-carbon double bond and epoxy group. The value of the ratio (r4 / r1) to the number of moles (r4) of heavy bonds is 0.514, and the total number of carbon-carbon double bonds in the added compound relative to the total number of moles of SiH units in the organohydrogensilicone The number of moles was 1.12 times.

  Further, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms was 1 / 235,872 times the total number of moles of SiH units of the organohydrogensilicone before the hydrosilylation reaction. . Further, when sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction proceeded quantitatively, and unreacted SiH units were not detected.

  After completion of the hydrosilylation reaction, 43 g of benzonitrile purified by dehydration and distillation under dry nitrogen was added to the reaction solution while maintaining the heating temperature. After stirring for 2 hours under an atmospheric pressure dry nitrogen atmosphere, the stirring was stopped. And cooled to room temperature.

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

  The obtained epoxy-modified silicone-containing component was introduced at a temperature of 40 ° C. and a pressure of 0. The low boiling compound was distilled off in a glass tube oven at 2 kPa to obtain an epoxy-modified silicone-containing component with reduced low boiling compound. This operation was repeated for the remaining epoxy-modified silicone obtained by distilling off 1,4-dioxane obtained above to obtain 210 g of [epoxy-modified silicone 9a] with reduced low boiling point compounds.

The obtained [epoxy-modified silicone 9a] had a structure represented by the following average composition formula (H-9) having a number average molecular weight of 2,000.
(Me ₂ YSiO _1/2 ) _7.32 (MeZSiO _2/2 ) _7.32 (Me [VCHO] SiO _2/2 ) _4.78 (H-9)
Here, Y in the average composition formula (H-9) represents a divalent organic group represented by —CH ₂ —CH ₂ —, and Z represents a bond with a divalent hydrocarbon group Y. In addition, (Me [VCHO] SiO _2/2 ) represents a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit by an anti-markovnikov by a hydrosilylation reaction. ]

Since no unreacted SiH unit was detected, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.
The compound represented by the general formula (1) contained in the [epoxy-modified silicone 9a] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 1.85, The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.38. In [Epoxy-modified silicone 9a], the content of components having a molecular weight of 800 or less was 22%, and the content of components having a molecular weight of 10,000 or more was 23%. Furthermore, the epoxy value of [Epoxy-modified silicone 9a] was 0.24, the transition metal component contained was only platinum, and the content of this component was 5 ppm in terms of platinum element.

As the volatile compound remaining in [epoxy-modified silicone 9a], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.002 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.
[Epoxy-modified silicone 9a] showed no increase in molecular weight even when stored at 25 ° C. for 1 week.

[Production Example 10 of Epoxy-Modified Silicone]
At the time of hydrosilylation reaction, 25 g of 1,3-divinyltetramethyldisiloxane purified by dehydration distillation was used, 171.5 g of 4-vinylcyclohexene oxide purified by dehydration distillation was used, and 500 ppm of platinum in terms of platinum element. [Epoxy-modified silicone production example 6], except that 2.4 g of a 1,4-dioxane solution of platinum divinyltetramethyldisilicone complex contained was added and the hydrosilylation reaction time was 15 hours. The hydrosilylation reaction was carried out.

  At the start of the reaction, the ratio between the total number of SiH units (r1) of the organohydrogensilicone and the number of moles (r2) of the carbon-carbon double bonds of the silicone having a coexisting carbon-carbon double bond ( The value of r2 / r1) is 0.202, and the total number of SiH units of the organohydrogensilicone (r1), and the carbon-carbon 2 of the compound <A> having a coexisting carbon-carbon double bond and epoxy group. The value of the ratio (r4 / r1) to the number of moles of heavy bonds (r4) is 1.04, and the total number of carbon-carbon double bonds in the added compound relative to the total number of moles of SiH units in the organohydrogensilicone. The number of moles was 1.24 times.

  Further, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms was 1 / 216,216 times the total number of moles of SiH units of the organohydrogensilicone before the hydrosilylation reaction. . Further, when sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction proceeded quantitatively, and unreacted SiH units were not detected.

  After completion of the hydrosilylation reaction, 43 g of benzonitrile purified by dehydration and distillation under dry nitrogen was added to the reaction solution while maintaining the heating temperature. After stirring for 2 hours under an atmospheric pressure dry nitrogen atmosphere, the stirring was stopped. And cooled to room temperature.

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

  The obtained epoxy-modified silicone-containing component was introduced at a temperature of 40 ° C. and a pressure of 0. The low boiling compound was distilled off in a glass tube oven at 2 kPa to obtain an epoxy-modified silicone-containing component with reduced low boiling compound. This operation was repeated with respect to the remaining epoxy-modified silicone obtained by distilling off 1,4-dioxane obtained above to obtain 225 g of [epoxy-modified silicone 10a] in which low boiling point compounds were reduced.

The obtained [epoxy-modified silicone 10a] had a structure represented by the following average composition formula (H-10) having a number average molecular weight of 900.
(Me ₂ YSiO _1/2 ) _1.02 (MeZSiO _2/2 ) _1.02 (Me [VCHO] SiO _2/2 ) _4.04 (H-10)
Here, Y in the average composition formula (H-10) represents a divalent organic group represented by —CH ₂ —CH ₂ —, and Z represents a bond with a divalent hydrocarbon group Y. In addition, (Me [VCHO] SiO _2/2 ) represents a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit by an anti-markovnikov by a hydrosilylation reaction. ]

Since no unreacted SiH unit was detected, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.
The compound represented by the general formula (1) contained in the [epoxy-modified silicone 10a] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 0.25, The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.17. In [Epoxy-modified silicone 10a], the content of components having a molecular weight of 800 or less was 46.5%, and the content of components having a molecular weight of 10,000 or more was 9%. Furthermore, the epoxy value of [epoxy modified silicone 10a] was 0.45, the transition metal component contained was only platinum, and the content of the component was 5 ppm in terms of platinum element.

As the volatile compound remaining in [epoxy-modified silicone 10a], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.001 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.
[Epoxy-modified silicone 10a] was not observed to increase in molecular weight even when stored at 25 ° C. for 1 week.

[Production Example 11 of Epoxy-Modified Silicone]
During hydrosilylation reaction, 55.8 g of 1,3-divinyltetramethyldisiloxane purified by dehydration distillation was used, 118.2 g of 4-vinylcyclohexene oxide purified by dehydration distillation was used, and 500 ppm in terms of platinum element. Except that 2.4 g of a 1,4-dioxane solution of a platinum divinyltetramethyldisilicone complex containing platinum was added and the hydrosilylation reaction time was 55 hours, [Epoxy-modified silicone production example 6] and Similarly, a hydrosilylation reaction was performed.

  At the start of the reaction, the ratio between the total number of SiH units (r1) of the organohydrogensilicone and the number of moles (r2) of the carbon-carbon double bonds of the silicone having a coexisting carbon-carbon double bond ( The value of r2 / r1) is 0.450, the total number of SiH units of the organohydrogen silicone (r1), and the carbon-carbon 2 of the compound <A> having a coexisting carbon-carbon double bond and epoxy group. The value of the ratio (r4 / r1) to the number of moles of heavy bonds (r4) is 0.715, and the total number of carbon-carbon double bonds in the added compound with respect to the total number of moles of SiH units in the organohydrogensilicone. The number of moles was 1.17 times.

  Further, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms was 1 / 216,216 times the total number of moles of SiH units of the organohydrogensilicone before the hydrosilylation reaction. . Further, when sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction proceeded quantitatively, and unreacted SiH units were not detected.

  After completion of the hydrosilylation reaction, 84.9 g of benzonitrile purified by dehydration distillation under dry nitrogen was added to the reaction solution while maintaining the heating temperature, and the mixture was stirred for 2 hours under an atmospheric pressure dry nitrogen atmosphere. Stop and cool to room temperature.

1,4-dioxane was distilled off from the cooled reaction solution using an evaporator at a heating temperature of 40 ° C. under reduced pressure to obtain an epoxy-modified silicone-containing component.
The obtained epoxy-modified silicone-containing component was introduced at a temperature of 40 ° C. and a pressure of 0. The low boiling compound was distilled off in a glass tube oven at 2 kPa to obtain an epoxy-modified silicone-containing component with reduced low boiling compound. This operation was repeated for the remaining epoxy-modified silicone obtained by distilling off 1,4-dioxane obtained above to obtain 215 g of [epoxy-modified silicone 11a] with reduced low boiling point compounds.

[Epoxy-modified silicone 11a] thus obtained had a structure represented by the following average composition formula (H-11) having a number average molecular weight of 1,400.
(Me ₂ YSiO _1/2 ) _3.70 (MeZSiO _2/2 ) _3.70 (Me [VCHO] SiO _2/2 ) _4.53 (H-11)
Here, Y in the average composition formula (H-11) represents a divalent organic group represented by —CH ₂ —CH ₂ —, and Z represents a bond with a divalent hydrocarbon group Y. In addition, (Me [VCHO] SiO _2/2 ) represents a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit by an anti-markovnikov by a hydrosilylation reaction. ]

Since no unreacted SiH unit was detected, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.
The compound represented by the general formula (1) contained in the [epoxy-modified silicone 11a] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 0.83, The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.31. In addition, the content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 10a] was 29.8%, and the content of components having a molecular weight of 10,000 or more was 11%. Furthermore, the epoxy value of [epoxy-modified silicone 11a] was 0.32, and the transition metal component contained was only platinum, and the content of this component was 5 ppm in terms of platinum element.

As the volatile compound remaining in [epoxy-modified silicone 11a], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.001 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.
[Epoxy-modified silicone 11a] did not increase in molecular weight even when stored at 25 ° C. for 1 week.

[Production Example 12 of Epoxy-Modified Silicone]
During hydrosilylation reaction, 89 g of 1,3-divinyltetramethyldisiloxane purified by dehydration distillation was used, 60.7 g of 4-vinylcyclohexene oxide purified by dehydration distillation was used, and 500 ppm of platinum in terms of platinum element. Except that 2.4 g of a 1,4-dioxane solution of platinum divinyltetramethyldisilicone complex contained was added and that the hydrosilylation reaction time was 110 hours, as in [Production Example 6 of Epoxy-Modified Silicone]. The hydrosilylation reaction was carried out.

  At the start of the reaction, the ratio between the total number of SiH units (r1) of the organohydrogensilicone and the number of moles (r2) of the carbon-carbon double bonds of the silicone having a coexisting carbon-carbon double bond ( The value of r2 / r1) is 0.72, the total number of SiH units of the organohydrogen silicone (r1), and the carbon-carbon 2 of the compound <A> having a coexisting carbon-carbon double bond and epoxy group. The value of the ratio (r4 / r1) to the number of moles of heavy bonds (r4) is 0.37, and the total number of carbon-carbon double bonds in the added compound relative to the total number of moles of SiH units in the organohydrogensilicone. The number of moles was 1.09 times.

  Further, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms was 1 / 216,216 times the total number of moles of SiH units of the organohydrogensilicone before the hydrosilylation reaction. . Further, when sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction proceeded quantitatively, and unreacted SiH units were not detected.

  After completion of the hydrosilylation reaction, 84.9 g of benzonitrile purified by dehydration distillation under dry nitrogen was added to the reaction solution while maintaining the heating temperature, and the mixture was stirred for 2 hours under an atmospheric pressure dry nitrogen atmosphere. Stop and cool to room temperature.

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

  The obtained epoxy-modified silicone-containing component was introduced at a temperature of 40 ° C. and a pressure of 0. The low boiling compound was distilled off in a glass tube oven at 2 kPa to obtain an epoxy-modified silicone-containing component with reduced low boiling compound. This operation was repeated for the remaining epoxy-modified silicone obtained by distilling off the 1,4-dioxane obtained above, to obtain 200 g of [epoxy-modified silicone 12a] with reduced low boiling point compounds.

The obtained [epoxy-modified silicone 12a] had a structure represented by the following average composition formula (H-12) having a number average molecular weight of 2,700.
(Me ₂ YSiO _1/2 ) _12.0 (MeZSiO _2/2 ) _12.0 (Me [VCHO] SiO _2/2 ) _4.7 (H-12)
[Wherein Y in the average composition formula (H-12) represents a divalent organic group represented by —CH ₂ —CH ₂ —, and Z represents a bond with a divalent hydrocarbon group Y. In addition, (Me [VCHO] SiO _2/2 ) represents a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit by an anti-markovnikov by a hydrosilylation reaction. ]

Since no unreacted SiH unit was detected, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.
The compound represented by the general formula (1) contained in the [epoxy-modified silicone 11a] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 4.70, The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.42. The content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 12a] was 9%, and the content of components having a molecular weight of 10,000 or more was 40.4%. Furthermore, the epoxy value of [epoxy-modified silicone 12a] was 0.17, the transition metal component contained was only platinum, and the content of this component was 6 ppm in terms of platinum element.
As the volatile compound remaining in [epoxy-modified silicone 12a], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less.

Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.002 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.
[Epoxy-modified silicone 12a] was not observed to increase in molecular weight even when stored at 25 ° C. for 1 week.

[Production Example 13 of Epoxy-Modified Silicone]
During the hydrosilylation reaction, 87 g of 1,3-divinyltetramethyldisiloxane purified by dehydration distillation was used, 64.1 g of 4-vinylcyclohexene oxide purified by dehydration distillation was used, and 500 ppm of platinum in terms of platinum element. Except that 2.4 g of a 1,4-dioxane solution of platinum divinyltetramethyldisilicone complex contained was added and that the hydrosilylation reaction time was 110 hours, as in [Production Example 6 of Epoxy-Modified Silicone]. The hydrosilylation reaction was carried out.

  At the start of the reaction, the ratio between the total number of SiH units (r1) of the organohydrogensilicone and the number of moles (r2) of the carbon-carbon double bonds of the silicone having a coexisting carbon-carbon double bond ( The value of r2 / r1) is 0.702, the total number of SiH units of the organohydrogen silicone (r1), and the carbon-carbon 2 of the compound <A> having a coexisting carbon-carbon double bond and epoxy group. The value of the ratio (r4 / r1) to the number of moles (r4) of heavy bonds is 0.388, and the total number of carbon-carbon double bonds in the added compound with respect to the total number of moles of SiH units in the organohydrogensilicone. The number of moles was 1.09 times.

  Further, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms was 1 / 216,216 times the total number of moles of SiH units of the organohydrogensilicone before the hydrosilylation reaction. . Further, when sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction proceeded quantitatively, and unreacted SiH units were not detected.

After completion of the hydrosilylation reaction, 84.9 g of benzonitrile purified by dehydration distillation under dry nitrogen was added to the reaction solution while maintaining the heating temperature, and the mixture was stirred for 2 hours under an atmospheric pressure dry nitrogen atmosphere. Stop and cool to room temperature.
1,4-dioxane was distilled off from the cooled reaction solution using an evaporator at a heating temperature of 40 ° C. under reduced pressure to obtain an epoxy-modified silicone-containing component.

  The obtained epoxy-modified silicone-containing component was introduced at a temperature of 40 ° C. and a pressure of 0. The low boiling compound was distilled off in a glass tube oven at 2 kPa to obtain an epoxy-modified silicone-containing component with reduced low boiling compound. This operation was repeated for the remaining epoxy-modified silicone obtained by distilling off the 1,4-dioxane obtained above to obtain 205 g of [epoxy-modified silicone 11a] in which low boiling point compounds were reduced.

[Epoxy-modified silicone 13a] thus obtained had a structure represented by the following average composition formula (H-13) having a number average molecular weight of 2,600.
(Me ₂ YSiO _1/2 ) _11.24 (MeZSiO _2/2 ) _11.24 (Me [VCHO] SiO _2/2 ) _4.78 (H-13)
Here, Y in the average composition formula (H-13) represents a divalent organic group represented by —CH ₂ —CH ₂ —, and Z represents a bond with a divalent hydrocarbon group Y. In addition, (Me [VCHO] SiO _2/2 ) represents a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit by an anti-markovnikov by a hydrosilylation reaction. ]

Since no unreacted SiH unit was detected, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.
The compound represented by the general formula (1) contained in the [epoxy-modified silicone 13a] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is a compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 3.65, The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.41. In addition, the content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 13a] was 11.8%, and the content of components having a molecular weight of 10,000 or more was 37.7%. Furthermore, the epoxy value of [epoxy modified silicone 13a] was 0.18, the transition metal component contained was only platinum, and the content of this component was 6 ppm in terms of platinum element.

As the volatile compound remaining in [epoxy-modified silicone 13a], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.001 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.
[Epoxy-modified silicone 13a] showed no increase in molecular weight even when stored at 25 ° C. for 1 week.

[Production Example 14 of Epoxy-Modified Silicone]
(1) Synthesis of Si-H-containing silicone An n-hexane solution of Si-H-containing silicone obtained by performing the same operation as the synthesis of epoxy-modified silicone in Production Example 7 (1) Si-H-containing silicone, After the solvent was distilled off at 65 ° C. and 26 kPa for 1 hour and then the pressure was reduced to 670 Pa over 0.5 hour, the low molecular weight oligomer was removed over 4 hours under the conditions of 150 ° C. and 50 Pa. A dimethylsiloxane polymer [Si-H containing silicone 14a] 61 having a bond was obtained. The number average molecular weight of the dimethylsiloxane polymer having SiH bonds at both ends was 1,100.

(2) Production of epoxy-modified silicone In the hydrosilylation reaction, 1,3,5,7-tetramethylcyclotetrasiloxane purified by dehydration distillation and 1,3-divinyltetramethyldisiloxane purified by dehydration distillation (1) above 60 g of [Si—H-containing silicone 14a] obtained in the above), 22 g of dehydrated and purified 4-vinylcyclohexene oxide, 330 g of dehydrated and purified 1,4-dioxane, Epoxy-modified silicone according to [Epoxy-modified silicone production example 7] except that 1.4 g of a 1,4-dioxane solution of a platinum divinyltetramethyldisilicone complex containing 500 ppm of platinum in terms of platinum element was added. The hydrosilylation reaction was carried out in the same manner as in the production method.

  At the start of the reaction, the ratio between the total number of SiH units (r1) of the organohydrogensilicone and the number of moles (r2) of the carbon-carbon double bonds of the silicone having a coexisting carbon-carbon double bond ( The value of r2 / r1) is 0, the total number of SiH units of the organohydrogen silicone (r1), and the carbon-carbon double bond of the compound <A> having a coexisting carbon-carbon double bond and epoxy group. The ratio (r4 / r1) to the number of moles of (r4) is 1.62, the total number of carbon-carbon double bonds in the added compound relative to the total number of SiH units of the organohydrogensilicone Was 1.62 times.

  In addition, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms was 1 / 30,390 times the total number of moles of SiH units in the organohydrogensilicone before the hydrosilylation reaction. . Further, when sampling was performed immediately before the hydrosilylation reaction was stopped, the hydrosilylation reaction proceeded quantitatively, and unreacted SiH units were not detected.

  At this time, the temperature of the reaction solution was between 65 ° C and 100 ° C. After the reaction for 5 hours, the hydrosilylation reaction proceeded quantitatively, and no unreacted SiH unit was detected. Subsequently, the heating of the reaction solution was stopped and the mixture was allowed to cool to room temperature.

  After the cooling was completed, 330 g of acetonitrile dehydrated and purified under dry nitrogen was added to the reaction solution, and the mixture was stirred for 2 hours under an atmospheric pressure dry nitrogen atmosphere, and then the stirring was stopped. Next, 270 g of activated carbon heated and dried at 150 ° C. for 3 hours under a dry nitrogen stream was added, and the activated carbon treatment was performed for 48 hours under a dry nitrogen atmosphere. After the activated carbon treatment was completed, the activated carbon was filtered using a PTFE membrane filter having a pore size of 1 μm to collect the filtrate. Further, the activated carbon separated by the above operation was washed with 500 g of 1,4-dioxane purified by dehydration distillation under nitrogen, and the activated carbon was similarly filtered using a membrane filter to recover the washing solution. The resulting filtrate was mixed. 1,4-dioxane and acetonitrile were distilled off from the collected liquid mixture using an evaporator at a heating temperature of 40 ° C. under reduced pressure to obtain an epoxy-modified silicone-containing component.

  The obtained epoxy-modified silicone-containing component was introduced with dry nitrogen at a flow rate of 10 mL / min in terms of atmospheric pressure, similarly to “Epoxy-modified silicone production example 1” except that the treatment time was 4 hours. However, the low-boiling compound was distilled off in a glass tube oven at a temperature of 40 ° C. and a pressure of 0.2 kPa to obtain an epoxy-modified silicone-containing component in which the low-boiling compound was reduced. This operation was repeated for the remaining epoxy-modified silicone obtained by distilling off 1,4-dioxane obtained above to obtain 60 g of [epoxy-modified silicone 14a] with reduced low boiling point compounds.

[Epoxy-modified silicone 14a] thus obtained had a structure represented by the following average composition formula (H-14) having a number average molecular weight of 1350.
(Me ₂ [VCHO] SiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₁₃ (H-14)
[Here, (Me ₂ [VCHO] SiO _2/2 ) in the average composition formula (H-7) represents a unit in which vinylcyclohexene oxide is added to a dimethylhydrogensiloxy unit by an anti-Markovnikov by a hydrosilylation reaction. ]

Since no unreacted SiH unit was detected, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.
Further, the [epoxy-modified silicone 14a] did not contain the compounds represented by the general formulas (1) and (2). In addition, the value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.133. In addition, the content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 14a] was 8%, and the content of components having a molecular weight of 10,000 or more was 19%. Furthermore, the epoxy value of [epoxy-modified silicone 14a] was 0.15, the transition metal component contained was only platinum, and the content of this component was 0.8 ppm in terms of platinum element.

As the volatile compound remaining in [epoxy-modified silicone 14a], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.001 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.
[Epoxy-modified silicone 14a] was not observed to increase in molecular weight even when stored at 25 ° C. for 1 week.

[Example 1]
1) Production of [Epoxy-modified silicone 1b] [Epoxy-modified silicone 1b] was produced by uniformly mixing 80 parts by mass of [Epoxy-modified silicone 1a] and 20 parts by mass of [Epoxy-modified silicone 2a].
[Epoxy-modified silicone 1b] thus obtained had a structure represented by the following average composition formula (I-1) having a number average molecular weight of 1,800.
(Me ₂ YSiO _1/2 ) _5.51 (MeZSiO _2/2 ) _5.51 (Me [VCHO] SiO _2/2 ) _5.35 (I-1)
[Here, (Me ₂ [VCHO] SiO _2/2 ) in the average composition formula (I-1) represents a unit in which vinylcyclohexene oxide is added to an anti-Markovnikov by a hydrosilylation reaction to a dimethylhydrogensiloxy unit. ]

  [Epoxy-modified silicone 1b] contained no SiH unit, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.

  The compound represented by the general formula (1) contained in the [epoxy-modified silicone 1b] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 0.34, The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.337. In addition, the content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 1b] was 30.0%, and the content of components having a molecular weight of 10,000 or more was 21.2%. Furthermore, the epoxy value of [epoxy-modified silicone 1b] was 0.29, the transition metal component contained was only platinum, and the content of this component was 0.5 ppm in terms of platinum element.

As the volatile compound remaining in [epoxy-modified silicone 1b], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less.
Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.001 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.

2) Manufacture and characterization of [curable resin composition-1b] 100 parts by weight of obtained [epoxy-modified silicone 1b], Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride) Acid mixture) 51.9 parts by mass, 1,2-propanediol 3 parts by mass, and diazabicycloundecene octylate 0.3 parts by mass under nitrogen, stirred until the whole becomes homogeneous, and then removed. It foamed and [curable resin composition-1b] was obtained. [Curable resin composition-1b] was poured into a mold under nitrogen and subjected to a curing reaction at 120 ° C. for 1 hour and further at 150 ° C. for 2 hours to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Example 2]
1) Production of [Epoxy-modified silicone 2b] [Epoxy-modified silicone 2b] was produced by uniformly mixing 80 parts by mass of [Epoxy-modified silicone 4a] and 20 parts by mass of [Epoxy-modified silicone 2a].
The obtained [epoxy-modified silicone 2b] had a structure represented by the following average composition formula (I-2) having a number average molecular weight of 2,000.
(Me ₂ YSiO _1/2 ) _6.25 (MeZSiO _2/2 ) _6.25 (Me [VCHO] SiO _2/2 ) _5.60 (I-2)
[Here, (Me ₂ [VCHO] SiO _2/2 ) in the average composition formula (I-2) represents a unit in which vinylcyclohexene oxide is added to an anti-Markovnikov by a hydrosilylation reaction to a dimethylhydrogensiloxy unit. ]

  [Epoxy-modified silicone 2b] contained no SiH unit, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.

  The compound represented by the general formula (1) contained in the [epoxy-modified silicone 2b] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 0.34, The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.345. In [Epoxy-modified silicone 2b], the content of components having a molecular weight of 800 or less was 38.0%, and the content of components having a molecular weight of 10,000 or more was 24.6%. Furthermore, the epoxy value of [epoxy-modified silicone 2b] was 0.29, the transition metal component contained was only platinum, and the content of this component was 0.4 ppm in terms of platinum element.

  As the volatile compound remaining in [epoxy-modified silicone 2b], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.002 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.

2) Manufacture and evaluation of [curable resin composition-2b] 100 parts by weight of the obtained [epoxy-modified silicone 2b], 47.2 parts by weight of methylhexahydrophthalic anhydride, 3 parts by weight of 1,3-propanediol Then, 0.3 part by mass of diazabicycloundecene octylate was mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain [curable resin composition-2b]. [Curable resin composition-2b] was poured into a mold under nitrogen, and a curing reaction was performed at 120 ° C. for 1 hour, further at 140 ° C. for 2 hours, and further at 160 ° C. for 1 hour to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Example 3]
1) Production of [Epoxy-modified silicone 3b] [Epoxy-modified silicone 3b] was produced by uniformly mixing 90 parts by mass of [Epoxy-modified silicone 5a] and 10 parts by mass of [Epoxy-modified silicone 2a].
The obtained [epoxy-modified silicone 3b] had a structure represented by the following average composition formula (I-3) having a number average molecular weight of 1,150.
(Me ₂ YSiO _1/2 ) _2.44 (MeZSiO _2/2 ) _4.24 (Me [VCHO] SiO _2/2 ) _2.44 (I-3)
[Here, (Me ₂ [VCHO] SiO _2/2 ) in the average composition formula (I-3) represents a unit in which vinylcyclohexene oxide is added to a dimethylhydrogensiloxy unit by an anti-Markovnikov by a hydrosilylation reaction. ]

  [Epoxy-modified silicone 3b] did not contain SiH units, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.

  The compound represented by the general formula (1) contained in the [epoxy-modified silicone 3b] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 0.42. The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.268. In addition, the content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 3b] was 37.0%, and the content of components having a molecular weight of 10,000 or more was 9.7%. Furthermore, the epoxy value of [epoxy-modified silicone 3b] was 0.37, the transition metal component contained was only platinum, and the content of this component was 0.5 ppm in terms of platinum element.

  As the volatile compound remaining in [epoxy-modified silicone 3b], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.001 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.

2) Manufacture and characterization of [curable resin composition-3b] 100 parts by weight of obtained [epoxy-modified silicone 3b], Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride) Acid mixture) 65.3 parts by mass, 1,2-propanediol 3 parts by mass, diazabicycloundecene octylate 0.3 parts by mass under nitrogen, stirring until the whole becomes uniform, It foamed and [curable resin composition-3b] was obtained. [Curable resin composition-3b] was poured into a mold under nitrogen and subjected to a curing reaction at 120 ° C. for 1 hour and further at 150 ° C. for 2 hours to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Example 4]
1) Production of [Epoxy Modified Silicone 4b] [Epoxy Modified Silicone 4b] was produced by uniformly mixing 75 parts by mass of [Epoxy Modified Silicone 6a] and 25 parts by mass of [Epoxy Modified Silicone 7a].
[Epoxy-modified silicone 4b] thus obtained had a structure represented by the following average composition formula (I-4) having a number average molecular weight of 1,700.
(Me ₂ [VCHO] SiO _1/2 ) _0.76 (Me ₂ YSiO _1/2 ) _4.47 (Me ₂ SiO _2/2 ) _3.80
(MeZSiO _2/2 ) _4.47 (Me [VCHO] SiO _2/2 ) _3.23 (I-5)
[Wherein (Me ₂ [VCHO] SiO _2/2 ) in the average composition formula (I-5) is a unit in which vinylcyclohexene oxide is added to a dimethylhydrogensiloxy unit by an anti-markovnikov by a hydrosilylation reaction, (Me ₂ [VCHO] SiO _2/2 ) each represents a unit in which vinylcyclohexene oxide is added to an anti-Markovnikov by a hydrosilylation reaction to a dimethylhydrogensiloxy unit. ]

  [Epoxy-modified silicone 4b] contained no SiH unit, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.

  The compound represented by the general formula (1) contained in the [epoxy-modified silicone 4b] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 0.42. The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 1.56. The content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 4b] was 22.6%, and the content of components having a molecular weight of 10,000 or more was 19.4%. Furthermore, the epoxy value of [Epoxy-modified silicone 4b] was 0.23, the transition metal component contained was only platinum, and the content of this component was 3.6 ppm in terms of platinum element.

  As the volatile compound remaining in [epoxy-modified silicone 4b], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.002 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.

2) Manufacture and characteristic evaluation of [curable resin composition-4b] 90 parts by weight of the obtained [epoxy-modified silicone 4b], 10 parts by weight of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanedicarboxylate Parts, RIKACID MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) 44.7 parts, 1,2-propanediol 3 parts, diazabicycloundecene octylate 0.3 part by mass was mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain [curable resin composition-4b]. [Curable resin composition-4b] was poured into a mold under nitrogen and subjected to a curing reaction at 120 ° C. for 1 hour and further at 140 ° C. for 3 hours to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Example 5]
1) Production of [Epoxy-modified silicone 5b] [Epoxy-modified silicone 5b] was produced by uniformly mixing 50 parts by mass of [Epoxy-modified silicone 8a] and 50 parts by mass of [Epoxy-modified silicone 9a].
[Epoxy-modified silicone 5b] thus obtained had a structure represented by the following average composition formula (I-5) having a number average molecular weight of 1,500.
(Me ₂ YSiO _1/2 ) _4.03 (MeZSiO _2/2 ) _4.03 (Me [VCHO] SiO _2/2 ) _4.80 (I-5)
[Here, (Me ₂ [VCHO] SiO _2/2 ) in the average composition formula (I-5) represents a unit in which vinylcyclohexene oxide is added to an anti-Markovnikov by a hydrosilylation reaction to a dimethylhydrogensiloxy unit. ]

  [Epoxy-modified silicone 5b] contained no SiH unit, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.

  The compound represented by the general formula (1) contained in the [epoxy-modified silicone 5b] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is a compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 0.65, The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.313. The content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 5b] was 29.6%, and the content of components having a molecular weight of 10,000 or more was 16.1%. Furthermore, the epoxy value of [epoxy modified silicone 5b] was 0.32, and the transition metal component contained was only platinum, and the content of the component was 4.5 ppm in terms of platinum element.

  As the volatile compound remaining in [epoxy-modified silicone 5b], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.002 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.

2) Manufacture and characterization of [curable resin composition-5b] 100 parts by weight of obtained [epoxy-modified silicone 5b], Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride) Acid mixture) 56.9 parts by mass, 1,2-propanediol 3 parts by mass, and diazabicycloundecene octylate 0.3 parts by mass under nitrogen, stirring until the whole is uniform, Foamed to obtain [Curable Resin Composition-5b]. [Curable resin composition-5b] was poured into a mold under nitrogen and subjected to a curing reaction at 120 ° C. for 1 hour and further at 150 ° C. for 2 hours to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Example 6]
1) Production of [Epoxy Modified Silicone 6b] [Epoxy Modified Silicone 6b] was produced by uniformly mixing 27 parts by mass of [Epoxy Modified Silicone 10a] and 73 parts by mass of [Epoxy Modified Silicone 4a].
The obtained [epoxy-modified silicone 6b] had a structure represented by the following average composition formula (I-6) having a number average molecular weight of 1,900.
(Me ₂ YSiO _1/2 ) _6.11 (MeZSiO _2/2 ) _6.11 (Me [VCHO] SiO _2/2 ) _5.37 (I-6)
[Here, (Me ₂ [VCHO] SiO _2/2 ) in the average composition formula (I-6) represents a unit in which vinylcyclohexene oxide is added to an anti-Markovnikov by a hydrosilylation reaction to a dimethylhydrogensiloxy unit. ]

  [Epoxy-modified silicone 6b] contained no SiH unit, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.

  The compound represented by the general formula (1) contained in the [epoxy-modified silicone 6b] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is a compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 0.67, The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.347. In addition, the content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 6b] was 25.5%, and the content of components having a molecular weight of 10,000 or more was 24.8%. Furthermore, the epoxy value of [epoxy-modified silicone 6b] was 0.28, the transition metal component contained was only platinum, and the content of this component was 1.7 ppm in terms of platinum element.

  As the volatile compound remaining in [epoxy-modified silicone 6b], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.002 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.

2) Manufacture and evaluation of [curable resin composition-6b] 100 parts by weight of obtained [epoxy-modified silicone 6b], Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride) Acid mixture) 49.6 parts by mass, 1,2-propanediol 3 parts by mass, and diazabicycloundecene octylate 0.3 parts by mass under nitrogen and stirring until the whole becomes homogeneous Foamed to obtain [Curable Resin Composition-6b]. [Curable resin composition-6b] was poured into a mold under nitrogen and subjected to a curing reaction at 120 ° C. for 1 hour, further at 140 ° C. for 2 hours, and further at 160 ° C. for 1 hour to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Example 7]
1) Production of [Epoxy Modified Silicone 7b] [Epoxy Modified Silicone 7b] was produced by uniformly mixing 40 parts by mass of [Epoxy Modified Silicone 4a] and 70 parts by mass of [Epoxy Modified Silicone 5a].
[Epoxy-modified silicone 7b] thus obtained had a structure represented by the following average composition formula (I-7) having a number average molecular weight of 1,530.
(Me ₂ YSiO _1/2 ) _4.32 (MeZSiO _2/2 ) _4.32 (Me [VCHO] SiO _2/2 ) _4.72 (I-7)
[Here, (Me ₂ [VCHO] SiO _2/2 ) in the average composition formula (I-7) represents a unit in which vinylcyclohexene oxide is added to an anti-Markovnikov by a hydrosilylation reaction to a dimethylhydrogensiloxy unit. ]

  [Epoxy-modified silicone 7b] contained no SiH unit, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.

  The compound represented by the general formula (1) contained in the [epoxy-modified silicone 7b] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 0.81. The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.323. In [Epoxy-modified silicone 7b], the content of components having a molecular weight of 800 or less was 27.6%, and the content of components having a molecular weight of 10,000 or more was 16.8%. Furthermore, the epoxy value of [Epoxy-modified silicone 7b] was 0.31, and the transition metal component contained was only platinum, and the content of this component was 0.5 ppm in terms of platinum element.

  As the volatile compound remaining in [epoxy-modified silicone 7b], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.001 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.

2) Manufacture and evaluation of [curable resin composition-7b] 100 parts by weight of obtained [epoxy-modified silicone 7b], Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride) Acid mixture) 54.8 parts by mass, 1,2-propanediol 3 parts by mass, diazabicycloundecene octylate 0.3 parts by mass under nitrogen, stirring until the whole is uniform, It foamed and [curable resin composition-7b] was obtained. [Curable resin composition-7b] was poured into a mold under nitrogen, and a curing reaction was performed at 120 ° C. for 1 hour and further at 150 ° C. for 2 hours to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Example 8]
1) Production of [Epoxy-modified silicone 8b] [Epoxy-modified silicone 8a] [Epoxy-modified silicone 8a] 40 parts by mass, [Epoxy-modified silicone 9a] 50 parts by mass, [Epoxy-modified silicone 2a] 10 parts by mass [Epoxy-modified silicone 8b] Silicone 8b] was produced.
[Epoxy-modified silicone 8b] thus obtained had a structure represented by the following average composition formula (I-8) having a number average molecular weight of 1,470.
(Me ₂ YSiO _1/2 ) _3.70 (MeZSiO _2/2 ) _3.70 (Me [VCHO] SiO _2/2 ) _4.93 (I-8)
[Wherein (Me ₂ [VCHO] SiO _2/2 ) in the average composition formula (I-8) represents a unit in which vinylcyclohexene oxide is added to a dimethylhydrogensiloxy unit by an anti-Markovnikov by a hydrosilylation reaction. ]

  [Epoxy-modified silicone 8b] contained no SiH unit, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.

  The compound represented by the general formula (1) contained in the [epoxy-modified silicone 8b] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 0.42. The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.300. In [Epoxy-modified silicone 8b], the content of components having a molecular weight of 800 or less was 35.8%, and the content of components having a molecular weight of 10,000 or more was 15.2%. Furthermore, the epoxy value of [epoxy modified silicone 8b] was 0.33, the transition metal component contained was only platinum, and the content of this component was 4.3 ppm in terms of platinum element.

  As the volatile compound remaining in [epoxy-modified silicone 8b], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.002 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.

2) Manufacture and characterization of [curable resin composition-8b] 100 parts by weight of obtained [epoxy-modified silicone 8b], Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride) Acid mixture) 59.4 parts by weight, 1,2-propanediol 3 parts by weight, diazabicycloundecene octylate 0.3 parts by weight are mixed under nitrogen, stirred until the whole becomes uniform, Foamed to obtain [Curable Resin Composition-8b]. [Curable resin composition-8b] was poured into a mold under nitrogen and subjected to a curing reaction at 120 ° C. for 1 hour and further at 150 ° C. for 2 hours to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Example 9]
Production and evaluation of [curable resin composition-9b] 100 parts by mass of the obtained [epoxy-modified silicone 4b] and 0.1 part by mass of a thermosetting cationic polymerization catalyst (Adekaoptomer CP-66 manufactured by Asahi Denka) The mixture was mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain [Curable Resin Composition-9b]. [Curable resin composition-9b] was poured into a mold under nitrogen and subjected to a curing reaction at 120 ° C. for 1 hour and further at 140 ° C. for 3 hours to obtain a cured product. Table 1 shows the performance of the obtained cured product.

[Comparative Example 1]
1) Production of [Epoxy-modified silicone 1c] [Epoxy-modified silicone 1c] was produced by uniformly mixing 45 parts by mass of [Epoxy-modified silicone 1a] and 55 parts by mass of [Epoxy-modified silicone 7a].
[Epoxy-modified silicone 1c] thus obtained had a structure represented by the following average composition formula (J-1) having a number average molecular weight of 1,600.
(Me ₂ [VCHO] SiO _1/2 ) _1.53 (Me ₂ YSiO _1/2 ) _2.65 (Me ₂ SiO _2/2 ) _7.65
(MeZSiO _2/2 ) _2.65 (Me [VCHO] SiO _2/2 ) _1.62 (J-1)
Here, (Me ₂ [VCHO] SiO _2/2 ) in the average composition formula (J-1) is a unit in which vinylcyclohexene oxide is added to a dimethylhydrogensiloxy unit by anti-markovnikov by a hydrosilylation reaction, (Me ₂ [VCHO] SiO _2/2 ) each represents a unit in which vinylcyclohexene oxide is added to an anti-Markovnikov by a hydrosilylation reaction to a dimethylhydrogensiloxy unit. ]

  [Epoxy-modified silicone 1c] contained no SiH unit, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.

  The compound represented by the general formula (1) contained in the [epoxy-modified silicone 1c] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 2.10, The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.26. The content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 1c] was 20.2%, and the content of components having a molecular weight of 10,000 or more was 20.2%. Furthermore, the epoxy value of [epoxy-modified silicone 1c] was 0.20, the transition metal component contained was only platinum, and the content of this component was 4.2 ppm in terms of platinum element.

  As the volatile compound remaining in [epoxy-modified silicone 1c], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.001 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.

2) Manufacture and characterization of [curable resin composition-1c] 100 parts by weight of the obtained [epoxy-modified silicone 1c], Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride) Acid mixture) 35.7 parts by mass, 1,2-propanediol 3 parts by mass, diazabicycloundecene octylate 0.3 parts by mass under nitrogen, stirred until the whole becomes homogeneous, and then removed. It foamed and [curable resin composition-1c] was obtained. [Curable resin composition-1c] was poured into a mold under nitrogen, and a curing reaction was performed at 110 ° C. for 2 hours and further at 120 ° C. for 1 hour to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Comparative Example 2]
Production and Characterization of [Curable Resin Composition-2c] 100 parts by mass of [Epoxy-modified silicone 9b] obtained, Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride mixture) ) 42.5 parts by mass, 1,2-propanediol 3 parts by mass, diazabicycloundecene octylate 0.3 parts by mass under nitrogen, stirred until the whole becomes uniform, and then defoamed Thus, [curable resin composition-2c] was obtained. [Curable resin composition-2c] was poured into a mold under nitrogen and subjected to a curing reaction at 120 ° C. for 1 hour and further at 140 ° C. for 3 hours to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Comparative Example 3]
1) Production of [Epoxy Modified Silicone 3c] [Epoxy Modified Silicone 3c] was produced by uniformly mixing 90 parts by mass of [Epoxy Modified Silicone 8a] and 10 parts by mass of [Epoxy Modified Silicone 7a].
[Epoxy-modified silicone 3c] obtained had a structure represented by the following average composition formula (J-3) having a number average molecular weight of 1,000.
(Me ₂ [VCHO] SiO _1/2 ) _0.18 (Me ₂ YSiO _1/2 ) _1.56 (Me ₂ SiO _2/2 ) _0.90
(MeZSiO _2/2 ) _1.56 (Me [VCHO] SiO _2/2 ) _3.66 (J-3)
[Wherein (Me ₂ [VCHO] SiO _2/2 ) in the average composition formula (J-3) is a unit in which vinylcyclohexene oxide is added to a dimethylhydrogensiloxy unit by an anti-Markovnikov by a hydrosilylation reaction, (Me ₂ [VCHO] SiO _2/2 ) each represents a unit in which vinylcyclohexene oxide is added to an anti-Markovnikov by a hydrosilylation reaction to a dimethylhydrogensiloxy unit. ]

  [Epoxy-modified silicone 3c] contained no SiH unit, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.

  The compound represented by the general formula (1) contained in the [epoxy-modified silicone 3c] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 0.42. The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.221. The content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 1c] was 35.4%, and the content of components having a molecular weight of 10,000 or more was 9.8%. Furthermore, the epoxy value of [epoxy modified silicone 3c] was 0.38, the transition metal component contained was only platinum, and the content of the component was 3.9 ppm in terms of platinum element.

  As the volatile compound remaining in [epoxy-modified silicone 3c], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.001 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.

2) Manufacture and characterization of [curable resin composition-3c] 100 parts by weight of obtained [epoxy-modified silicone 3c], Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride) Acid mixture) 67.2 parts by mass, 3 parts by mass of 1,2-propanediol, and 0.3 parts by mass of diazabicycloundecene octylate are mixed under nitrogen and stirred until the whole becomes uniform. It foamed and [curable resin composition-3c] was obtained. [Curable resin composition-3c] was poured into a mold under nitrogen and subjected to a curing reaction at 120 ° C. for 1 hour and further at 150 ° C. for 2 hours to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Comparative Example 4]
1) Production of [Epoxy Modified Silicone 4c] [Epoxy Modified Silicone 4c] was produced by uniformly mixing 85 parts by mass of [Epoxy Modified Silicone 11a] and 15 parts by mass of [Epoxy Modified Silicone 2a].
[Epoxy-modified silicone 4c] thus obtained had a structure represented by the following average composition formula (J-4) having a number average molecular weight of 1,300.
(Me ₂ YSiO _1/2 ) _2.93 (MeZSiO _2/2 ) _2.93 (Me [VCHO] SiO _2/2 ) _4.64 (J-4)
[Here, (Me ₂ [VCHO] SiO _2/2 ) in the average composition formula (J-4) represents a unit in which vinylcyclohexene oxide is added to a dimethylhydrogensiloxy unit by an anti-Markovnikov by a hydrosilylation reaction. ]

  [Epoxy-modified silicone 4c] contained no SiH unit, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.

  The compound represented by the general formula (1) contained in the [epoxy-modified silicone 4c] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 0.38, The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.279. In [Epoxy-modified silicone 4c], the content of components having a molecular weight of 800 or less was 40.3%, and the content of components having a molecular weight of 10,000 or more was 9.4%. Furthermore, the epoxy value of [epoxy-modified silicone 4c] was 0.36, and the transition metal component contained was only platinum, and the content of this component was 4.6 ppm in terms of platinum element.

  As the volatile compound remaining in [epoxy-modified silicone 4c], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.001 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.

2) Production and Evaluation of [Curable Resin Composition-4c] 100 parts by mass of [Epoxy Modified Silicone 4c], Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride) Acid mixture) 63.7 parts by mass, 1,2-propanediol 3 parts by mass, diazabicycloundecene octylate 0.3 parts by mass under nitrogen, stirring until the whole is uniform, It foamed and [curable resin composition-4c] was obtained. [Curable resin composition-4c] was poured into a mold under nitrogen, and a curing reaction was performed at 120 ° C. for 1 hour and further at 150 ° C. for 2 hours to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Comparative Example 5]
1) Production of [Epoxy Modified Silicone 5c] [Epoxy Modified Silicone 5c] was produced by uniformly mixing 70 parts by mass of [Epoxy Modified Silicone 12a] and 30 parts by mass of [Epoxy Modified Silicone 2a].
[Epoxy-modified silicone 5c] thus obtained had a structure represented by the following average composition formula (J-5) having a number average molecular weight of 2,100.
(Me ₂ YSiO _1/2 ) _6.56 (MeZSiO _2/2 ) _6.02 (Me [VCHO] SiO _2/2 ) _6.56 (J-5)
[Here, (Me ₂ [VCHO] SiO _2/2 ) in the average composition formula (J-5) represents a unit in which vinylcyclohexene oxide is added to a dimethylhydrogensiloxy unit by an anti-Markovnikov by a hydrosilylation reaction. ]

  [Epoxy-modified silicone 5c] contained no SiH unit, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.

  The compound represented by the general formula (1) contained in the [epoxy-modified silicone 5c] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 0.21. The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.343. The content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 5c] was 37.0%, and the content of components having a molecular weight of 10,000 or more was 28.3%. Furthermore, the epoxy value of [Epoxy-modified silicone 5c] was 0.29, the transition metal component contained was only platinum, and the content of this component was 4.0 ppm in terms of platinum element.

  As the volatile compound remaining in [epoxy-modified silicone 5c], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.002 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.

2) Manufacture and characterization of [curable resin composition-5c] 100 parts by weight of the obtained [epoxy-modified silicone 5c], Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride) Acid mixture) 50.7 parts by mass, 1,2-propanediol 3 parts by mass, diazabicycloundecene octylate 0.3 part by mass are mixed under nitrogen and stirred until the whole becomes uniform. It foamed and [curable resin composition-5c] was obtained. [Curable resin composition-5c] was poured into a mold under nitrogen and cured at 120 ° C. for 1 hour, further at 140 ° C. for 2 hours, and further at 160 ° C. for 1 hour to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Comparative Example 6]
1) Production of [Epoxy Modified Silicone 6c] By uniformly mixing 35 parts by mass of [Epoxy Modified Silicone 13a], 10 parts by mass of [Epoxy Modified Silicone 2a], and 55 parts by mass of [Epoxy Modified Silicone 14a], [ Epoxy-modified silicone 6c] was produced.
The obtained [epoxy-modified silicone 6c] had a structure represented by the following average composition formula (J-6) having a number average molecular weight of 1,730.
(Me ₂ [VCHO] SiO _1/2 ) _1.41 (Me ₂ YSiO _1/2 ) _2.61 (Me ₂ SiO _2/2 ) _9.18
(MeZSiO _2/2 ) _2.61 (Me [VCHO] SiO _2/2 ) _2.05 (J-6)
[Wherein (Me ₂ [VCHO] SiO _2/2 ) in the average composition formula (J-6) is a unit in which vinylcyclohexene oxide is added to a dimethylhydrogensiloxy unit by an anti-Markovnikov addition by a hydrosilylation reaction, (Me ₂ [VCHO] SiO _2/2 ) each represents a unit in which vinylcyclohexene oxide is added to an anti-Markovnikov by a hydrosilylation reaction to a dimethylhydrogensiloxy unit. ]

  [Epoxy-modified silicone 6c] contained no SiH unit, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.

  The compound represented by the general formula (1) contained in the [epoxy-modified silicone 6c] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is a compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 0.30, The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.256. In addition, the content of components having a molecular weight of 800 or less in [Epoxy-modified silicone 6c] was 18.5%, and the content of components having a molecular weight of 10,000 or more was 23.6%. Furthermore, the epoxy value of [epoxy-modified silicone 6c] was 0.20, and the transition metal component contained was only platinum, and the content of this component was 2.4 ppm in terms of platinum element.

  As the volatile compound remaining in [epoxy-modified silicone 6c], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.001 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.

2) Manufacture and characterization of [curable resin composition-6c] 100 parts by weight of obtained [epoxy-modified silicone 6c], Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride) Acid mixture) 35.7 parts by mass, 1,2-propanediol 3 parts by mass, and diazabicycloundecene octylate 0.3 parts by mass under nitrogen, stirred until the whole becomes homogeneous, and then removed. It foamed and [curable resin composition-6c] was obtained. [Curable resin composition-6c] was poured into a mold under nitrogen and subjected to a curing reaction at 110 ° C. for 2 hours and further at 120 ° C. for 1 hour to obtain a cured product. Table 2 shows the performance of the obtained cured product.

[Comparative Example 7]
During hydrosilylation reaction, 75 g of 1,3-divinyltetramethyldisiloxane purified by dehydration distillation was used, 84.9 g of 4-vinylcyclohexene oxide purified by dehydration distillation was used, and 500 ppm of platinum in terms of platinum element was used. Except that 2.2 g of 1,4-dioxane solution of the platinum divinyltetramethyldisilicone complex contained was added and the hydrosilylation reaction time was 80 hours, the same as [Production Example 6 of Epoxy-Modified Silicone] The hydrosilylation reaction was carried out.

  At the start of the reaction, the ratio between the total number of SiH units (r1) of the organohydrogensilicone and the number of moles (r2) of the carbon-carbon double bonds of the silicone having a coexisting carbon-carbon double bond ( The value of r2 / r1) is 0.605, the total number of moles of SiH units of organohydrogensilicone (r1), and the carbon-carbon 2 of the compound <A> having a coexisting carbon-carbon double bond and epoxy group. The value of the ratio (r4 / r1) to the number of moles (r4) of heavy bonds is 0.514, and the total number of carbon-carbon double bonds in the added compound relative to the total number of moles of SiH units in the organohydrogensilicone The number of moles was 1.12 times.

  Further, the number of moles of the catalyst used for starting the hydrosilylation reaction in terms of metal atoms was 1 / 235,872 times the total number of moles of SiH units of the organohydrogensilicone before the hydrosilylation reaction. .

After completion of the hydrosilylation reaction, 43 g of benzonitrile purified by dehydration and distillation under dry nitrogen was added to the reaction solution while maintaining the heating temperature. After stirring for 2 hours under an atmospheric pressure dry nitrogen atmosphere, stirring was stopped. And cooled to room temperature. When the solution was sampled after cooling and analyzed by ¹ H-NMR, it was confirmed that the conversion rate of SiH units was 95%, and the remaining 5% of SiH units were unreacted. 1,4-dioxane was distilled off from the cooled reaction solution using an evaporator at a heating temperature of 40 ° C. under reduced pressure to obtain an epoxy-modified silicone-containing component.

  The obtained epoxy-modified silicone-containing component was introduced at a temperature of 40 ° C. and a pressure of 0. The low boiling compound was distilled off in a glass tube oven at 2 kPa to obtain an epoxy-modified silicone-containing component with reduced low boiling compound. This operation was repeated with respect to the remaining epoxy-modified silicone obtained by distilling off 1,4-dioxane obtained above, to obtain 195 g of [epoxy-modified silicone 15a] in which low boiling point compounds were reduced.

[Epoxy-modified silicone 7c] thus obtained had a structure represented by the following average composition formula (J-7) having a number average molecular weight of 1,900.
(Me ₂ YSiO _1/2 ) _7.22 (MeZSiO _2/2 ) _7.22
(Me [VCHO] SiO _2/2 ) _4.12 (Me [VCHO] SiO _2/2 ) _0.60 (J-7)
Here, Y in the average composition formula (J-7) represents a divalent organic group represented by —CH ₂ —CH ₂ —, and Z represents a bond with a divalent hydrocarbon group Y. In addition, (Me [VCHO] SiO _2/2 ) represents a unit in which vinylcyclohexene oxide is added to a hydrogen methylsiloxy unit by an anti-markovnikov by a hydrosilylation reaction. ]

Since no unreacted SiH unit was detected, g = 0 in the average composition formula (3), and the value of [g / (a + b + c + d + e + f + g + h + i + j)] was 0.
The compound represented by the general formula (1) contained in the [epoxy-modified silicone 7c] is a compound represented by the chemical formula (25) (total mass number 759 with the mass of sodium), The compound represented by the formula (2) is the compound represented by the chemical formula (26) (total mass number 697 with the mass of sodium), and the value of [WB] / [WA] is 1.85, The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] in the average composition formula (3) was 0.38. In [Epoxy-modified silicone 7c], the content of components having a molecular weight of 800 or less was 22%, and the content of components having a molecular weight of 10,000 or more was 22%. Furthermore, the epoxy value of [Epoxy-modified silicone 7c] was 0.24, the transition metal component contained was only platinum, and the content of this component was 5 ppm in terms of platinum element.

  As the volatile compound remaining in [epoxy-modified silicone 7c], only 1,4-dioxane was detected, and the total amount of the remaining volatile compound was 0.001% by mass or less. Further, as the low boiling point compound, 4-ethylidenylcyclohexene oxide formed by the internal transition of the carbon-carbon double bond of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide was detected, and the residual amount thereof was They were 0.001 mass% and 0.002 mass%, respectively. The residual amount of the deactivator or deactivator of the hydrosilylation catalyst was 0.001% by mass or less, and other compounds were not detected.

  When [Epoxy-modified silicone 7c] was stored at 25 ° C. for 1 week, the molecular weight was increased and the viscosity was increased by about 20%. Therefore, the storage stability was judged to be poor.

[Example 10]
1) Manufacture of die-bonding material [Epoxy-modified silicone 8a] manufactured in [Epoxy-modified silicone production example 8] was added to Ricacid MH-700G (product of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride / hexahydrophthalic anhydride mixture). ) 71.3 parts by mass, 1,2-propanediol 3 parts by mass, diazabicycloundecene octylate 0.3 parts by mass under nitrogen, stirred until the whole becomes uniform, then defoamed Thus, a die bond material for an optical semiconductor element was obtained.

2) Production of optical semiconductor element A light emitting element having a main emission peak of 460 nm using the die bond material for optical semiconductor element manufactured in 1) above for a housing material made of polyphthalamide with lead electrode heated and dried at 150 ° C. for 2 hours. Was mounted and cured at 120 ° C. for 1 hr and further at 150 ° C. for 2 hours to fix the light emitting element. Then, after electrically connecting a light emitting element and a lead electrode with a gold wire, [curable resin composition-1b] is inject | poured into a type | mold under nitrogen, 120 degreeC is 1 hour, Furthermore, 150 degreeC 2 A time curing reaction was performed to produce 20 optical semiconductor elements having the structure shown in FIG. Table 3 shows the results of solder reflow resistance of the obtained optical semiconductor light emitting device. Even if the optical semiconductor light-emitting device obtained by this operation was energized at room temperature at 50 mA for 200 hours, peeling between the device and the sealing portion and a decrease in luminance were not observed.

[Example 11]
Using [Curable Resin Composition-2b], and curing conditions after injecting [Curable Resin Composition-2b] into the mold were 120 ° C. for 1 hour, 140 ° C. for 2 hours, and subsequently 160. Twenty optical semiconductor elements having the structure shown in FIG. 1 were produced in the same manner as in Example 10 except that the temperature was 1 hour at ° C. Table 3 shows the results of solder reflow resistance of the obtained optical semiconductor light emitting device. Even if the optical semiconductor light-emitting device obtained by this operation was energized at room temperature at 50 mA for 200 hours, peeling between the device and the sealing portion and a decrease in luminance were not observed.

[Example 12]
Except for using [Curable Resin Composition-3b], and curing conditions after injecting [Curable Resin Composition-3b] into the mold at 120 ° C. for 1 hour, and further at 150 ° C. for 2 hours. In the same manner as in Example 10, 20 optical semiconductor elements having the structure shown in FIG. Table 3 shows the results of solder reflow resistance of the obtained optical semiconductor light emitting device. Even if the optical semiconductor light-emitting device obtained by this operation was energized at room temperature at 50 mA for 200 hours, peeling between the device and the sealing portion and a decrease in luminance were not observed.

[Example 13]
Except that [curable resin composition-4b] was used, and that the curing conditions after injecting [curable resin composition-4b] into the mold were 1 hour at 120 ° C and 3 hours at 140 ° C. In the same manner as in Example 10, 20 optical semiconductor elements having the structure shown in FIG. Table 3 shows the results of solder reflow resistance of the obtained optical semiconductor light emitting device. Even if the optical semiconductor light-emitting device obtained by this operation was energized at room temperature at 50 mA for 200 hours, peeling between the device and the sealing portion and a decrease in luminance were not observed.

[Example 14]
Except that [curable resin composition-5b] was used, and that the curing conditions after injecting [curable resin composition-5b] into the mold were 120 ° C for 1 hour, and further 150 ° C for 2 hours. In the same manner as in Example 10, 20 optical semiconductor elements having the structure shown in FIG. Table 3 shows the results of solder reflow resistance of the obtained optical semiconductor light emitting device. Even if the optical semiconductor light-emitting device obtained by this operation was energized at room temperature at 50 mA for 200 hours, peeling between the device and the sealing portion and a decrease in luminance were not observed.

[Example 15]
[Curable resin composition-6b] was used, and the curing conditions after injecting [curable resin composition-6b] into the mold were 120 ° C for 1 hour, 140 ° C for 2 hours, and then 160 ° C. 20 optical semiconductor elements having the structure shown in FIG. 1 were produced in the same manner as in Example 10 except that the time was 1 hour. Table 3 shows the results of solder reflow resistance of the obtained optical semiconductor light emitting device. Even if the optical semiconductor light-emitting device obtained by this operation was energized at room temperature at 50 mA for 200 hours, peeling between the device and the sealing portion and a decrease in luminance were not observed.

[Example 16]
Except for using [Curable Resin Composition-7b] and curing conditions after injecting [Curable Resin Composition-7b] into the mold at 120 ° C. for 1 hour, and further at 150 ° C. for 2 hours. In the same manner as in Example 10, 20 optical semiconductor elements having the structure shown in FIG. Table 3 shows the results of solder reflow resistance of the obtained optical semiconductor light emitting device. Even if the optical semiconductor light-emitting device obtained by this operation was energized at room temperature at 50 mA for 200 hours, peeling between the device and the sealing portion and a decrease in luminance were not observed.

[Example 17]
Except for using [Curable Resin Composition-8b], and curing conditions after injecting [Curable Resin Composition-8b] into the mold at 120 ° C. for 1 hour, and further at 150 ° C. for 2 hours. In the same manner as in Example 10, 20 optical semiconductor elements having the structure shown in FIG. Table 3 shows the results of solder reflow resistance of the obtained optical semiconductor light emitting device. Even if the optical semiconductor light-emitting device obtained by this operation was energized at room temperature at 50 mA for 200 hours, peeling between the device and the sealing portion and a decrease in luminance were not observed.

[Example 18]
Except for using [Curable Resin Composition-9b] and curing conditions after injecting [Curable Resin Composition-9b] into the mold at 120 ° C. for 1 hour and further at 140 ° C. for 3 hours. In the same manner as in Example 10, 20 optical semiconductor elements having the structure shown in FIG. Table 3 shows the results of solder reflow resistance of the obtained optical semiconductor light emitting device. Even if the optical semiconductor light-emitting device obtained by this operation was energized at room temperature at 50 mA for 200 hours, peeling between the device and the sealing portion and a decrease in luminance were not observed.

[Comparative Example 8]
Except for using [Curable Resin Composition-1c], and curing conditions after injecting [Curable Resin Composition-1c] into a mold at 110 ° C. for 2 hours, and further at 120 ° C. for 1 hour. In the same manner as in Example 10, 20 optical semiconductor elements having the structure shown in FIG. Table 4 shows the results of solder reflow resistance of the obtained optical semiconductor light emitting device.

[Comparative Example 9]
Except for using [Curable Resin Composition-2c] and curing conditions after injecting [Curable Resin Composition-2c] into the mold at 120 ° C. for 1 hour, and further at 140 ° C. for 3 hours. In the same manner as in Example 10, 20 optical semiconductor elements having the structure shown in FIG. Table 4 shows the results of solder reflow resistance of the obtained optical semiconductor light emitting device.

[Comparative Example 10]
Except that [curable resin composition-3c] was used, and that the curing conditions after injecting [curable resin composition-3c] into the mold were 120 ° C for 1 hour, and further 150 ° C for 2 hours. In the same manner as in Example 10, 20 optical semiconductor elements having the structure shown in FIG. Table 4 shows the results of solder reflow resistance of the obtained optical semiconductor light emitting device.

[Comparative Example 11]
Except for using [Curable Resin Composition-4c], and curing conditions after injecting [Curable Resin Composition-4c] into a mold at 120 ° C. for 1 hour, and further at 150 ° C. for 2 hours. In the same manner as in Example 10, 20 optical semiconductor elements having the structure shown in FIG. Table 4 shows the results of solder reflow resistance of the obtained optical semiconductor light emitting device.

[Comparative Example 12]
Using [Curable Resin Composition-5c], and curing conditions after injecting [Curable Resin Composition-5c] into a mold were 1 hour at 120 ° C., 2 hours at 140 ° C., and 160 Twenty optical semiconductor elements having the structure shown in FIG. 1 were produced in the same manner as in Example 10 except that the temperature was 1 hour at ° C. Table 2 shows the results of solder reflow resistance of the obtained optical semiconductor light emitting device.

[Comparative Example 13]
Except for using [Curable Resin Composition-6c], and curing conditions after injecting [Curable Resin Composition-6c] into the mold at 110 ° C. for 2 hours and further at 120 ° C. for 1 hour. In the same manner as in Example 10, 20 optical semiconductor elements having the structure shown in FIG. Table 4 shows the results of solder reflow resistance of the obtained optical semiconductor light emitting device.

  According to the present invention, an epoxy-modified silicone having transparency, light resistance, heat resistance, heat discoloration resistance, crack resistance, adhesion, solder reflow resistance, and suitable for use as a light emitting device sealing material, the epoxy modified silicone And a curable resin composition for sealing a light-emitting element, as well as excellent adhesion to an element or a package material formed using the resin composition, without cracks, and with little decrease in luminance over a long period of time It is possible to provide a light emitting component such as an excellent light emitting diode.

  In addition, according to the present invention, it is possible to provide a curable resin composition that is suitable for injection molding, and is suitable as a lens material that is hard and has excellent step stability after curing.

DESCRIPTION OF SYMBOLS 1 Light emitting element 2 Light emitting element die bond material 3 Light emitting element sealing material 4 Gold wire 5 Lead electrode 6 Heat sink 7 Housing material

Claims (10)

An average composition formula comprising at least a compound represented by the following general formula (1) and a compound represented by the following general formula (2) and satisfying the following (a) to (e): Epoxy-modified silicone represented by 3).
(A) The content of the compound represented by the general formula (1) [WA] calculated from the peak intensity obtained when measured by matrix-assisted ionization time-of-flight mass spectrometry by the following formula (1) The ratio [WB] / [WA] of the content [WB] of the compound represented by the general formula (2) to 0.10 or more and 2.00 or less,

(B) The value of [g / (a + b + c + d + e + f + g + h + i + j)] is 0.020 or less,
(C) The value of [(a + b) / (a + b + c + d + e + f + g + h + i + j)] is 0.25 or more and 0.35 or less,
(D) the content of components having a molecular weight of 800 or less is 20% or more and 40% or less,
(E) The content of components having a molecular weight of 10,000 or more is 10% or more and 25% or less

[Wherein R ¹ is each independently A) an unsubstituted or substituted carbon having an aliphatic hydrocarbon unit composed of one or more structures selected from a chain, branched and cyclic structure group A monovalent aliphatic organic group having a number of 1 to 24 and an oxygen number of 0 to 5, B) an unsubstituted or substituted aromatic hydrocarbon unit, which is unsubstituted or substituted as necessary A monovalent fragrance having an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of chain, branched and cyclic, having 6 to 24 carbon atoms and 0 to 5 oxygen atoms A group organic group, C) having an aliphatic and / or aromatic hydrocarbon unit composed of one or more structures selected from the group consisting of an unsubstituted or substituted chain, branched, and cyclic structure. 5 to 26, oxygen number 0 to 5, and silicon number 1 represents at least one organic group selected from the group consisting of a monovalent organic group which is 1.
R ² each independently has 4 or more carbon atoms having an aliphatic hydrocarbon unit having one or more types of structures selected from the group consisting of D) unsubstituted or substituted, chain, branched, and cyclic structures. And an organic group containing an epoxy group having an oxygen number of 1 or more and 5 or less.
R ³ each independently has A) an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of an unsubstituted or substituted chain, branched and cyclic structure, and having 1 or more carbon atoms A monovalent aliphatic organic group having 24 or less and an oxygen number of 0 or more and 5 or less, B) an unsubstituted or substituted aromatic hydrocarbon unit, which is optionally substituted or substituted, a chain, A monovalent aromatic organic group having 6 to 24 carbon atoms and 0 to 5 oxygen atoms, which has an aliphatic hydrocarbon unit composed of one or more structures selected from the group consisting of branched and cyclic structures; C) having 5 or more and 26 or less carbon atoms, having an aliphatic and / or aromatic hydrocarbon unit having one or more structures selected from the group consisting of unsubstituted, substituted, and chain-like, branched and cyclic structures 1 in which the oxygen number is 0 or more and 5 or less, and the silicon number is 1. A monovalent organic group, E) a monovalent structure comprising one or more structures selected from the group consisting of a chain-like and a branched-chain, unsubstituted or substituted, having 2 to 6 carbon atoms, including a carbon-carbon double bond It represents at least one organic group selected from the group consisting of aliphatic organic groups.
X represents an unsubstituted or substituted divalent hydrocarbon group having one or more structures selected from the group consisting of a chain and a branch having 2 to 6 carbon atoms.
Each Y independently represents a divalent hydrocarbon group having one or more structures selected from the group consisting of a chain and a branched group, which are unsubstituted or substituted with 2 to 6 carbon atoms.
Furthermore, Z represents a bond with a divalent hydrocarbon group Y.
In the formula, t each independently represents an integer of 0 or more, u represents each independently an integer of 3 or more, and v represents an integer of 0 or more.
A, b, c, d, e, f, g, h, i, j represent the number of moles of each structural unit present in 1 mol of the epoxy-modified silicone, and a, e, f exceeds 0. B, c, d, g, h, i, and j are values that are 0 or more and satisfy e = a + d + i. The chain in the general formulas (1) and (2) may be random or block. ] The epoxy-modified silicone according to claim 1, wherein an epoxy value of the epoxy-modified silicone represented by the average composition formula (3) is 0.20 or more and 0.40 or less. The epoxy-modified silicone according to claim 1 or 2, wherein a value of v in the general formula (2) is 0 or more and 9 or less. The value of [(h + i + j) / (a + b + c + d + e + f + g + h + i + j)] of the epoxy-modified silicone represented by the average composition formula (3) is in a range of 0.040 or less. The epoxy-modified silicone according to item. A curable resin composition comprising 100 parts by mass of the epoxy-modified silicone according to any one of claims 1 to 4 and 1 part by mass or more and 200 parts by mass or less of a curing agent for epoxy resin. The curable resin composition according to claim 5, further comprising 0.001 part by mass or more and 10 parts by mass or less of a curing accelerator. A curable resin composition comprising 100 parts by mass of the epoxy-modified silicone according to any one of claims 1 to 4 and 0.001 to 10 parts by mass of a cationic polymerization catalyst. The sealing material for light emitting elements which consists of curable resin composition of any one of Claim 5 to 7. The light emitting component sealed with the sealing material for light emitting elements of Claim 8. A lens comprising the curable resin composition according to any one of claims 5 to 7.

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