JP2011208094A - Polyorganosiloxane, method for producing the same, curable resin composition containing the same and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable polyorganosiloxane enabling a cured product to be formed, the cured product having good transparency, excellent light resistance, heat yellowing resistance and thermal shock resistance and no tackiness, to provided a curable resin composition using the same, and to provided luminous parts and an optical semiconductor device.SOLUTION: The polyorganosiloxane is represented by the average composition formula (1): RSiOand contains (A) a siloxane unit having at least a fluorine-substituted phenyl group as a substituent as Rin the average composition formula (1) and (B) a siloxane unit having in one molecule at least one curable functional group selected from the group consisting of an organic group containing a carbon-carbon double bond, an epoxy group, an episulfide group, a thiocarbonate group, a dithiocarbonate group and a trithiocarbonate group as a substituent as Rin the average composition formula (1), wherein the ratio between the contents of the components (A) and (B) is in a predetermined range. In the formula, Rs each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent organic group comprising one or more structures selected from the group of unsubstituted or substituted chain, branched and cyclic structures, and n is a positive number satisfying 1≤n<2.

Description

  The present invention relates to a curable polyorganosiloxane that is excellent in transparency and light resistance, and that can be used for applications requiring stable and reproducible thermal shock resistance and tackiness in thermal cycle, and production thereof. The present invention relates to a method, a curable resin composition containing the method, and use thereof.

  Conventionally, an epoxy resin composition using an acid anhydride curing agent gives a transparent cured product and has high heat resistance and adhesiveness. Therefore, a light emitting diode (hereinafter abbreviated as LED) and a photodiode are used. It has been suitably used as an encapsulating resin for optical semiconductors. However, in recent years, the performance of optical semiconductors has improved, and as a sealing material for LEDs, in addition to the conventionally required good transparency, high heat resistance, and adhesiveness, heat yellowing resistance, and thermal shock resistance during thermal cycling Further, a cured product having excellent surface properties and having no surface tackiness is desired. Conventionally used bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, alicyclic epoxy resins, etc. In fact, a composition made of an epoxy resin cannot obtain sufficient characteristics. In response, curable polyorganosiloxane having a siloxane skeleton that is stable against heat or light as a repeating unit is being replaced as a resin for a light-emitting element sealing material.

The polyorganosiloxane can be broadly divided into a methyl silicone type having an alkyl group such as a methyl group represented by polydimethylsiloxane as a substituent, and a phenyl silicone type having a phenyl group represented by polyphenylmethylsiloxane as a substituent. There are two types. Methylsilicone polysiloxane is excellent in terms of deterioration of light resistance and the like, and in terms of thermal shock resistance in thermal cycling, but since tackiness remains on the surface of the cured product, foreign matters such as dust can be easily obtained. In fact, many problems still remain such as adhesion and loss of permeability.
On the other hand, phenylsilicone-based polysiloxanes can increase the hardness of a cured product, which has been a problem of methylsilicone-based polysiloxanes, and thus many proposals have been made as semiconductor sealing materials.

For example, Patent Document 1 proposes a curable polysiloxane containing a phenyl group and an epoxy group and having a glass transition temperature of −90 ° C. or more and 150 ° C. or less having a T structure as an essential constituent unit. However, the polysiloxane described in the publication has a low light resistance, and has not yet been a satisfactory level with respect to thermal shock resistance and adhesiveness.
For example, Patent Document 2 proposes a curable polysiloxane having a specific range of molecular weight having at least two epoxy groups in one molecule and a composition containing the polysiloxane. However, the resin composition obtained is not yet satisfactory in terms of light resistance, thermal shock resistance and adhesiveness. In addition, the publication discloses that a phenyl group may be substituted as a substituent of the siloxane skeleton, and that some or all of the hydrogen atoms may be substituted with halogen atoms such as fluorine. In addition, there is no description or suggestion of the substitution effect.
Thus, phenylsilicone-based polysiloxanes have low light resistance and are easily deteriorated by light. Therefore, improvement is required for use as a high-power LED encapsulant that generates strong light in the short wavelength range. It was. In response, many attempts have been made to improve the light stability of polysiloxanes having phenyl groups as substituents.

For example, Patent Document 3 discloses a method of adding a phenolic antioxidant and a hindered amine compound to a curable polysiloxane having a phenyl group as a substituent. However, when an antioxidant or the like that suppresses photodegradation is used, the effect of the antioxidant is limited to a relatively short time. On the other hand, a large amount of antioxidant is necessary to develop a long-term effect. Thus, there is a problem that transparency of a cured product obtained by curing the polysiloxane is lowered. Furthermore, when the modified product formed by the action of the antioxidant used is markedly colored and the effect of the antioxidant cannot be obtained, the cured product obtained by curing the polysiloxane is markedly colored. There were many problems. Furthermore, the patent document does not show any description or suggestion regarding a phenyl group having a fluorine atom as a substituent.
In addition, various attempts have been made to develop a material having excellent transparency and little change with time by improving the skeleton structure of a curable polysiloxane containing a phenyl group as a substituent.

  For example, Patent Document 4 discloses a polysiloxane containing a specific amount of phenyl group in the molecule and an alkenyl group, and the polysiloxane and at least two Si— in one molecule. A curable polysiloxane composition for a light-emitting diode containing a polysiloxane having an H group, an addition reaction catalyst, a silicon compound having an epoxy group and a specific functional group, and a liquid acid anhydride is disclosed. However, the light resistance is still inadequate, and the curable composition has problems in handling properties such as poor storage stability and increased viscosity during storage. In addition, the publication describes that part or all of the hydrogen of the phenyl group may be substituted with a halogen atom such as fluorine, bromine, chlorine, etc. Not done at all.

Registration No. 3263177 JP 2005-171021 A JP 2005-272697 A JP 2005-327777 A

  In view of the above circumstances, the present invention forms a cured product that has good transparency and excellent light resistance under heating conditions, as well as heat-resistant yellowing and thermal shock resistance and tack resistance in thermal cycle. It is an object of the present invention to provide a curable polyorganosiloxane that can be used, and a curable resin composition, a light-emitting component, and an optical semiconductor device using the same.

As a result of intensive studies in order to solve the above problems, the present inventor contains phenylsiloxane units having a specific number of fluorine atoms containing a phenyl group as a substituent in a specific ratio, and a curable functional group. The present inventors have found that a curable polyorganosiloxane having the above can solve the above-mentioned problems, and have completed the present invention.
That is, the present invention is as follows.
[1] A polyorganosiloxane represented by the following average composition formula (1), which contains at least the siloxane units of the following (A) and (B), and is represented by the following general formula (2) (A ) And (B) are polyorganosiloxanes having a component index α of 0.001 or more and 19 or less.

(Wherein R ¹ is each independently a monovalent structure composed of one or more structures selected from the group consisting of hydrogen, halogen atoms, hydroxyl groups, unsubstituted or substituted, chain, branched and cyclic structures. Represents an organic group, and n is a positive number satisfying 1 ≦ n <2.)

(A) In the average composition formula (1), as R ¹ , at least a siloxane unit having a phenyl group having a fluorine atom as a substituent as a substituent,
(B) A group consisting of an organic group, an epoxy group, an episulfide group, a thiocarbonate group, a dithiocarbonate group and a trithiocarbonate group containing a carbon-carbon double bond in one molecule as R ¹ in the average composition formula (1) A siloxane unit having at least one curable functional group selected from as a substituent.
Component index α = (αa) / (αb) (2)
(Here, in the general formula (2), αa is the content (mol%) of the component (A) with respect to the total Si amount in the polyorganosiloxane represented by the average composition formula (1), and αb is the average composition formula. (The content (mol%) of the component (B) with respect to the total amount of Si in the polyorganosiloxane represented by (1) is shown.)

[2] The polyorganosiloxane according to [1] above, wherein all of the aromatic hydrocarbon units contained as R ¹ are phenyl groups substituted with fluorine atoms.
[3] The above-mentioned [1] or [2], wherein all of the aromatic hydrocarbon units contained as R ¹ are phenyl groups substituted with 2 or more and 3 or less fluorine atoms The polyorganosiloxane of any one of Claims.
[4] The above [1] to [1], wherein the total content of siloxane units having a hydrolyzable group contained in the polyorganosiloxane as a substituent is 5 mol% or less based on the total amount of Si. 3]. The polyorganosiloxane according to any one of [3].
[5] The curable functional group contained in the polyorganosiloxane is at least one selected from the group consisting of a vinyl group, a methacryl group, an epoxy group, an episulfide group, a dithiocarbonate group, and a trithiocarbonate group. The polyorganosiloxane according to any one of [1] to [4] above.

[6] The above-mentioned [1], wherein the component index β of the D structural unit, T structural unit and Q structural unit constituting the polyorganosiloxane is in the range of 0.01 to 1.4. -The polyorganosiloxane of any one of [5].
Component index β = {(βD) / (βQ + βT)} (3)
(In the formula (3), βD is the content (mol%) of the D structural unit with respect to the total Si amount in the polyorganosiloxane represented by the average composition formula (1), and βQ is the average composition formula (1). The content (mol%) of the Q structural unit with respect to the total Si amount in the polyorganosiloxane represented by the formula, βT is the content of the T structural unit with respect to the total Si amount in the polyorganosiloxane represented by the average composition formula (1) The amount (mol%) is shown, and 0 ≦ {βQ / (βQ + βT + βD)} ≦ 0.1.)
[7] Any one of [1] to [6] above, wherein the content of the curable functional group contained in the polyorganosiloxane is 0.001 mol / 100 g or more and 1 mol / 100 g or less. The polyorganosiloxane described.

[8] The polyorganosiloxane according to any one of [1] to [7] above, wherein the condensation rate is 80% or more.
[9] The polyorganosiloxane according to any one of [1] to [8] above, wherein the polyorganosiloxane has a viscosity at 25 ° C. of 1,000 Pa · s or less.
[10] Obtained by hydrolyzing a reactive organosilicon compound having a hydrolyzable group represented by the following general formula (4) containing at least the following components (a) and (b) in the presence of water: When the polyorganosiloxane is produced by polycondensation of the intermediate after hydrolysis, the mixing index γ of the component (a) and the component (b) represented by the following general formula (5) is 0.001 or more. The method for producing a polyorganosiloxane according to the above [1], which satisfies a range of 19 or less.

(Wherein R ¹ is each independently a monovalent consisting of one or more structures selected from the group consisting of hydrogen, halogen atoms, hydroxyl groups, unsubstituted or substituted, chain, branched and cyclic structures. X represents independently a monovalent hydrolyzable group, and q and r satisfy the conditions of q ≧ 0, r> 0, 2 ≦ q + r ≦ 4. Is a positive number.)

(A) In the general formula (4), a reactive organosilicon compound having, as R ¹ , at least a phenyl group having a fluorine atom as a substituent as R ¹ .
(B) In the general formula (4), a group consisting of an organic group containing a carbon-carbon double bond, an epoxy group, an episulfide group, a thiocarbonate group, a dithiocarbonate group and a trithiocarbonate group as R ¹ in one molecule. A reactive organosilicon compound having at least one curable functional group selected from as a substituent.
Mixing index γ = (γa) / (γb) (5)
(In the formula (5), γa is the content (mol%) of the component (a) with respect to all reactive organosilicon compounds, and γb is the content of the component (b) with respect to all reactive organosilicon compounds. Amount (mol%) is indicated.)

[11] The mixing index δ of the reactive organosilicon compound having the hydrolyzable group represented by the general formula (6) is in the range of 0.01 to 1.4, 10] The process for producing a polyorganosiloxane according to 10];
Mixing index δ = {(δD) / (δQ + δT)} (6)
Here, in formula (6), δD is a reactive organosilicon having a hydrolyzable group where q = 2 in a reactive organosilicon compound having a hydrolyzable group represented by general formula (4) Compound content (mol%), δQ is a reactive organosilicon compound having a hydrolyzable group where q = 0 in the reactive organosilicon compound having a hydrolyzable group represented by the general formula (4) Content (mol%), δT of the reactive organosilicon compound having a hydrolyzable group of q = 1 in the reactive organosilicon compound having a hydrolyzable group represented by the general formula (4) The content (mol%) is shown, and 0 ≦ {δQ / (δQ + δT + δD)} ≦ 0.1.)
[12] The method for producing a polyorganosiloxane according to [10] or [11] above, wherein the hydrolyzable group is an alkoxy group.

[13] The above-mentioned [10], wherein alkoxide-based organotin is used as a catalyst when hydrolyzing in the presence of water and polycondensation of the obtained hydrolysis product to produce a polyorganosiloxane. -The manufacturing method of the polyorganosiloxane of any one of [12].
[14] The step of hydrolyzing the reactive organosilicon compound having a hydrolyzable group represented by the general formula (4) in the presence of water is reflux without distilling water or a solvent out of the reaction system. The method for producing a polyorganosiloxane according to any one of [10] to [13] above, wherein the method is performed by a process.
[15] The method for producing a polyorganosiloxane according to any one of [10] to [14] above, wherein the condensation ratio of the intermediate after completion of the hydrolysis step is 70% or more.
[16] A curable resin composition comprising the polyorganosiloxane according to any one of [1] to [9] above and a curing catalyst.
[17] A light-emitting component produced using the curable resin composition according to [16] above.
[18] A semiconductor device including the light-emitting component according to [17].

  According to the present invention, a cured product having no tackiness, good transparency, excellent light resistance under heating conditions, heat-resistant yellowing, and resistance to thermal shock in a thermal cycle is formed. It becomes possible to provide the modified resin composition which can be manufactured.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present invention”) will be described in detail. In addition, this invention is not limited to the form shown below.
The polyorganosiloxane in the present invention is a polyorganosiloxane represented by the following average composition formula (1), which contains at least the following siloxane units (A) and (B), and is represented by the following general formula (2): The component index α of the siloxane units represented by (A) and (B) is 0.001 or more and 19 or less.

(Wherein R ¹ is each independently a monovalent structure composed of one or more structures selected from the group consisting of hydrogen, halogen atoms, hydroxyl groups, unsubstituted or substituted, chain, branched and cyclic structures. Represents an organic group, and n is a positive number satisfying 1 ≦ n <2.)

(A) In the average composition formula (1), as R ¹ , at least a siloxane unit having a phenyl group having a fluorine atom as a substituent as a substituent,
(B) In the average composition formula (1), R ¹ is selected from the group consisting of an organic group containing a carbon-carbon double bond, an epoxy group, an episulfide group, a dithiocarbonate group, and a trithiocarbonate group as one molecule. Siloxane units having at least one curable functional group as a substituent,
Component index α = (αa) / (αb) (2)
(In the general formula (2), αa is the content (mol%) of the component (A) in the polyorganosiloxane represented by the average composition formula (1), and αb is the average composition formula (1). The content (mol%) of the component (B) in the polyorganosiloxane represented is shown.)

In the present invention, each R ¹ is independently a hydrogen atom, a halogen atom such as chlorine, bromine or iodine, a hydroxyl group, or [a] a chain, branched or cyclic structure which is unsubstituted or substituted. Having an aliphatic hydrocarbon unit having at least one structure selected from the group, having a carbon number of 1 to 24 (preferably 4 to 24) and an oxygen number of 0 to 5 (preferably 1 to 5) A monovalent aliphatic organic group, [b] from a structural group consisting of a chain, a branched chain and a ring, which has an unsubstituted or substituted aromatic hydrocarbon unit and is unsubstituted or substituted as necessary. At least one selected from the group consisting of monovalent aromatic organic groups having an aliphatic hydrocarbon unit having one or more selected structures and having 6 to 24 carbon atoms and 0 to 5 oxygen atoms Any of the above organic groups.

  The above [a] unsubstituted or substituted aliphatic hydrocarbon unit having one or more structures selected from the chain, branched, and cyclic structure groups, having 1 to 24 carbon atoms and oxygen Monovalent aliphatic organic groups having a number of 0 or more and 5 or less are classified into [a-1] an organic group not containing a curable functional group and [a-2] an organic group containing a curable functional group. Is done. As an aliphatic organic group which does not contain the curable functional group of [a-1], the organic group shown to the following [a-1-1]-[a-1-5], etc. are mentioned, for example.

[A-1-1]; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, sec-butyl group, n-pentyl group, isopentyl group, neopentyl group N-hexyl group, n-heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, etc. A chain organic group.
[A-1-2]: a monovalent organic group comprising a hydrocarbon containing a cyclic unit such as a cyclopentyl group, a methylcyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, or a norbornyl group.
[A-1-3]: An organic group containing an ether bond such as a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, a methoxypropyl group, an ethoxypropyl group, or a propoxypropyl group.

[A-1-4]; fluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, (trifluoromethyl) methyl group, pentafluoroethyl group, 3-fluoro-n-propyl group, 2- (trifluoro Methyl) ethyl group, (pentafluoroethyl) methyl group, heptafluoro-n-propyl group, 4-fluoro-n-butyl group, 3- (trifluoromethyl) -n-propyl group, 2- (pentafluoroethyl) Ethyl group, (heptafluoro-n-propyl) methyl group, nonafluoro-n-butyl group, 5-fluoro-n-pentyl group, 4- (trifluoromethyl) -n-butyl group, 3- (pentafluoroethyl) -N-propyl group, 2- (heptafluoro-n-propyl) ethyl group, (nonafluoro-n-butyl) methyl group, perfluoro-n- Nyl group, 6-fluoro-n-hexyl group, 5- (trifluoromethyl) -n-pentyl group, 4- (pentafluoroethyl) -n-butyl group, 3- (heptafluoro-n-propyl) -n -Propyl group, 2- (nonafluoro-n-butyl) ethyl group, (perfluoro-n-pentyl) methyl group, perfluoro-n-hexyl group, 7- (trifluoromethyl) -n-heptyl group, 6- (Pentafluoroethyl) -n-hexyl group, 5- (heptafluoro-n-propyl) -n-pentyl group, 4- (nonafluoro-n-butyl) -n-butyl group, 3- (perfluoro-n- Pentyl) -n-propyl, 2- (perfluoro-n-hexyl) ethyl, (perfluoro-n-heptyl) methyl, perfluoro-n-octyl, 9- (trif Oromethyl) -n-nonyl group, 8- (pentafluoroethyl) -n-octyl group, 7- (heptafluoro-n-propyl) -n-heptyl group, 6- (nonafluoro-n-butyl) -n-hexyl Group, 5- (perfluoro-n-pentyl) -n-pentyl group, 4- (perfluoro-n-hexyl) -n-butyl group, 3- (perfluoro-n-heptyl) -n-propyl group, Fluoroalkyl groups such as 2- (perfluoro-n-octyl) ethyl group, (perfluoro-n-nonyl) methyl group, perfluoro-n-decyl group, 4-fluorocyclopentyl group, 4-fluorocyclohexyl group.

[A-1-5]; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, iso Pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, Chain-like alkoxy groups composed of aliphatic hydrocarbons such as pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, etc., as well as cyclopentyloxy, methylcyclopentyloxy, cyclohexyloxy, methylcyclohexyloxy Cyclic group such as norbornyloxy group Alkoxy group consisting of hydrocarbons containing.

[A-2] Examples of the organic group containing a curable functional group include an organic group containing a carbon-carbon double bond, an epoxy group, an oxetanyl group, an acid anhydride group, an isocyanate group, and an isocyanurate. And monovalent organic groups having a reactive group such as a group, a carbamate group, a mercapto group, an episulfide group, a thiocarbonate group, a dithiocarbonate group, and a trithiocarbonate group. Specific examples of such an organic group include groups shown in [a-2-1] to [a-2-9] below.
[A-2-1]; vinyl group, allyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, acrylate organic group represented by the following general formula (7), and the following general formula (8 A monovalent organic group containing a carbon-carbon double bond such as a methacrylate organic group represented by

(In the formulas (7) and (8), R ² represents a divalent aliphatic hydrocarbon group selected from a chain and / or branched structure having 3 to 6 carbon atoms and 2 or less oxygen atoms. .)

[A-2-2]; a glycidoxyalkyl group in which a glycidyloxy group is bonded to an alkyl group having 4 or less carbon atoms such as β-glycidoxyethyl, γ-glycidoxypropyl, γ-glycidoxybutyl, Glycidyl group, β- (3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, β- (3,4 epoxy) A monovalent organic group having an epoxy group as a reactive group, such as a cyclohexyl) propyl group, a β- (3,4-epoxycyclohexyl) butyl group, and a β- (3,4-epoxycyclohexyl) pentyl group.
[A-2-3]; an oxetanyl group represented by the following general formula (9).

(Here, R ³ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ⁴ represents a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms.)

[A-2-4]; Acid anhydride group such as γ- (furandion) propyl group.
[A-2-5); mercapto group such as thiol group and 3-mercaptopropyl group.
[A-2-6]; an episulfide group represented by the following general formula (10) or general formula (11).

(In Formulas (10) and (11), R ⁵ represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms and 2 or less oxygen atoms.)
[A-2-7]; a thiocarbonate group represented by the following general formula (12).

(Here, R ⁵ represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms and 2 or less oxygen atoms.)
[A-2-8]; a dithiocarbonate group represented by the following general formula (13).

(Here, R ⁵ represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms and 2 or less oxygen atoms.)
[A-2-9]; a trithiocarbonate group represented by the following general formula (14).

(Here, R ⁵ represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms and 2 or less oxygen atoms.)

R ² in the general formula (7) and the general formula (8) may include an ether bond and / or an ester bond. Specific examples thereof include — (CH ₂ ) ₃ — and — (CH _2). ) ₄ −, — (CH ₂ ) ₅ —, — (CH ₂ ) ₆ —, —CH ₂ —CH (CH ₃ ) —, — (CH ₂ ) ₂ —CH (CH ₃ ) —, — (CH ₂ ) _{3 -CH (CH 3) -,} - (CH 2) 4 -CH (CH 3) -, - (CH 2) 2 -CH (CH 3) -, - (CH 2) 2 -CH (CH 2 -CH _{3) -, - CH 2 -CH} (CH 3) -CH 2 -, - CH 2 -CH (CH 2 -CH 3) -CH 2 -, - CH 2 -CH (CH 3) - (CH 2) 2 _{-, - CH 2 -CH (CH} 2 -CH 3) - (CH 2) 2 -, - CH 2 -CH (CH 3) - (C _{2) 3 -, - (CH} 2) 2 -CH (CH 3) -CH 2 -, - (CH 2) 2 -CH (CH 2 -CH 3) -CH 2 -, - (CH 2) 2 -CH _{(CH 3) - (CH 2} ) 2 -, - (CH 2) 3 -CH (CH 3) -CH 2 -, - CH 2 -O- (CH 2) 2 -, - CH 2 -O- (CH _{2) 3 -, - CH 2} -O- (CH 2) 4 -, - CH 2 -O- (CH 2) 5 -, - CH 2 -O-CH (CH 3) - (CH 2) 2 -, _{-CH 2 -O-CH 2 -CH (} CH 3) -CH 2 -, - CH 2 -O- (CH 2) 2 -CH (CH 3) -, - (CH 2) 2 -O-CH 2 - _{, -CH (CH 3) -CH 2} -O-CH 2 -, - CH 2 -CH (CH 3) -O-CH 2 -, - (CH 2) 2 -O-CH (CH _{3) -, - CH (CH} 3) -CH 2 -O-CH (CH 3) -, - CH 2 -CH (CH 3) -O-CH (CH 3) -, - (CH 2) 2 -O _{- (CH 2) 2 -,} - CH (CH 3) -CH 2 -O- (CH 2) 2 -, - CH 2 -CH (CH 3) -O- (CH 2) 2 -, - (CH 2 _{) 2 -O-CH (CH 3} ) -CH 2 -, - CH (CH 3) -CH 2 -O-CH (CH 3) -CH 2 -, - CH 2 -CH (CH 3) -O-CH _{(CH 3) -CH 2 -,} - (CH 2) 2 -O-CH 2 -CH (CH 3) -, - CH (CH 3) -CH 2 -O-CH 2 -CH (CH 3) -, _{-CH 2 -CH (CH 3) -O} -CH 2 -CH (CH 3) -, - (CH 2) 2 -O- (CH 2) 3 -, - CH (CH 3) - _{H 2 -O- (CH 2) 3} -, - CH 2 -CH (CH 3) -O- (CH 2) 3 -, - (CH 2) 2 -O-CH (CH 3) - (CH 2) _{2 -, - (CH 2)} 2 -O-CH 2 -CH (CH 3) -CH 2 -, - (CH 2) 2 -O- (CH 2) 2 -CH (CH 3) -, - (CH _{2) 2 -O- (CH 2)} 4 -, - (CH 2) 3 -O-CH 2 -, - (CH 2) 3 -O- (CH 2) 2 -, - (CH 2) 3 -O _{-CH (CH 3) -CH 2 -} , - (CH 2) 3 -O-CH 2 -CH (CH 3) -, - (CH 2) 3 -O- (CH 2) 3 -, - (CH 2 _{) 2 -O-CH 2 -O- (} CH 2) 2 -, - (CH 2) 2 -O- (CH 2) 2 -O- (CH 2) 2 -, - (CH 2) 2 -O- CH _{2 -O- (CH 2) 3 -,} - (CH 2) 2 -COO- (CH 2) 2 -, - (CH 2) 2 -COO- (CH 2) 3 -, etc. can be exemplified.

Specific examples of R ^{3 in} the general formula (9) include, for example, H, —CH ₃ , —CH ₂ —CH ₃ , — (CH ₂ ) ₂ —CH ₃ , — (CH ₂ ) ₃ —CH _3. , — (CH ₂ ) ₄ —CH ₃ , — (CH ₂ ) ₅ —CH ₃ , —CH (CH ₃ ) —CH ₃ , —CH (CH ₃ ) —CH ₂ —CH ₃ , —CH (CH ₃ ) _{- (CH 2) 2 -CH 3} , -CH (CH 3) - (CH 2) 3 -CH 3, -CH 2 -CH (CH 3) -CH 3, -CH 2 -CH (CH 3) -CH _{2 -CH 3, -CH 2 -CH (} CH 3) - (CH 2) 2 -CH 3, - (CH 2) 2 -CH (CH 3) -CH 3, - (CH 2) 2 -CH (CH _{3) -CH 2 -CH 3, -} (CH 2) 3 -CH (CH 3) -CH 3, -CH 2 -CH (CH 2 _{CH 3) -CH 2 -CH 3,} -CH 2 -CH 2 -CH (CH 2 -CH 3) -CH 3, etc. may be exemplified.

Specific examples of R ^{4 in} the general formula (9) include, 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 2) 2 -CH (CH 3) -, - (CH 2) 3 -CH ( _{CH 3) -, - (CH} 2) 4 -CH (CH 3) -, - (CH 2) 2 -CH (CH 3) -, - CH 2 -CH (CH 3) -CH 2 -, - CH 2 _{-CH (CH 3) - (CH} 2) 2 -, - CH 2 -CH (CH 3) - (CH 2) 3 -, - (CH 2) 2 -CH (CH 3) -CH 2 -, - ( _{CH 2) 2 -CH (CH 3} ) - (CH 2) 2 -, - (CH 2) 3 -CH (CH 3) -CH 2 -, etc. can be exemplified.

R ⁵ in the above general formulas (10) to (14) may contain an ether bond and / or an ester bond, and specific examples thereof include, for example, —CH ₂ —, — (CH ₂ ) ₂ —, _{- (CH 2) 3 -,} - (CH 2) 4 -, - (CH 2) 5 -, - (CH 2) 6 -, - (CH 2) 7 -, - (CH 2) 8 -, - ( _{CH 2) 9 -, - (} CH 2) 10 -, - CH (CH 3) -, - CH 2 -CH (CH 3) -, - (CH 2) 2 -CH (CH 3) -, - (CH ₂ ) ₃ —CH (CH ₃ ) —, — (CH ₂ ) ₄ —CH (CH ₃ ) —, — (CH ₂ ) ₂ —CH (CH ₃ ) —, — (CH ₂ ) ₂ —CH (CH ₂ ) _{-CH 3) -, - CH 2} -CH (CH 3) -CH 2 -, - CH 2 -CH (CH 2 -CH 3) -CH 2 -, - CH _{2 -CH (CH 3) - (} CH 2) 2 -, - CH 2 -CH (CH 2 -CH 3) - (CH 2) 2 -, - CH 2 -CH (CH 3) - (CH 2) 3 _{-, - (CH 2) 2} -CH (CH 3) -CH 2 -, - (CH 2) 2 -CH (CH 2 -CH 3) -CH 2 -, - (CH 2) 2 -CH (CH 3 _{) - (CH 2) 2 -} , - (CH 2) 3 -CH (CH 3) -CH 2 -, - CH 2 -O- (CH 2) 2 -, - CH 2 -O- (CH 2) 3 _{-, - CH 2 -O- (CH} 2) 4 -, - CH 2 -O- (CH 2) 5 -, - CH 2 -O-CH (CH 3) - (CH 2) 2 -, - CH 2 _{-O-CH 2 -CH (CH 3} ) -CH 2 -, - CH 2 -O- (CH 2) 2 -CH (CH 3) -, - (CH 2) 2 -O- _{H 2 -, - CH (CH} 3) -CH 2 -O-CH 2 -, - CH 2 -CH (CH 3) -O-CH 2 -, - (CH 2) 2 -O-CH (CH 3) _{-, - CH (CH 3)} -CH 2 -O-CH (CH 3) -, - CH 2 -CH (CH 3) -O-CH (CH 3) -, - (CH 2) 2 -O- ( _{CH 2) 2 -, - CH} (CH 3) -CH 2 -O- (CH 2) 2 -, - CH 2 -CH (CH 3) -O- (CH 2) 2 -, - (CH 2) 2 _{-O-CH (CH 3) -CH} 2 -, - CH (CH 3) -CH 2 -O-CH (CH 3) -CH 2 -, - CH 2 -CH (CH 3) -O-CH (CH _{3) -CH 2 -, - (} CH 2) 2 -O-CH 2 -CH (CH 3) -, - CH (CH 3) -CH 2 -O-CH 2 -CH (CH _{3) -, - CH 2 -CH} (CH 3) -O-CH 2 -CH (CH 3) -, - (CH 2) 2 -O- (CH 2) 3 -, - CH (CH 3) -CH _{2 -O- (CH 2) 3 -} , - CH 2 -CH (CH 3) -O- (CH 2) 3 -, - (CH 2) 2 -O-CH (CH 3) - (CH 2) 2 _{-, - (CH 2) 2} -O-CH 2 -CH (CH 3) -CH 2 -, - (CH 2) 2 -O- (CH 2) 2 -CH (CH 3) -, - (CH 2 _{) 2 -O- (CH 2) 4} -, - (CH 2) 3 -O-CH 2 -, - (CH 2) 3 -O- (CH 2) 2 -, - (CH 2) 3 -O- _{CH (CH 3) -CH 2 -} , - (CH 2) 3 -O-CH 2 -CH (CH 3) -, - (CH 2) 3 -O- (CH 2) 3 -, - (CH 2) _{2 -O-CH 2 -O- (CH} 2) 2 -, - (CH 2) 2 -O- (CH 2) 2 -O- (CH 2) 2 -, - (CH 2) 2 -O-CH _{2 -O- (CH 2) 3 -} , - (CH 2) 2 -COO- (CH 2) 2 -, - (CH 2) 2 -COO- (CH 2) 3 -, etc. can be exemplified.

  On the other hand, [b] one or more structures selected from the group consisting of chain, branched and cyclic, having an unsubstituted or substituted aromatic hydrocarbon unit and optionally substituted or substituted 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, the following [b-1-1] to [b -1-2] and the like.

[B-1-1]: Aromatic organic groups such as phenyl group, tolyl group, xylyl group, benzyl group, α-methylstyryl group, 3-methylstyryl group, 4-methylstyryl group.
[B-1-2]; 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 2,3,4-trifluorophenyl group, 2,3, 5-trifluorophenyl group, 2,4,5-trifluorophenyl group, 2,3,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,4,6-tetrafluoro It has at least one fluorine atom as a substituent such as phenyl group, 2,3,4,5-tetrafluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, etc. Aromatic organic radical.

Within the above range of carbon number and oxygen number, the organic group of R ¹ 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, or The ester bond may further contain heteroatoms such as nitrogen, phosphorus, boron and sulfur excluding oxygen and silicon atoms. Moreover, said [a] and [b] may be an organic group in which 1 type or 2 or more types of groups were mixed.

Here, the component index α in the present invention will be described.
The polyorganosiloxane used in the present invention comprises (A) a siloxane unit having a phenyl group having a fluorine atom as a substituent in one molecule as R ¹ in (A) average composition formula (1), and (B) In the average composition formula (1), R ¹ is selected from the group consisting of an organic group containing a carbon-carbon double bond, an epoxy group, an episulfide group, a thiocarbonate group, a dithiocarbonate group, and a trithiocarbonate group as one molecule. And a siloxane unit having at least one curable functional group as a substituent, and the component index α used in the present invention is the above-mentioned “(A) average composition formula (1) as R ¹ in one molecule, a phenyl group having a fluorine atom as a substituent and siloxane units "having a substituent" (B) Rights In the composition formula (1), as R ¹ in one molecule, a carbon - selected organic group containing a carbon double bond, an epoxy group, episulfide group, thiocarbonate group, a dithiocarbonate group and a trithiocarbonate group the group consisting of The component ratio with the “siloxane unit having at least one curable functional group as a substituent” is a value calculated by the following formula (2).
Component index α = (αa) / (αb) (2)
(Here, in the general formula (2), αa is the content (mol%) of the component (A) with respect to the total Si amount in the polyorganosiloxane represented by the average composition formula (1), and αb is the average composition formula. (The content (mol%) of the component (B) with respect to the total amount of Si in the polyorganosiloxane represented by (1) is shown.)

  In the present invention, the above component index α indicates that the cured product obtained by curing the polyorganosiloxane of the present invention does not have tackiness, while maintaining high heat yellowing and light resistance under heating conditions. In order to secure the fluidity and storage stability of the modified resin composition, it is necessary that the range be 0.001 or more. On the other hand, the cured product obtained by curing the polyorganosiloxane of the present invention is highly heat-resistant yellowing, a cured product having no tack while maintaining light resistance under heating conditions, In order to secure the fluidity of the curable resin composition containing the organosiloxane, it is necessary to set it to a range of 19 or less. The value of α is more preferably in the range of 0.2 to 5, more preferably 0.3 to 2.

Since the light resistance of the cured product obtained by curing the polyorganosiloxane produced by the present invention is improved and the heat-resistant yellowing is further improved, [b] unsubstituted or substituted contained as R ¹ Having an aliphatic hydrocarbon unit having at least one kind of structure selected from a chain, branched, and cyclic structure group, which is substituted or substituted as necessary. All of the monovalent aromatic organic groups having 6 to 24 carbon atoms and 0 to 5 oxygen atoms are preferably [b-1-2], and [b] unsubstituted or substituted. Carbon having an aromatic hydrocarbon unit and having an aliphatic hydrocarbon unit having one or more structures selected from a chain, branched, and cyclic structure group, which is unsubstituted or substituted as necessary The number is 6 or more and 24 or less, and the oxygen number is More preferably, all of the monovalent aromatic organic groups of 0 or more and 5 or less are phenyl groups substituted with 2 or more and 3 or less of fluorine atoms. More preferably, R ¹ is a hydroxyl group, [a-1-1] to [a-1-4], [a-2-1], [a-2-2], [a-2-6] to [a-2-6] a-2-9] is more preferably a phenyl group substituted with at least one organic group selected from the group consisting of 2 or more and 3 or less fluorine atoms, and a hydroxyl group [a-1-1]. ], [A-1-2], [a-2-1], [a-2-2], [a-2-6], [a-2-8], [a-2-9] It is more preferably a phenyl group substituted with at least one organic group selected from the group and 2 or more and 3 or less fluorine atoms, and a hydroxyl group, [a-1-1], [a-1- 2], methacrylate organic group, [a-2-2], [a-2-6], [a-2-8], at least one organic selected from the group [a-2-9] Group and 2 Particularly preferred is a phenyl group substituted with 3 or more and 3 or less fluorine atoms, and is a hydroxyl group, [a-1-1], [a-1-2], [a-2-1], [a- 2-2] is most preferably a phenyl group substituted with at least one organic group selected from the group consisting of 2 and 3 or less fluorine atoms.

  Next, the hydrolyzable group contained in the polyorganosiloxane in the present invention will be described. The hydrolyzable group in the present invention is a fatty acid having one or more structures selected from a chlorine, bromine, iodine, or unsubstituted or substituted structural group consisting of a chain, a branch, and a ring. A monovalent alkoxy group having a group hydrocarbon unit and having 1 to 20 carbon atoms.

  Monovalent alkoxy having 1 or more and 20 or less carbon atoms, which is an unsubstituted or substituted aliphatic hydrocarbon unit having at least one structure selected from a chain, branched chain and cyclic structure group Examples of the group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, and isopentyloxy. Group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyl Consists of aliphatic hydrocarbons such as oxy, hexadecyloxy, heptadecyloxy, octadecyloxy Jo alkoxy group, as well as, a cyclopentyloxy group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, an alkoxy group, or the like made of hydrocarbons containing cyclic units etc. norbornyl group. These organic groups may be organic groups in which one type or two or more types are mixed.

  Among these organic groups, X is unsubstituted or substituted because it is easy to remove compounds by-produced by hydrolysis and polycondensation, and the reactivity to the hydrolysis of reactive organosilicon compounds tends to increase. A monovalent alkoxy group having an aliphatic hydrocarbon unit composed of one or more structures selected from a chain, branched, and cyclic structure group and having 1 to 20 carbon atoms. Are more preferable, and a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group are more preferable, and a methoxy group and an ethoxy group are still more preferable.

In the present invention, the heat resistance of the cured product obtained by curing the polyorganosiloxane and the thermal shock resistance at the time of thermal cycle and the adhesion are improved, so that the hydrolyzable group contained in the polyorganosiloxane is substituted with a substituent. The total content of siloxane units as is preferably 5 mol% or less, more preferably 3 mol% or less, still more preferably 1 mol% or less, and more preferably 0.5 mol% or less with respect to the total Si amount. It is further particularly preferable that it is not included at all. The total content of siloxane units having hydrolyzable groups as substituents with respect to the total Si contained in the polyorganosiloxane contains the peak area of the internal standard substance obtained by ²⁹ Si-NMR measurement and the residual hydrolyzable groups. It can be quantified by calculating the area ratio of the peak area derived from Si.

The condensation rate of the polyorganosiloxane of the present invention is preferably 80% or more, from the viewpoint of storage stability of the polyorganosiloxane, that is, from the viewpoint of suppressing the viscosity of the resin during storage and improving handleability, and 82% or more. Is more preferably 85% or more, and particularly preferably 88% or more.
The condensation rate of the polyorganosiloxane alkoxysilane compound of the present invention can be calculated by the following method according to the unit structure of siloxane.

<Calculation method of condensation rate>
Condensation ratio is a value from ²⁹ Si-NMR measurement results of polyorganosiloxanes obtained by the following procedure.
0.15 g of polyorganosiloxane is dissolved in 1 g of deuterated chloroform. A solution obtained by adding 0.015 g of Cr (acac) ₃ to the solution and dissolving is used as an NMR measurement solution. Using this NMR measurement solution, ²⁹ Si-NMR measurement under proton complete decoupling conditions is performed with 6,000 integrations (apparatus: α-400 manufactured by JASCO Corporation).

Based on the obtained spectrum, the following D0 structure, D1 structure, D structure consisting of D2 structure, T structure consisting of the following T0 structure, T1 structure, T2 structure, T3 structure, Q0 structure, Q1 structure, Q2 Based on the integral value of each peak corresponding to the Q structure consisting of the structure, the Q3 structure, and the Q4 structure, the calculation is performed according to the following formula (15).
Condensation rate (%) = (D1 × 1 + D2 × 2 + T1 × 1 + T2 × 2 + T3 × 3 + Q1 ×
1 + Q2 × 2 + Q3 × 3 + Q4 × 4) / {(D0 + D1 + D2) × 2 + (T0 + T1 + T2 + T3) × 3 + (Q0 + Q1 + Q2 + Q3 + Q4) × 4} × 100 (15)

Here, D0, D1, D2, T0, T1, T2, T3, Q0, Q1, Q2, Q3, and Q4 each represent the following.
D0: Total integrated value of signals derived from the D0 structure represented by the following formula (16) in the polyorganosiloxane of the average composition formula (1).
D1: Total integrated value of signals derived from the D1 structure represented by the following formula (17) in the polyorganosiloxane of the average composition formula (1).
D2: Total integrated value of signals derived from the D1 structure represented by the following formula (17) in the polyorganosiloxane of the average composition formula (1).
T0: Total integrated value of signals derived from the T0 structure represented by the following formula (18) in the polyorganosiloxane of the average composition formula (1).
T1: Total integrated value of signals derived from the T1 structure represented by the following formula (19) in the polyorganosiloxane of the average composition formula (1).
T2: Total integrated value of signals derived from the T2 structure represented by the following formula (19) in the polyorganosiloxane of the average composition formula (1).
T3: Total integrated value of signals derived from the T3 structure represented by the following formula (19) in the polyorganosiloxane of the average composition formula (1).
Q0: Total integrated value of signals derived from the Q0 structure represented by the following formula (20) in the polyorganosiloxane of the average composition formula (1).
Q1: Total integrated value of signals derived from the Q1 structure represented by the following formula (21) in the polyorganosiloxane of the average composition formula (1).
Q2: Total integrated value of signals derived from the Q2 structure represented by the following formula (21) in the polyorganosiloxane of the average composition formula (1).
Q3: Total integrated value of signals derived from the Q3 structure represented by the following formula (21) in the polyorganosiloxane of the average composition formula (1).
Q4: Total integrated value of signals derived from the Q4 structure represented by the following formula (21) in the polyorganosiloxane of the average composition formula (1).

In the formula (16), R ⁶ is an arbitrary organic group, Y is selected from a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, an unsubstituted or substituted structure group consisting of a chain, a branched, and a ring. It is a hydrolyzable group selected from the group consisting of monovalent alkoxy groups having an aliphatic hydrocarbon unit having a structure of at least a species and having 1 to 20 carbon atoms.

In the formula (17), R ⁶ is an arbitrary organic group, Y is selected from a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, an unsubstituted or substituted structure group consisting of a chain, a branch, and a ring. It is a hydrolyzable group selected from the group consisting of monovalent alkoxy groups having an aliphatic hydrocarbon unit having a structure of at least a species and having 1 to 20 carbon atoms.

In the formula (18), R ⁶ is an arbitrary organic group, Y is selected from a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, an unsubstituted or substituted structure group consisting of a chain, a branched, and a ring. It is a hydrolyzable group selected from the group consisting of monovalent alkoxy groups having an aliphatic hydrocarbon unit having a structure of at least a species and having 1 to 20 carbon atoms.

In the formula (19), R ⁶ is an arbitrary organic group, Y is selected from a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, an unsubstituted or substituted structure group consisting of a chain, a branched, and a ring. It is a hydrolyzable group selected from the group consisting of monovalent alkoxy groups having an aliphatic hydrocarbon unit having a structure of at least a species and having 1 to 20 carbon atoms.

In the formula (20), R ⁶ is an arbitrary organic group, Y is selected from a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, an unsubstituted or substituted structure group consisting of a chain, a branch, and a ring. It is a hydrolyzable group selected from the group consisting of monovalent alkoxy groups having an aliphatic hydrocarbon unit having a structure of at least a species and having 1 to 20 carbon atoms.

In the formula (21), R ⁶ is an arbitrary organic group, Y is selected from the group consisting of a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, an unsubstituted or substituted structure group consisting of a chain, a branch, and a ring. It is a hydrolyzable group selected from the group consisting of monovalent alkoxy groups having an aliphatic hydrocarbon unit having a structure of at least a species and having 1 to 20 carbon atoms.

Next, the component index β used in the present invention will be described.
The component index β of the present invention comprises the content of the D structural unit composed of the above D0, D1, and D2 structures relative to the total amount of Si constituting the polyorganosiloxane, and comprises the above T0 structure, T1 structure, T2 structure, and T3 structure. Based on the content of T structural unit, Q0 structure, Q1 structure, Q2 structure, Q3 structure, and Q structural unit consisting of Q4 structure, it is a value calculated according to the following formula (3), specifically , Using the same measurement as the ²⁹ Si-NMR measurement used when calculating the condensation rate, the total area value of the above D structural units relative to the total value of the peak areas of all Si derived from polyorganosiloxane, T Each fraction of the total area value of the structural unit and the total area value of the Q structural unit is a value defined as the content (mol%) of the D structural unit, the T structural unit, and the Q structural unit, respectively.
Component index β = {(βD) / (βQ + βT)} (3)
(In the formula (3), βD is the content (mol%) of the D structural unit with respect to the total Si amount in the polyorganosiloxane represented by the average composition formula (1), and βQ is the average composition formula (1). The content (mol%) of the Q structural unit with respect to the total Si amount in the polyorganosiloxane represented by the formula, βT is the content of the T structural unit with respect to the total Si amount in the polyorganosiloxane represented by the average composition formula (1) The amount (mol%) is shown, and 0 ≦ {βQ / (βQ + βT + βD)} ≦ 0.1.)

In the present invention, the component index β is 0.01 or more because the fluidity of the polyorganosiloxane is improved and the handling property tends to be improved. On the other hand, the cured product obtained by curing the polyorganosiloxane is used. It is preferably 1.4 or less, more preferably in the range of 0.03 or more and 1.2 or less, and in the range of 0.05 or more and 1.0 or less because the thermal shock resistance tends to be improved. More preferably it is.
Although there is no restriction | limiting in particular about the viscosity in 25 degreeC of the polyorganosiloxane of this invention, The fluidity | liquidity as a liquid can be ensured and there exists a tendency for a handleability to increase, and mixing with the additive added as needed Therefore, the liquid is preferably 1,000 Pa · s or less, more preferably 500 Pa · s or less, still more preferably 300 Pa · s or less, and 200 Pa · s or less. It is particularly preferred that

The content of the curable functional group contained in the polyorganosiloxane of the present invention is such that the hardness of the cured product obtained by curing the curable functional group is increased, and the handleability of the cured product is increased. The content of the curable functional group contained in 100 g of siloxane is preferably 0.001 mol or more, more preferably 0.01 mol or more, still more preferably 0.1 mol or more, The amount is particularly preferably 0.15 mol or more. On the other hand, since the storage stability of the polyorganosiloxane itself is increased, the content of the curable functional group contained in 100 g of the polyorganosiloxane is preferably 1 mol or less, and 0.8 mol or less. More preferably, it is 0.6 mol or less.
For example, when the curable functional group is an epoxy group, the content of the curable functional group can be quantified by measuring the epoxy equivalent based on JIS K-7236. Further, when the curable functional group is other functional group, it can be quantified by a method such as ¹ H-NMR measurement in which an internal standard substance coexists.

Next, an example of a specific method for producing the polyorganosiloxane of the present invention will be described.
The polyorganosiloxane of the present invention contains at least the following components (a) and (b) represented by the following general formula (4) and has a hydrolyzable group represented by the general formula (5). A reactive organic silicon compound having a hydrolyzable group in which the mixing index γ of the reactive organic silicon compound is in the range of 0.001 to 19 is obtained by a hydrolysis step in the presence of water, and a hydrolysis step. It can manufacture by passing through the polycondensation process which polycondenses the obtained intermediate body.

(Here, each R ¹ is independently a hydrogen atom, a halogen atom, a hydroxyl group, or an unsubstituted or substituted one or more structures selected from a chain, branched, and cyclic structure group. X represents each independently a monovalent hydrolyzable group, and q and r are q ≧ 0, r> 0, and 2 ≦ q + r ≦ 4. Is a positive number satisfying.)

(A) In the general formula (4), a reactive organosilicon compound having, as R ¹ , at least a phenyl group having a fluorine atom as a substituent as R ¹ .
(B) In the general formula (4), a group consisting of an organic group containing a carbon-carbon double bond, an epoxy group, an episulfide group, a thiocarbonate group, a dithiocarbonate group and a trithiocarbonate group as R ¹ in one molecule. A reactive organosilicon compound having at least one curable functional group selected from as a substituent.
Mixing index γ = (γa) / (γb) (5)
(In the formula (5), γa is the content (mol%) of the component (a) with respect to all reactive organosilicon compounds, and γb is the content of the component (b) with respect to all reactive organosilicon compounds. Amount (mol%) is indicated.)

In the present invention, the substituent R ¹ in the general formula (4) is the same as that in the above average composition formula (1).
X in the general formula (4) of the present invention will be described. In the present invention, X represents a monovalent hydrolyzable group. Examples of such hydrolyzable groups include a chlorine atom, a bromine atom, an iodine atom, an unsubstituted or substituted chain, branched, and And monovalent alkoxy groups having one or more aliphatic hydrocarbon units selected from a cyclic structural group and having 1 to 20 carbon atoms.

  Monovalent alkoxy having 1 or more and 20 or less carbon atoms, which is an unsubstituted or substituted aliphatic hydrocarbon unit having at least one structure selected from a chain, branched chain and cyclic structure group Examples of the group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, and isopentyloxy. Group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyl Consists of aliphatic hydrocarbons such as oxy, hexadecyloxy, heptadecyloxy, octadecyloxy Jo alkoxy group, as well as, a cyclopentyloxy group, methylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, an alkoxy group, or the like made of hydrocarbons containing cyclic units etc. norbornyl group. These organic groups may be organic groups in which one type or two or more types are mixed.

  Among these organic groups, X is unsubstituted or substituted because it is easy to remove compounds by-produced by hydrolysis and polycondensation, and the reactivity to the hydrolysis of reactive organosilicon compounds tends to increase. A monovalent alkoxy group having an aliphatic hydrocarbon unit composed of one or more structures selected from a chain, branched, and cyclic structure group and having 1 to 20 carbon atoms. Are more preferable, and a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group are more preferable, and a methoxy group and an ethoxy group are still more preferable.

As the reactive organosilicon compound having a hydrolyzable group represented by the general formula (1) used in the present invention, q and r satisfy the conditions of q ≧ 0, r> 0, 2 ≦ q + r ≦ 4. There is no particular limitation as long as it is a positive number. In addition, a partial condensate of the compound represented by the general formula (4) can be allowed to coexist without departing from the present invention.
In the present invention, as the reactive organosilicon compound represented by the general formula (1), q = 0 and r = 4 in the general formula (4), specifically, the hydrolyzable group X is present on the silicon atom. It is also possible to use four bonded compounds. Examples of such alkoxysilane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane. The reactive organosilicon compound represented by the general formula (1) can be used as one kind or a mixture of two or more kinds.

Next, the mixing index γ in the present invention will be described.
In the present invention, γ is a reaction having, as a substituent, a phenyl group having a fluorine atom as a substituent in one molecule as R ¹ in (a) general formula (4), which is used when producing a polyorganosiloxane. An organic organosilicon compound, and (b) in general formula (4), as R ¹ , an organic group containing a carbon-carbon double bond in one molecule, an epoxy group, an episulfide group, a thiocarbonate group, a dithiocarbonate group, and The value defined by the component index calculated by the following formula (2), the component ratio with the reactive organosilicon compound having at least one curable functional group selected from the group consisting of trithiocarbonate groups as a substituent It is.
Mixing index γ = (γa) / (γb) (5)
(In the formula (5), γa is the content (mol%) of the component (a) with respect to all reactive organosilicon compounds, and γb is the content of the component (b) with respect to all reactive organosilicon compounds. Amount (mol%) is indicated.)

  In the present invention, as the component index γ, the cured product obtained by curing the polyorganosiloxane obtained by the production method of the present invention does not have tackiness, and has high heat-resistant yellowing and heating conditions. In order to ensure the fluidity and storage stability of the modified resin composition while maintaining the light resistance, the range of 0.001 or more is obtained by curing the polyorganosiloxane of the present invention. While the cured product has high heat-resistant yellowing and light resistance under heating conditions, the fluidity of the curable resin composition containing the polyorganosiloxane obtained by the method of the present invention and the thermal shock resistance of the cured product In order to ensure the property, it is necessary to set the range to 19 or less. The value of α is more preferably in the range of 0.2 to 5, more preferably 0.3 to 2.

In the present invention, the amount of the component of the reactive organosilicon compound having an organic group containing a curable functional group as R ¹ is not particularly limited as long as the above mixing index γ is satisfied. Since the hardness of the cured product obtained by curing the polyorganosiloxane obtained by the production method is increased and the handleability of the cured product is increased, the content of the curable functional group contained in 100 g of the polyorganosiloxane is preferably Contained in 100 g of polyorganosiloxane, since the storage stability of the polyorganosiloxane itself is increased so that it is 0.001 mol or more, more preferably 0.01 mol or more, and even more preferably 0.1 mol or more. The content of the curable functional group is preferably 1 mol or less, more preferably 0.8 mol or less, still more preferably 0.6 mol or less. It can be appropriately selected so that.

Next, the mixing index δ used in the method for producing the polyorganosiloxane of the present invention will be described. In the present invention, the component index δ is a hydrolyzable group in which n = 2 among the reactive organosilicon compounds having a hydrolyzable group represented by the general formula (4) used when producing the polyorganosiloxane. ΔD (mol%) representing the content of the reactive organosilicon compound having δ, δQ (mol%) representing the content of the reactive organosilicon compound having a hydrolyzable group where n = 0, and n = 1 is a value defined by a mixing index calculated by the following formula (6) from δT (mol%) representing the content of the reactive organosilicon compound having a hydrolyzable group of 1.
Mixing index δ = {(δD) / (δQ + δT)} (6)
Here, in formula (6), δD is a reactive organosilicon having a hydrolyzable group where n = 2 in a reactive organosilicon compound having a hydrolyzable group represented by general formula (4) Compound content (mol%), δQ is a reactive organosilicon compound having a hydrolyzable group where n = 0 in the reactive organosilicon compound having a hydrolyzable group represented by the general formula (4) Content (mol%), δT of the reactive organosilicon compound having a hydrolyzable group of q = 1 in the reactive organosilicon compound having a hydrolyzable group represented by the general formula (4) The content (mol%) is shown, and 0 ≦ {δQ / (δQ + δT + δD)} ≦ 0.1.)

  In the present invention, the component index δ is preferably 0.01 or more because the fluidity of the polyorganosiloxane obtained by the production method of the present invention tends to be improved and the handleability tends to be improved. On the other hand, it is preferably 1.4 or less and preferably in the range of 0.03 or more and 1.2 or less because the thermal shock resistance of the cured product obtained by curing the polyorganosiloxane tends to be improved. More preferably, it is in the range of 0.05 or more and 1.0 or less.

Next, the amount of water used for hydrolysis will be described. Here, the ratio between the amount of water to be added (number of moles) and the amount of the hydrolyzable group (number of moles) in the reactive organosilicon compound represented by the general formula (4) is expressed by the following formula (22). It is defined as a mixture index ε represented by
Mixing index ε = (εw) / (εs) (22)
(In the formula (22), εw represents the amount of water added (mol number), while εs represents the amount of X (mol number) in the general formula (4).)

In the present invention, the mixing index ε is 0.1 or more because the reaction rate of hydrolysis can be increased, the molecular weight of the condensate obtained by hydrolysis can be increased, and the subsequent polycondensation reaction can be easily performed. The range is preferably 5 or less, more preferably 0.2 or more and 3 or less, and further preferably 0.3 or more and 1.5 or less.
In the present invention, the timing of adding water is not particularly limited, it may be added until the end of the step of producing an intermediate by hydrolysis, a method of batch addition at the start of the reaction, sequential addition during the reaction Any of the method of adding or continuously adding during the reaction may be used. Among these, the method of adding all at once at the start of the reaction is preferably used.

  In the hydrolysis reaction of the present invention, a solvent can be used as necessary. The solvent used in the present invention is not particularly limited, and one or more selected from the group consisting of a reactive organosilicon compound having a hydrolyzable group represented by the general formula (4), a polyorganosiloxane, and water. It is possible to use a solvent that dissolves the compound. Examples of such a solvent 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, Ether solvents such as anisole; 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- Aromatic hydrocarbon solvents such as xylene and ethylbenzene; ester solvents such as ethyl acetate and butyl acetate; methanol, ethanol, butanol, Propanol, n- butanol, butyl cellosolve, alcohol-based solvents such as butyl carbitol. These solvents can be used as one kind or a mixture of two or more kinds.

Among these, since both the water and the reactive organosilicon compound having a hydrolyzable group represented by the general formula (1) can be dissolved and the reaction rate of hydrolysis can be increased, an ether solvent , A ketone solvent, and an alcohol solvent are preferable, a solvent containing 50% by mass or more of an ether solvent is more preferable, and at least one selected from the group consisting of 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and propylene glycol dimethyl ether or Two or more kinds of mixed solvents are more preferable, and 1,4-dioxane and tetrahydrofuran are particularly preferable.
Although there is no limitation in particular about the addition amount of a solvent, with respect to the total mass of the reactive organosilicon compound which has a hydrolysable group represented by the said General formula (4) from the point which can raise the reaction rate of hydrolysis. 0.01-fold mass to 20-fold mass is preferred, 0.02-fold mass to 15-fold mass is more preferred, and 0.03-fold mass to 10-fold mass is still more preferred.

In the present invention, the timing of adding the solvent is not particularly limited, and before adding water for subjecting the reactive organosilicon compound having a hydrolyzable group represented by the general formula (4) to a hydrolysis reaction, Alternatively, it may be added between the start and end of the hydrolysis reaction. Either of the method of adding at the beginning of the reaction, the method of adding sequentially during the reaction, or the method of adding continuously during the reaction A method may be used. Among these, a method of adding all at the beginning of the reaction is preferably used.
Although the hydrolysis reaction can proceed even without a catalyst, it is preferable to use a catalyst because the reaction rate of hydrolysis can be increased. The catalyst used is not particularly limited as long as it is a conventionally known catalyst, but is appropriately selected in consideration of heat-resistant yellowing required for polyorganosiloxane.

  Specific examples of the catalyst used include, for example, metals (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium. , Boron, cadmium, manganese, bismuth, etc.), organic metals (lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic, Organic oxides such as cerium, boron, cadmium, manganese, bismuth, organic acid salts, organic halides, alkoxides, etc.), inorganic bases (magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide) , Sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.), organic bases (ammonia, tetramethylammonium hydroxide, etc.), cation exchange Examples thereof include resins and anion exchange resins. These catalysts can be used alone or in combination of two or more.

  Among the above organic metals, organic tin is preferable because the reaction rate is high and the condensation rate of polyorganosiloxane can be increased. The organic tin refers to one in which at least one organic group is bonded to a tin atom, and examples of the structure include monoorganotin, diorganotin, triorganotin, and tetraorganotin. Examples of the organic tin include tin tetrachloride, monobutyltin trichloride, monobutyltin oxide, monooctyltin trichloride, tetra n-octyltin, tetra n-butyltin, dibutyltin oxide, dibutyltin diacetate, dibutyltin dioctate, dibutyl Tin diversate, dibutyltin dilaurate, dibutyltin oxylaurate, dibutyltin stearate, dibutyltin dioleate, dibutyltin / silicon ethyl reactant, dibutyltin salt and silicate compound, dioctyltin salt and silicate compound, dibutyltin bis ( Acetylacetonate), dibutyltin bis (ethyl malate), dibutyltin bis (butylmalate), dibutyltin bis (2-ethylhexylmalate), dibutyltin bis (benzylmalate), dibutyltin bis Allyl malate), dibutyltin bis (oleylmalate), dibutyltin malate, dibutyltin bis (O-phenylphenoxide), dibutyltin bis (2-ethylhexylmercaptoacetate), dibutyltin bis (2-ethylhexylmercaptopropionate) Dibutyltin bis (isononyl 3-mercaptopropionate), dibutyltin bis (isooctylthioglycolate), dibutyltin bis (3-mercaptopropionate), dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, Dioctyltin dioctate, dioctyltin didodecyl mercapto, dioctyltin versatate, dioctyltin distearate, dioctyltin bis (ethyl malate), dioctyltin bis (octylmalate), dioctyl Rutin malate, dioctyltin bis (isooctylthioglycolate), dioctyltin bis (2-ethylhexyl mercaptoacetate), dibutyltin dimethoxide, dibutyltin diethoxide, dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin diethoxide, dioctyltin dibutoxide, Examples include tin octylate and tin stearate.

Among the above organic metals, an alkali organic metal that exhibits alkalinity when a ligand is liberated is preferable. By using an alkali organic metal as the hydrolysis condensation catalyst, the storage stability of the polyorganosiloxane obtained in the present invention tends to be good.
Among the alkali organic metals, alkali organic tin is preferable, and alkoxide organic tin is particularly preferable. Examples of the alkoxide-based organic tin include dibutyltin dimethoxide, dibutyltin diethyloxide, dibutyltin dibutoxide, dioctyltin dimethoxide, dioctyltin diethyloxide, dioctyltin dibutoxide and the like.
The amount of the catalyst to be added is not particularly limited, but it is possible to stably obtain the hydrolysis promoting effect and improve the heat-resistant yellowing required for the polyorganosiloxane. The range of 0.0001 parts by mass or more and 10 parts by mass or less is preferable, and the range of 0.01 parts by mass or more and 5 parts by mass or less is more preferable with respect to 100 parts by mass of the total mass of the organic organosilicon compound.

In the present invention, the timing of adding the catalyst is not particularly limited, and can be added until the hydrolysis is completed, for example, a method of batch addition at the start of the reaction, a method of sequential addition during the reaction, Alternatively, any method of continuously adding during the reaction may be used. Among these, the method of adding all at once at the start of the reaction is preferably used.
The reaction temperature during the hydrolysis is usually in the range of 0 ° C. or higher and 200 ° C. or lower. If the reaction temperature is less than 0 ° C, water used for hydrolysis may solidify, and if it exceeds 200 ° C, the resulting polyorganosiloxane may be colored. From the viewpoint of increasing the reaction rate and suppressing the modification of the polyorganosiloxane, the reaction temperature is preferably in the range of 20 ° C to 150 ° C, more preferably in the range of 40 ° C to 120 ° C, and more preferably in the range of 50 ° C to 100 ° C. A range is more preferred. The reaction temperature need not be constant as long as it is within the above range, and may be changed during the reaction.
The reaction time for the hydrolysis is not particularly limited because it varies depending on the reactive organosilicon compound, but from the viewpoint of improving the reaction rate and suppressing the modification of the polyorganosiloxane, it is 0.1 hours or more and less than 100 hours. The range is preferably 0.5 hours or more and less than 80 hours, more preferably 1 hour or more and less than 50 hours, and particularly preferably 2 hours or more and less than 30 hours.

In the present invention, the hydrolysis reaction can be performed in an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide or lower saturated hydrocarbon, or in the air. Among these gases, from the viewpoint of suppressing modification of the polyorganosiloxane, an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide or lower saturated hydrocarbon is preferable, and nitrogen, helium, neon, Argon, krypton, xenon and carbon dioxide are more preferred, nitrogen and helium are more preferred, and nitrogen is particularly preferred.
Moreover, when performing a hydrolysis reaction, it can carry out in the environment of the said gas atmosphere, the distribution | circulation of the said gas, under pressure reduction, pressurization, or these combinations. The pressure need not be constant and may be changed during the reaction.

  Among these, it is possible to suppress the distillation of water and solvents added for hydrolysis to the outside of the system, and by performing a stable hydrolysis reaction, condensation is performed after the subsequent polycondensation reaction step is performed. Since the polyorganosiloxane has a high rate and storage stability, that is, it suppresses the viscosity of the resin during storage and has high handleability, the reaction mode is as follows: i) water or solvent is removed from the reaction system. It is preferable to carry out the hydrolysis step by a method selected from the group consisting of a method in which the reaction is carried out by a refluxing step not accompanied by ii), a method in which the reaction is carried out in a closed pressure system, or i) water or a solvent. A method in which the reaction is carried out by a refluxing step that does not involve distilling out of the reaction system is more preferably used. As a specific example of the above-mentioned i) method for carrying out the reaction by a refluxing process that does not involve distillation of water or solvent out of the reaction system, for example, a cooling pipe is attached to the upper part of the reaction vessel, and the generated water or solvent is removed. Examples include a method of reacting while fluxing. In addition, as a specific example of the method for carrying out the reaction in a sealed pressure system, for example, a method for carrying out the reaction while stirring and / or circulating the reaction solution in a sealed container can be exemplified.

  The reaction apparatus for performing the hydrolysis reaction is not particularly limited because it varies depending on the structure and molecular weight of the polyorganosiloxane. For example, a closed pressure tank reactor, a tank reactor equipped with a reflux pipe, a loop reactor, One type or two or more types of devices such as a surface renewal type stirring tank, a surface renewal type biaxial kneader, and a biaxial horizontal type stirrer can be used.

The condensation rate of the intermediate obtained by the hydrolysis step of the present invention is not particularly limited, but the polyorganosiloxane produced by the subsequent polycondensation step is subjected to hydroxyl groups and / or It has an aliphatic hydrocarbon unit consisting of one or more kinds of structures selected from the group consisting of a chain, a branched, and a cyclic group that is a chlorine atom, bromine atom, iodine atom, unsubstituted or substituted, and has 1 carbon atom There is a hydrolyzable group selected from the group consisting of monovalent alkoxy groups having a value of 20 or less, and the functional group undergoes a significant increase in polyorganosiloxane by condensing after storage if necessary during storage. Since viscosity and gelation are caused and storage stability may deteriorate, it is preferably 70% or more, more preferably 78% or more, and further preferably 80% or more, 3% or more is particularly preferable.
The condensation rate of the intermediate obtained by the hydrolysis step in the present invention can be calculated by the same method as the method for calculating the condensation rate of the polyorganosiloxane of the present invention.

  Next, the polycondensation reaction step in the present invention will be described. In the polycondensation reaction step, it is necessary to carry out the condensation reaction while removing by-products such as alcohol generated in the hydrolysis step and water and solvent added in the hydrolysis step. A method of circulating, a method of performing under reduced pressure, a method of circulating an inert gas under reduced pressure, a method of polycondensation while adjusting the reaction temperature and / or operating pressure in multiple stages, and a method of combining these It is preferable to use it. The reaction can also be carried out with one reactor or a combination of a plurality of reactors. In the present invention, when the reaction solution is phase-separated after the hydrolysis is performed in the presence or absence of a solvent, the organic solvent layer is separated from the reaction solution and then subjected to the polycondensation reaction step. It is also possible to provide.

  Since the polycondensation reaction in the present invention is carried out following the hydrolysis reaction, the polycondensation reaction step can be carried out without newly adding a catalyst, or can be carried out by adding a new catalyst. It is. When a catalyst is newly added, a catalyst that can be used in the hydrolysis step can be used. When a catalyst is newly added, the amount of the catalyst added is preferably in the range of 0.0001 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total mass of the reactive organosilicon compound to be subjected to hydrolysis. A range of 0.01 parts by mass or more and 5 parts by mass or less is more preferable.

  Although there is no limitation in particular about the reaction temperature at the time of performing a polycondensation reaction, it is the range of 0 to 200 degreeC normally. If the reaction temperature is less than 0 ° C, the reaction rate may decrease and the reaction time may be long. If the reaction temperature exceeds 200 ° C, the resulting polyorganosiloxane may be colored. From the viewpoint of increasing the reaction rate and suppressing the modification of the polyorganosiloxane, the reaction temperature is preferably in the range of 20 ° C. or higher and 180 ° C. or lower, more preferably in the range of 40 ° C. or higher and 160 ° C. or lower, and 60 ° C. or higher and 140 ° C. or lower. A range is more preferred. 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 the present invention, the polycondensation reaction can be carried out in an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide or lower saturated hydrocarbon, or in the air. Among these gases, from the viewpoint of suppressing modification of the polyorganosiloxane, an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, carbon dioxide or lower saturated hydrocarbon is preferable, and nitrogen, helium, neon, Argon, krypton, xenon and carbon dioxide are more preferred, nitrogen and helium are more preferred, and nitrogen is particularly preferred.

In addition, the polycondensation reaction can be performed under the atmosphere of the gas, under the circulation of the gas, under reduced pressure, under pressure, or in a combination of these. The pressure need not be constant and may be changed during the reaction. Among these, water produced by polycondensation can be distilled off, and a polycondensation reaction can be carried out at a high reaction rate. Therefore, the reaction is preferably carried out under reduced pressure, and it is preferably 1.333 Pa or more and 5.333 × 10 ^4. It is more preferable to carry out the reaction in a pressure range of Pa or less. Further, in the above-described reduced pressure state, a method of circulating an inert gas, a method of performing the operation while adjusting the operation temperature and / or the operation pressure in multiple stages, etc. are exemplified as one of the preferable modes implemented in the present invention. it can.

The reaction time for performing the polycondensation reaction is not particularly limited because it varies depending on the structure of the polyorganosiloxane to be obtained. From the viewpoint of improving the reaction rate and suppressing the modification of the polyorganosiloxane, the reaction time is 0.1. A range of not less than 100 hours and not less than 100 hours is preferable, a range of not less than 0.5 hours and less than 80 hours is more preferable, a range of not less than 1 hour and less than 50 hours is further preferable, and a range of not less than 1 hour and less than 30 hours is particularly preferable.
The reaction apparatus for performing the polycondensation reaction is not particularly limited because it varies depending on the structure and molecular weight of the polyorganosiloxane.For example, a rotary evaporator, a vertical stirring tank equipped with a distillation pipe, a surface renewal stirring tank, Thin film evaporator, surface renewal type biaxial kneader, biaxial horizontal agitator, wet wall reactor, free fall perforated plate reactor, volatile components are distilled off while dropping the compound along the support One kind or two or more kinds of apparatuses such as a reactor to be used can be used in combination.

  The polyorganosiloxane obtained after the polycondensation reaction is not particularly limited by the production method of the present invention, but the fluidity as a liquid can be secured, the handling property tends to increase, and is added as necessary. Since mixing with additives tends to be easy, it is preferably a liquid having a viscosity of 1,000 Pa · s or less, more preferably a liquid having a viscosity of 500 Pa · s or less, at a temperature of 25 ° C. Further, a liquid having a viscosity of 300 Pa · s or less is more preferable, and a liquid having a viscosity of 200 Pa · s or less is particularly preferable.

Further, the content of the hydrolyzable group contained in the polyorganosiloxane obtained after the polycondensation reaction by the production method of the present invention is such that the cured product obtained by curing the polyorganosiloxane has a resistance to thermal cycle. Since the thermal shock resistance and adhesiveness are improved, the total content of siloxane units having a hydrolyzable group contained in the polyorganosiloxane as a substituent is 5 mol% or less based on the total Si amount. Preferably, it is 3 mol% or less, more preferably 1% or less, still more preferably 0.5% or less, and it is desirable that it is not contained at all. The total content of siloxane units having hydrolyzable groups as substituents with respect to the total Si contained in the polyorganosiloxane contains the peak area of the internal standard substance obtained by ²⁹ Si-NMR measurement and the residual hydrolyzable groups. It can be quantified by calculating the area ratio of the peak area derived from Si.

The polyorganosiloxane obtained by the present invention has excellent transparency that can be used for applications requiring transparency, and has stable and reproducible cold and thermal shock resistance in a thermal cycle, so that a light emitting diode It is suitably used as a sealing material. Further, since the polyorganosiloxane obtained by the present invention gives a hardened product having excellent dimensional stability, it is a spectacle lens, a lens for optical equipment, a CD or DVD pickup lens, an automotive headlamp lens, a projector. It is also suitably used as a lens material such as a lens for use. Further, the light-emitting element and / or the optical lens obtained above 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 light, an indicator light, It can be suitably used as a semiconductor device such as a display device, a light source of a planar light emitter, a display, decoration, and various lights.
In addition, the polyorganosiloxane obtained by the present invention can be used as various optical members such as optical fibers, optical waveguides, optical filters, optical adhesives, optical disk substrates, display substrates, antireflection coatings and other coating materials. is there. Moreover, it can use suitably also as resin for raw materials, such as a photosensitive resin and a fluorescent resin.

  When used in the above applications, the polyorganosiloxane obtained by the present invention includes, as necessary, conventionally known epoxy resins, silicone resins, silicone resins having curable functional groups, acrylic resins, urea resins, imide resins. It can be used as a curable resin composition appropriately blended with organic resins such as vinyl ethers, curable compounds such as vinyl ethers, curing catalysts for reacting curable functional groups contained in the polyorganosiloxane of the present invention, and the like. it can. The curing catalyst used varies depending on the type of curable functional group contained in the polyorganosiloxane, but an imidazole compound, a quaternary ammonium salt, an amine compound, an aluminum chelate compound, an organic phosphine compound, a metal carboxylate, Acetylacetone chelate compound, Lewis acid catalyst, cationic polymerization initiator, photo radical initiator, thermal radical initiator, onium salt, mineral acid, organic acid, phosphonium salt, silicic acid, tetrafluoroboric acid, anionic polymerization initiator, Examples include photoacid generators. These can be used as one kind or a mixture of two or more kinds.

  Specific examples of these compounds include 2-methylimidazole and 2-ethyl-4-methylimidazole as imidazole compounds. Examples of amine compounds include 1,8-diaza-bicyclo (5,4,0) undecene-7, trimethylamine, benzyldimethylamine, triethylamine, dimethylbenzylamine, 2,4,6-trisdimethylaminomethylphenol, Those salts are mentioned. Examples of the quaternary ammonium salt include tetramethylammonium chloride, benzyltrimethylammonium bromide, and tetrabutylammonium bromide. Examples of the aluminum chelate compound include aluminum ethyl acetoacetate / diisopropylate, aluminum trisethyl acetoacetate, aluminum alkyl acetoacetate / diisopropylate, aluminum bisethyl acetoacetate / monoacetylacetonate, aluminum trisacetylacetonate, etc. Can be mentioned. Examples of the organic phosphine compound include tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium-0,0-diethyl phosphorodithioate, and the like. Examples of metal carboxylates and acetylacetone chelate compounds include chromium (III) tricarboxylate, tin octylate, chromium acetylacetonate, and the like. Moreover, as a commercial item, U-CAT SA1, U-CAT 2026, U-CAT 18X, etc. manufactured by San Apro can be exemplified.

Examples of the cationic polymerization initiator include Lewis acid catalysts typified by BF ₃ · amine complexes, PF ₅ , BF ₃ , AsF ₅ , SbF ₅ , phosphonium salts, quaternary ammonium salts, sulfonium salts, benzyl Examples include ammonium salts, benzylpyridinium salts, benzylsulfonium salts, hydrazinium salts, carboxylic acid esters, sulfonic acid esters, and amine imides. Moreover, as a commercial item, for example, SI-100L, SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.), which is a cationic polymerization initiator based on sulfonium salt, CP-66, CP-77 (manufactured by Asahi Denka Kogyo Co., Ltd.) ) And the like, ultraviolet curable cationic polymerization catalysts represented by diaryl iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, and the like.
Examples of the photo radical initiator include carbonyl compounds such as acetophenone compounds, benzoin ether compounds, and benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, phosphine oxide compounds, and the like. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglycone Oxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropane-1-one Carbonyl compounds such as 1-hydroxy-cyclohexyl-phenylketone; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvalero; Examples include peroxide compounds such as benzoyl peroxide and ditertiary butyl peroxide. Moreover, IRGACURE184 (made by CIBA company) can be illustrated as a commercial item.

Furthermore, examples of the thermal radical initiator include organic peroxides such as benzoyl peroxide, lauryl peroxide, t-butyl peroxide, cumene hydroperoxide, and azo compounds such as azobisisobutyronitrile.
Among these, as a combination of a curable functional group and a curing catalyst to be used, [a] When the curable functional group has a carbon-carbon double bond, the curing catalyst is a photo radical initiator, a thermal radical. Preferably, at least one curing catalyst selected from the group consisting of an initiator and an anionic polymerization initiator is used. [B] When the curable functional group is an epoxy group, the curing catalyst is an imidazole compound, quaternary ammonium salt, phosphonium salt, amine compound, aluminum chelate compound, organic phosphine compound, metal carboxylate or acetylacetone. At least one curing catalyst selected from the group consisting of chelate compounds is preferably used. Furthermore, when [c] the curable functional group is at least one selected from the group consisting of episulfide, dithiocarbonate, and trithiocarbonate, the curing catalyst includes amines, phosphines, mineral acids, Lewis acids, At least one curing catalyst selected from the group consisting of organic acids, silicic acids, and tetrafluoroboric acid is preferably used. [D] When the curable functional group is an oxetanyl group, as the curing catalyst, at least one curing catalyst selected from the group consisting of a cationic polymerization catalyst and a photoacid generator is preferably used.

  In general, the amount of these curing catalysts is preferably 0.001 part by mass or more and more preferably 0.005 part by mass or more for increasing the curing rate with respect to 100 parts by mass of the polyorganosiloxane. More preferably, the content is 0.01 parts by mass or more. On the other hand, since heat-resistant yellowing increases, it is preferably 10 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 1 part by mass or less, and 0.5 parts by mass or less. It is particularly preferred.

Among the above, when the curable functional group contained in the polyorganosiloxane contains an epoxy group, a curing agent can be blended. The curing agent used is not particularly limited. For example, acid anhydride compounds, amine compounds, amide compounds, phenol compounds, and the like can be used. In particular, aromatic acid anhydrides and cyclic aliphatic acid anhydrides can be used. An acid anhydride compound such as an aliphatic acid anhydride is preferable, and a carboxylic acid anhydride is more preferable.
The acid anhydride compounds include alicyclic acid anhydrides, and alicyclic carboxylic acid anhydrides are preferred among carboxylic acid anhydrides. These curing agents may be used alone or in combination of two or more.

  Specific examples of the curing agent include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride. , Methylhexahydrophthalic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, tetra Polyamide resins, bisphenols, phenols (phenols, alkyl-substituted phenols) synthesized from ethylenepentamine, dimethylbenzylamine, ketimine compounds, dimer of linolenic acid and ethylenediamine Naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and polycondensates of various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and aromatic dimethylol, or bis Examples include condensates of methoxymethyl biphenyl with naphthols or phenols, biphenols and modified products thereof, imidazole, boron trifluoride-amine complexes, guanidine derivatives, and the like.

Specific examples of the alicyclic carboxylic acid anhydride include 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, “4-methylhexahydro Phthalic anhydride / hexahydrophthalic anhydride = 70/30 ”, 4-methylhexahydrophthalic anhydride,“ methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride / bicyclo [2.2. 1] heptane-2,3-dicarboxylic anhydride "and the like.
Among these curing agents, since the light resistance of the cured product obtained by curing the polyorganosiloxane of the present invention tends to increase, 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 curing agent used is preferably 1 part by mass or more and 200 parts by mass or less, and more preferably 2 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the polyorganosiloxane obtained by the present invention. When the amount of the curing agent used is less than 1 part by mass with respect to 100 parts by mass of the polyorganosiloxane, the curing speed may decrease. On the other hand, when it exceeds 200 parts by mass, the moisture resistance as a cured product may deteriorate. is there.
Furthermore, among the above, when the curable functional group contained in the polyorganosiloxane contains an acid anhydride group, a resin having a conventionally known epoxy group as the curable functional group can be blended.

  The resin having an epoxy group as a curable functional group used in the present invention is not particularly limited. For example, an alicyclic epoxy resin, an aliphatic epoxy resin, a polyfunctional epoxy resin composed of a glycidyl etherified product of a polyphenol compound, Polyfunctional epoxy resin that is glycidyl etherified product of novolak resin, nuclear hydride of aromatic epoxy resin, heterocyclic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, epoxy resin obtained by glycidylation of halogenated phenols And conventionally known epoxy resins such as other silicone compounds having an epoxy group as a functional group. These epoxy resins may be used alone or in combination.

The alicyclic epoxy resin that can be used in the present invention is not particularly limited as long as it is an epoxy resin having an alicyclic epoxy group, and examples thereof include a cyclohexene oxide group, a tricyclodecene oxide group, and a cyclopentene oxide. An epoxy resin having a group or the like can be given. Specific examples of the alicyclic epoxy resin include 4-vinyl epoxycyclohexane, dioctyl epoxyhexahydrophthalate, and di-2-ethylhexyl epoxyhexahydrophthalate as monofunctional alicyclic epoxy compounds. Examples of the bifunctional alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4 -Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, bis (3,4-epoxy-6-methyl) (Cyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethyl Glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexane carboxylate), 1,2,8,9- diepoxylimonene, and the like. Examples of the polyfunctional alicyclic epoxy compound include 1,2-epoxy-4- (2-oxiranyl) cyclohexene adduct of 2,2-bis (hydroxymethyl) -1-butanol. Furthermore, as what is marketed as a polyfunctional alicyclic epoxy compound, Epolide GT401, EHPE3150 (made by Daicel Chemical Industries Ltd.), etc. are mentioned.
The typical example of an alicyclic epoxy resin is shown below.

The aliphatic epoxy resin that can be used in the present invention is not particularly limited, and specifically, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, pentaerythritol. And glycidyl ethers of polyhydric alcohols such as xylylene glycol derivatives.
The following are typical examples of aliphatic epoxy resins.

The polyfunctional epoxy resin comprising a glycidyl etherified product of a polyphenol compound that can be used in the present invention is not particularly limited, and specifically, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol. Tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, dimethyl bisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol) , 4,4'-Butiri -Bis (3-methyl-6-t-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, 2,6-di (t-butyl) hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, 1,1 Examples include phenols having a fluorene skeleton such as di (4-hydroxyphenyl) fluorene, polyfunctional epoxy resins that are glycidyl etherification products of polyphenol compounds of phenolized polybutadiene, and the following glycidyl etherification products of phenols having a bisphenol skeleton. The typical example of the polyfunctional epoxy resin which is is shown.

  When a polyfunctional epoxy resin that is a glycidyl etherified product of a polyphenol compound is used, these repeating units (n in the chemical formula showing the above representative examples) are not particularly limited, but preferably 0 or more and 50 It is less than the range. If the number of repeating units is 50 or more, the fluidity is lowered, which may cause a practical problem. From the viewpoint of increasing the reactivity with the alkoxysilane compounds, and further from the viewpoint of increasing the fluidity of the resulting modified resin composition, the range of the repeating unit is preferably in the range of 0 to 10, more preferably 0.001 or more. The range is 2 or less.

The polyfunctional epoxy resin that is a glycidyl etherified product of novolak resin is not particularly limited, and examples thereof include phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthol. Glycidyl etherification products of various novolac resins such as novolak resins made from various phenols such as phenols, xylylene skeleton-containing phenol novolak resins, dicyclopentadiene skeleton-containing phenol novolak resins, biphenyl skeleton-containing phenol novolak resins, and fluorene skeleton-containing phenol novolak resins. Etc.
Below, the typical example of the polyfunctional epoxy resin which is the glycidyl etherification product of a novolak resin is shown.

  The nuclear hydride of the aromatic epoxy resin that can be used in the present invention is not particularly limited. For example, a glycidyl etherified product of a phenol compound (bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, etc.) or Nuclear hydrides of aromatic rings of various phenols (phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, etc.), nuclear hydrides of glycidyl ethers of novolac resins, etc. Is mentioned.

There is no limitation in particular as a heterocyclic epoxy resin, For example, the heterocyclic epoxy resin etc. which have heterocyclic rings, such as an isocyanuric ring and a hydantoin ring, are mentioned.
The glycidyl ester-based epoxy resin is not particularly limited, and examples thereof include epoxy resins composed of carboxylic acids such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester.
The glycidylamine epoxy resin is not particularly limited, and examples thereof include epoxy resins obtained by glycidylating amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivatives, diaminomethylbenzene derivatives, and the like. It is done.
Epoxy resins obtained by glycidylation of halogenated phenols are not particularly limited. For example, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, Examples thereof include epoxy resins obtained by glycidyl etherification of halogenated phenols such as chlorinated bisphenol A.

  Among the above, a cured product obtained by curing the target modified resin composition of the present invention is excellent in transparency, heat yellowing resistance, light resistance, and thermal shock resistance during thermal cycling. One or more kinds selected from the group consisting of alicyclic epoxy resins, aliphatic epoxy resins, polyfunctional epoxy resins composed of glycidyl ethers of polyphenol compounds, and nuclear hydrides of aromatic epoxy resins. It is preferably a polyfunctional epoxy resin, one or more polyfunctional epoxy selected from the group consisting of an alicyclic epoxy resin, a polyfunctional epoxy resin comprising a glycidyl etherified product of a polyphenol compound, and a nuclear hydride of an aromatic epoxy resin. More preferably, it is a resin.

When the polyorganosiloxane of the present invention is used for the above-mentioned use, in addition to a curing catalyst and a curing agent, if necessary, a light stabilizer, an antioxidant, a silane coupling agent, a modifier, a colorant, a phosphor, It can be used as a curable resin composition appropriately blended with conventionally known additives such as inorganic fillers. In curable resin compositions, plasticizers, flame retardants, stabilizers, antistatic agents, impact resistance enhancers, light diffusing agents, antifoaming agents, foaming agents, antibacterial / anti-antimicrobial agents commonly used as additives for resins Molding agents, conductive fillers, antifogging agents, and the like can be blended. In addition to the curable resin composition, a conventionally known hydrocarbon-based curable compound may be blended.
The light stabilizer used is not particularly limited, and examples thereof include benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based, nickel-based, triazine-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like. It is done.
The antioxidant used is not particularly limited. For example, organic phosphorus antioxidants such as triphenyl phosphate and phenylisodecyl phosphite, and organic compounds such as distearyl-3,3′-thiodipropinate. Examples thereof include sulfur-based antioxidants and phenol-based antioxidants such as 2,6-di-tert-butyl-p-cresol.

  The silane coupling agent used is not particularly limited. For example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid Xylpropylmethyldiethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxy (Cyclohexyl) ethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, N- (2-aminoethyl) aminomethyl Trimethoxysilane, 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) tri Methoxysilane, (N-phenylaminomethyl) methyldimethoxysilane, (N-cyclohexyl) Minomethyl) triethoxysilane, (N-cyclohexylaminomethyl) methyldiethoxysilane, piperazinomethyltrimethoxysilane, piperazinomethyltriethoxysilane, 3-piperazinopropyltrimethoxysilane, 3-piperazinopropyl Methyldimethoxysilane, 3-ureidopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltri Ethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3- (trimethoxysilyl) propylsuccinic anhydride 3- (triethoxysilyl) propyl succinic anhydride, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxy Silane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane , Methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxy Silane, methylcyclohexyldimethoxysilane, methylcyclohexyldiethoxysilane, methylcyclopentyldimethoxysilane, methylcyclopentyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-methacryloxypropyl triethoxysilane, etc. are mentioned. Moreover, the partial condensate of these silane coupling agents can also be used.

  The modifier used is not particularly limited as long as it imparts flexibility to the cured product obtained by reacting the curable functional group contained in the polyorganosiloxane of the present invention and improves the peel adhesion. . Examples of the modifier used include polyols containing two or more hydroxyl groups in one molecule, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3- Propanediol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,2-butanediol, 1,4-butanediol, neopentyl glycol, glycerin, erythritol, trimethylolpropane, 1,2,4-butanetriol, etc. Aliphatic polyols, polycarbonate diols, and silicones having a silanol group at the terminal are preferably used. These modifiers can be used as one kind or a mixture of two or more kinds.

  The colorant used is not particularly limited. For example, phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavantron, perinone, perylene, dioxazine, condensed azo, azomethine-based various organic dyes, titanium oxide, lead sulfate, Examples thereof include inorganic pigments such as chrome yellow, zinc yellow, chrome vermillion, valve shell, cobalt purple, bitumen, ultramarine, carbon black, chrome green, chrome oxide, cobalt green and the like. These colorants may be used alone or in combination of two or more.

The phosphor in the present invention is a substance that emits fluorescence, that is, absorbs energy such as an electron beam, X-rays, ultraviolet rays, and an electric field, and emits a part of the absorbed energy as visible light (emission). It is not particularly limited as long as it is a substance to be used. Of these, inorganic phosphors that generally exhibit excellent light-emitting properties are preferred.
In the case of using an inorganic phosphor, in order to express the performance of the inorganic phosphor, an element B called an activator (emission center) is generally introduced into a compound A called a matrix. It is used and is usually written as “matrix A: activator B”.

In particular, when the fluorescent resin composition is used as a sealing material for a light emitting diode, it is preferable to use a cerium-activated yttrium aluminate phosphor (YAG: Ce phosphor) for the reasons described later. When using as, it is preferable to use a phosphorescent phosphor. These may be used alone or in combination of two or more.
The blending amount of the phosphor is preferably, as a mass ratio, resin composition: phosphor = 30: 70 to 95: 5, more preferably 50:50 to 80:20 (100 in total). When the blending amount of the phosphor is larger than the resin composition: phosphor = 30: 70, the fluidity as the phosphor resin composition may be deteriorated. When the blending amount is less than 95: 5, the phosphor as the phosphor The function may be insufficient.

The matrix A and the activator B are not particularly limited, and examples of the matrix A include oxide phosphors and nitride phosphors. Examples of the activator B include rare earth elements such as europium (Eu) and cerium (Ce).
As the above-described oxide phosphor, for example, “YAG: Ce phosphor” in which the base A is yttrium aluminate (Y ₃ Al ₅ O ₁₂ : hereinafter referred to as YAG) and the activator B is cerium (Ce). Well known. When this is irradiated with blue light (around 460 nm), yellow light emission occurs efficiently. In this phosphor, a part of Y of “Y ₃ Al ₅ O ₁₂ ” is replaced with another Gd, Tb, or the like, or a part of Al is replaced with Ga or the like to change the structure of the base A. Therefore, the emission peak position can be shifted to the long wavelength side or the short wavelength side, which is very useful.

In other words, the “YAG: Ce phosphor” means that the base A is YAG or a part of Y is replaced with another Gd, Tb or the like, or a part of Al is replaced with Ga or the like. There is no particular limitation as long as the structure of A is changed and the activator B is a phosphor of Ce. Specific examples thereof include “Y ₃ Al ₅ O ₁₂ : Ce ³⁺ ” and “(Y ₃ , Gd _0.9 ) Al ₅ O ₁₂ : Ce ³⁺ ”.
As another example of the oxide phosphor, the base A is strontium barium silicate (Sr, Ba) ₂ SiO ₄ and europium (Eu) is introduced as the activator B, “(Sr, Ba) ₂ SiO ₄ : Eu phosphor ”is known. In this system, the emission color can be adjusted from green to orange by changing the composition ratio of Sr and Ba.

Examples of the nitride phosphor described above include the following.
α-Sialon phosphor: Base A is a crystal in which a metal ion such as Ca, aluminum and oxygen are dissolved in α-type silicon nitride crystal, and “(M _p (Si, Al) ₁₂ (O, N)” in represented by ₁₆ "where, M is a metal ion, p is shows the amount of solid solution specifically" _{Ca p (Si, Al) 12} (O, N) 16:.. Eu ", and the like.
β-sialon phosphor: the matrix A is represented by a composition of “Si _6-q Al _q O _q N _{8 -q} ” in which aluminum and oxygen are dissolved in a β-type silicon nitride crystal. Here, q represents the amount of solid solution. Specifically, _{"Si 6-q Al q O q} N 8-q: Eu ", and the like.
CaAlSiN ₃ phosphor: The base A is a nitride crystal obtained by reacting calcium nitride, aluminum nitride, and silicon nitride at a high temperature of 1800 ° C., and specifically includes “CaAlSiN ₃ : Eu”.

Specific examples of the inorganic phosphor include, for example, those having a red emission color such as “6MgO · As ₂ O ₅ : Mn ⁴⁺ , Y (PV) O ₄ : Eu”, “CaLa _0.1 Eu. _0.9 Ga ₃ O ₇ ”,“ BaY _0.9 Sm _0.1 Ga ₃ O ₇ ”,“ Ca (Y _0.5 Eu _0.5 ) (Ga _0.5 In _0.5 ) ₃ O ₇ ” , “Y ₃ O ₃ : Eu, YVO ₄ : Eu”, “Y ₂ O ₂ : Eu”, “3.5MgO · 0.5MgF ₂ GeO ₂ : Mn ⁴⁺ ”, “(Y · Cd) BO ₂ : Eu” Or the like.

Examples of blue light-emitting colors include “(Ba, Ca, Mg) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ ”, “(Ba, Mg) ₂ Al ₁₆ O ₂₇ : Eu ²⁺ ”, “ “Ba ₃ MgSi ₂ O ₈ : Eu ²⁺ ”, “BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ ”, “(Sr, Ca) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ ”, “(Sr, Ca) ₁₀ ( PO ₄ ) ₆ Cl ₂ .nB ₂ O ₃ : Eu ²⁺ ”,“ Sr ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu ²⁺ ”,“ (Sr, Ba, Ca) ₅ (PO ₄ ) ₃ Cl: Eu ²⁺ ” , “Sr ₂ P ₂ O ₇ : Eu”, “Sr ₅ (PO ₄ ) ₃ Cl: Eu”, “(Sr, Ca, Ba) ₃ (PO ₄ ) ₆ Cl: Eu”, “SrO · P ₂ O ₅ · _B 2 _{O 5:} Eu "," _(BaCa) 5 (P O ₄ ) ₃ Cl: Eu ”,“ SrLa _0.95 Tm _0.05 Ga ₃ O ₇ ”,“ ZnS: Ag ”,“ GaWO ₄ ”,“ Y ₂ SiO ₆ : Ce ”,“ ZnS: Ag, Ga ” , Cl ”,“ Ca ₂ B ₄ OCl: Eu ²⁺ ”,“ BaMgAl ₄ O ₃ : Eu ²⁺ ”,“ (M1, Eu) ₁₀ (PO ₄ ) ₆ Cl ₂ (M1 is Mg, Ca, Sr, and At least one element selected from the group consisting of Ba) "and the like.

Examples of green light-emitting colors include “Y ₃ Al ₅ O ₁₂ : Ce ³⁺ (YAG)”, “Y ₂ SiO ₅ : Ce ³⁺ , Tb ³⁺ ”, “Sr ₂ Si ₃ O ₈ .2SrCl”. ₂ : Eu ”,“ BaMg ₂ Al ₁₆ O ₂₇ : Eu ²⁺ , Mn ²⁺ ”,“ ZnSiO ₄ : Mn ”,“ Zn ₂ SiO ₄ : Mn ”,“ LaPO ₄ : Tb ”,“ SrAl ₂ O ₄ : Eu ”,“ SrLa _0.2 Tb _0.8 Ga ₃ O ₇ ”,“ CaY _0.9 Pr _0.1 Ga ₃ O ₇ ”,“ ZnGd _0.8 Ho _0.2 Ga ₃ O ₇ ”,“ SrLa _{0 .6} Tb _0.4 Al ₃ O ₇ , ZnS: Cu, Al ”,“ (Zn, Cd) S: Cu, Al ”,“ ZnS: Cu, Au, Al ”,“ Zn ₂ SiO ₄ : Mn ”, "ZnSiO _4: Mn", "Z S: Ag, Cu "," (Zn · Cd) S: Cu "," ZnS: Cu "," GdOS: Tb, "" LaOS: Tb, "" YSiO _4: Ce · Tb "," ZnGeO _4: Mn ”,“ GeMgAlO: Tb ”,“ SrGaS: Eu ²⁺ ”,“ ZnS: Cu · Co ”,“ MgO · nB ₂ O ₃ : Ge, Tb ”,“ LaOBr: Tb, Tm ”,“ La ₂ O ₂ S ” : Tb "and the like.
Further, “YVO ₄ : Dy” having a white emission color, “CaLu _0.5 Dy _0.5 Ga ₃ O ₇ ” having a yellow emission color, and the like can be given.

Specific examples of the organic phosphor include, for example, 1,4-bis (2-methylstyryl) benzene (Bis-MSB), trans-4,4′-diphenylstilbene (DPS) having a blue emission color. ) And stilbene dyes such as 7-hydroxy-4-methylcoumarin (coumarin 4).
Examples of commercially available products having yellow to green fluorescent colors include Brilliantsulfoflavine FF, Basic yellow HG, SINLOIHI COLOR FZ-5005 (manufactured by SINLOIHI), and the like.
As what has a yellowish-red fluorescent color, Eosine, Rhodamine 6G, Rhodamine B etc. are mentioned as a commercial item, for example.

In general phosphors, when light, an electron beam or the like, which is an irradiation excitation source, is cut off, light emission is immediately attenuated and disappears. However, as an exception, there is a phosphor that exhibits afterglow for several seconds to several tens of hours after the excitation source is cut off, and this is called a phosphorescent phosphor. The type is not particularly limited as long as it exhibits this property. Specifically, for example, “CaS: Eu, Tm”, “CaS: Bi”, “CaAl ₂ O ₄ : Eu, Nd ”,“ CaSrS: Bi ”,“ Sr ₂ MgSi ₂ O ₇ : Eu, Dy ”,“ Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy ”,“ SrAl ₂ O ₄ : Eu, Dy ”,“ SrAl ₂ O ” ₄ : Eu ”,“ ZnS: Cu ”,“ ZnS: Cu, Co ”,“ Y ₂ O ₂ S: Eu, Mg, Ti ”,“ CaS: Eu, Tm ”, etc. Among them, long afterglow “Sr ₂ MgSi ₂ O ₇ : Eu, Dy”, “Sr ₄ Al ₁₄ O ₂₅ : Eu, Dy”, “SrAl ₂ O ₄ : Eu, Dy”, “SrAl ₂ O ₄ : Eu” are preferable. .

The method for producing the fluorescent resin composition of the present invention is not particularly limited. For example, while stirring the curable resin composition and the phosphor simultaneously or separately as necessary, the mixture is stirred with a mixing device described later. Examples thereof include a method of mixing and dispersing, and a method of performing a defoaming treatment under reduced pressure, if necessary, following the above method.
Although the said mixing apparatus is not specifically limited, For example, a raikai machine, a 3 roll mill, a ball mill, a planetary mixer, a line mixer, a homogenizer, a homodisper etc. are mentioned.

  The inorganic filler used is not particularly limited, and examples thereof include silicas (fused crushed silica, crystal crushed silica, spherical silica, fumed silica, colloidal silica, precipitated silica, etc.), silicon carbide, silicon nitride, boron nitride, Calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, aluminum oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, titanic acid Examples include barium, glass fiber, carbon fiber, molybdenum disulfide. In particular, silicas, calcium carbonate, aluminum oxide, aluminum hydroxide, calcium silicate and the like are preferable, and silicas are more preferable in consideration of physical properties of the cured product. These inorganic fillers may be used alone or in combination of two or more.

The compounding amount of the above additives is usually in the range of 0.001 parts by mass or more and 100 parts by mass or less for each additive with respect to 100 parts by mass of the polyorganosiloxane obtained by the present invention.
The curable resin composition containing the polyorganosiloxane of the present invention can be made into a cured product by a known method. Among them, the method of curing by heating or the method of curing by irradiating with light is a method that is easy to operate and generally used, and can be exemplified as a preferable method in the present invention. The temperature for curing by heating is not particularly limited because it depends on the epoxy resin or curing agent used, but is usually in the range of 20 to 200 ° C.
On the other hand, the light used for curing by irradiation with light is preferably ultraviolet light or visible light, and more preferably ultraviolet light. Examples of the light source include low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultrahigh-pressure mercury lamp, UV lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, argon ion laser, helium cadmium laser, Examples of the light source include a helium neon laser, a krypton ion laser, various semiconductor lasers, a YAG laser, an excimer laser, a light emitting diode, a CRT light source, and a plasma light source.
The curing reaction described above can be performed in air, or in an inert gas atmosphere such as nitrogen, helium, or argon as necessary.

The emission wavelength of the light-emitting diode encapsulated with the curable resin composition containing the polyorganosiloxane of the present invention can be widely used from infrared to red, green, blue, violet, and ultraviolet. The material can be used practically to light having a wavelength of 250 nm to 550 nm, which is deteriorated due to insufficient light resistance. As a result, a white light-emitting diode having a long life, high energy efficiency, and high color reproducibility can be obtained. Here, the emission wavelength refers to the main emission peak wavelength.
As a specific example of the light emitting element to be used, for example, a light emitting element formed by stacking semiconductor materials on a substrate can be exemplified. In this case, examples of the semiconductor material include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaAlN, and SiC.

Examples of the substrate include sapphire, spinel, SiC, Si, ZnO, and GaN single crystal. If necessary, a buffer layer may be formed between the substrate and the semiconductor material. Examples of these buffer layers include GaN and AlN.
The method for laminating the semiconductor material on the substrate is not particularly limited, but for example, MOCVD method, HDVPE method, liquid phase growth method and the like are used.
Examples of the structure of the light emitting element include a homojunction having a MIS junction, a PN junction, and a PIN junction, a heterojunction, and a double heterostructure. A single or multiple quantum well structure may also be used.

  A light emitting diode can be manufactured by sealing a light emitting element using the curable resin composition containing the polyorganosiloxane of this invention. In this case, the light-emitting element can be sealed only with the curable resin composition, but can be sealed with another curable resin composition in combination. When other curable resin composition is used in combination, after sealing with a curable resin composition containing the polyorganosiloxane obtained by the present invention, the periphery is sealed with another curable resin composition. Or after sealing with another curable resin composition, the circumference | surroundings can also be sealed with the curable resin composition obtained by this invention. Examples of other curable resin compositions include epoxy resins, silicone resins, acrylic resins, urea resins, imide resins, and glass.

  As a method for sealing a light emitting device using a curable resin composition containing the polyorganosiloxane of the present invention, for example, a curable resin composition is injected in advance into a mold mold, and the light emitting device is fixed thereto. For example, a method of curing after immersing a lead frame or the like, a method of injecting a curable resin composition into a mold frame in which a light emitting element is inserted, and a method of curing. In this case, examples of the method for injecting the curable resin composition include injection by a dispenser, transfer molding, injection molding and the like. Still other sealing methods include a method in which a curable resin composition is dropped onto a light-emitting element and applied by stencil printing, screen printing, or a mask, and cured, or a cup having a light-emitting element disposed in the lower part. Examples of the method include injecting a curable resin composition into a resin using a dispenser and curing the composition.

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

  Further, for example, (a) a curable resin composition containing the polyorganosiloxane of the present invention, and (b) a resin obtained by further adding an oxetane compound to the curable resin composition containing the polyorganosiloxane of the present invention. (C) a fluorescent resin composition obtained by further adding a phosphor to the curable resin composition containing the polyorganosiloxane of the present invention of the present invention, and (a) to (c), a curing agent and A curable resin composition to which a curing accelerator is added, or a photosensitive resin composition in which a photoacid generator is further added to the above (a) to (c), for example, (d) of the present invention. A conductive resin composition obtained by further adding conductive metal powder to the curable resin composition containing the polyorganosiloxane of the present invention, and (e) the curable resin composition containing the polyorganosiloxane of the present invention. In addition, insulating powder is added An rim resin composition, a curable resin composition obtained by adding a curing agent and a curing accelerator to the above (d) and (e), or a photoacid generator in addition to the above (d) and (e). The photosensitive resin composition to which an agent is added can be usefully used as a coating agent that is less susceptible to polymerization inhibition by oxygen.

The coating agent in the present invention is not particularly limited as long as it is a material for forming a coating film on the surface of a substance and covering it, and the main use purpose is as follows, if necessary, It is also possible to mix pigments, pigments and the like with the coating agent and use them as paints and inks.
(1) Protection of coatings and substrates, imparting durability, maintaining aesthetics (ultraviolet rays, infrared rays, oxidation, corrosion, scratches,
Protection from dust, dirt, temperature, humidity, etc.)
(2) Glossiness imparted to coatings and substrates (3) Water repellent treatment to coatings and substrates (4) Non-slip processing for flooring, etc. (5) Sealing and insulation of electronic components

  A coating agent containing at least the curable resin composition containing the polyorganosiloxane of the present invention is applied by a conventionally known method, and then cured to form a coating film. At this time, the application methods include brush coating, roller coating, spray coating, bar coater, roll coater, baking coating, dip coating, electrodeposition coating, electrostatic coating, powder coating, vapor deposition, plating, and other coating techniques. Printing techniques such as inkjet, laser printing, rotary printing, gravure printing, and screen printing, on the other hand, as a method of forming a coating film, a method of curing by heating, or a method of curing by irradiating light, Each is preferably used.

  The application of the coating agent containing at least the curable resin composition containing the polyorganosiloxane of the present invention and the coating film formed using the same is not particularly limited. For example, the coating agent (paint, resin, Coating and adhesion of plastics, metals, steel pipes, automobiles, buildings, optical fibers, etc.), optical discs (DVD, CD, Blu-ray discs, etc.), inks (inkjet printers, gravure printing, flexographic printing, resist for printed wiring boards, UV printing) Applications), printing plate making materials (PS flat plate, photosensitive resin relief plate, photosensitive material for screen plates, etc.), photoresist (semiconductor resist, printed wiring board resist, photofabrication resist, etc.), printed wiring board, IC Pattern formation and liquid for various electronic parts including LSI Color filter forming materials for PDP displays, sealing materials for liquid crystals and organic EL, peripheral materials for semiconductors and light emitting diodes (sealing materials, lens materials, substrate materials, die bonding materials, chip coating materials, laminated plates, optical fibers, optical waveguides , Optical filters, adhesives for electronic components, coating materials, sealing materials, insulating materials, photoresists, encap materials, potting materials, optical transmission layers and interlayer insulating layers of optical disks, printed wiring boards, laminates, light guide plates, Anti-reflective coating, etc., paint (corrosion-resistant paint, maintenance, marine paint, corrosion-resistant lining, primer for automobiles and home appliances, beverages / beer cans, external lacquer, extruded tube paint, general anti-corrosion paint, maintenance equipment, for woodwork products Lacquer, electrodeposition primer for automobile, other electrodeposition coating for industrial use, beverage / beer can inner surface lacquer, coil coater Coating, drum / can inner coating, wood coating, acid-resistant lining, wire enamel, insulation coating, automotive primer, various metal products, anti-corrosion and anti-corrosion coating, pipe interior and exterior coating, electrical component insulation coating, etc.), composite materials ( Pipes and tanks for chemical plants, aircraft materials, automotive components, various sports equipment, carbon fiber composite materials, aramid fiber composite materials, etc.), civil engineering and building materials (floor materials, paving materials, membranes, anti-slip and thin pavement, concrete) Jointing / raising, anchor embedding adhesion, precast concrete bonding, tile bonding, crack repairing of concrete structures, grouting and leveling of pedestals, anticorrosion / waterproofing of water and sewage facilities, corrosion resistant laminated linings for tanks, iron structures Anti-corrosion coating, mastic painting of building exterior walls, etc.), adhesive (metal, glass, ceramics, cement concrete) Adhesives of the same or different materials such as cleats, wood, and plastics, adhesives for assembly of automobiles, railway vehicles, aircraft, etc., adhesives for manufacturing prefabricated composite panels, etc .: Including one-component, two-component, and sheet types . ), Aircraft / automobile / plastic molding jigs (resin molds such as press molds, stretched dies, matched dies, vacuum molding / blow molding molds, master models, casting patterns, laminated jigs, various inspection jigs, etc.), It can be used as a modifier / stabilizer (fiber resin processing, stabilizer for polyvinyl chloride, additive to synthetic rubber, etc.) and the like. Among these, it is useful for coating agents, paints, adhesives, and optical modeling resin applications.

The present invention will be specifically described below.
The characteristics of the index and the modified resin composition used in the present invention are quantified by the following method.
<Calculation of component index α>
The component index α is a value obtained by the following procedure from the ¹ H-NMR measurement result and ²⁹ Si-NMR measurement result of polyorganosiloxane.
<1> Measurement of ¹ H-NMR was performed according to the following procedure.
In a sample bottle, 10 mg of polyorganosiloxane is weighed, and 970 mg of chloroform-d (Wako Pure Chemical Industries, Ltd.) is added and dissolved. The solution is transferred to an NMR tube having a diameter of 5 mmφ, and ¹ H-NMR measurement is performed 600 times (apparatus: α-400 manufactured by JASCO Corporation).
¹ H-NMR was measured.

<2> ²⁹ Si-NMR was measured according to the following procedure.
In a dried sample bottle, 0.15 g of polyorganosiloxane is dissolved in 1 g of dehydrated chloroform. A solution obtained by adding 0.015 g of dried Cr (acac) ₃ to the solution and dissolving is used as an NMR measurement solution. The sample solution is transferred to a dried NMR measurement sample tube, and ²⁹ Si-NMR measurement under proton complete decoupling conditions is performed with 6,000 integrations (apparatus: α-400 manufactured by JASCO Corporation).
Based on the spectrum obtained by < ²⁹ > ²⁹ Si-NMR measurement, the following D0 structure, D1 structure, and D structure consisting of D2 structure, T0 structure, T1 structure, T2 structure, T3 structure Based on the integrated value of each peak corresponding to the Q structure composed of the T structure, Q0 structure, Q1 structure, Q2 structure, Q3 structure, and Q4 structure, the content ratio of each component is calculated.

Next, the content ratio of the functional group bonded to Si is calculated from the <1> ¹ H-NMR measurement result, and the D structure, the T0 structure, the T1 structure, and the T2 composed of the D0 structure, the D1 structure, and the D2 structure. The abundance ratio of each structure is calculated according to the content ratio of functional groups bonded to Si with respect to the structure, T structure composed of T3 structure, Q0 structure, Q1 structure, Q2 structure, Q3 structure, and Q4 structure.
The component index α is calculated by the following general formula (2) based on the abundance ratio of each structure obtained above.
Component index α = (αa) / (αb) (2)

Here, αa and αb represent the following.
αa: In the average composition formula (1) with respect to the total amount of Si in the polyorganosiloxane represented by the average composition formula (1), R ¹ is a phenyl group having a fluorine atom as a substituent in one molecule as a substituent. Content (mol%) of the siloxane unit possessed as [(A) of the present invention],
αb: an organic group containing a carbon-carbon double bond in one molecule as R ¹ in the average composition formula (1) with respect to the total amount of Si in the polyorganosiloxane represented by the average composition formula (1), Content (mol%) of a siloxane unit having at least one curable functional group selected from the group consisting of an epoxy group, an episulfide group, a thiocarbonate group, a dithiocarbonate group and a trithiocarbonate group as a substituent [of the present invention ( B)].

Here, D0, D1, D2, T0, T1, T2, T3, Q0, Q1, Q2, Q3, and Q4 each represent the following.
D0: Total integrated value of signals derived from the D0 structure represented by the following formula (16) in the polyorganosiloxane of the average composition formula (1).
D1: Total integrated value of signals derived from the D1 structure represented by the following formula (17) in the polyorganosiloxane of the average composition formula (1).
D2: Total integrated value of signals derived from the D1 structure represented by the following formula (17) in the polyorganosiloxane of the average composition formula (1).
T0: Total integrated value of signals derived from the T0 structure represented by the following formula (18) in the polyorganosiloxane of the average composition formula (1).
T1: Total integrated value of signals derived from the T1 structure represented by the following formula (19) in the polyorganosiloxane of the average composition formula (1).
T2: Total integrated value of signals derived from the T2 structure represented by the following formula (19) in the polyorganosiloxane of the average composition formula (1).
T3: Total integrated value of signals derived from the T3 structure represented by the following formula (19) in the polyorganosiloxane of the average composition formula (1).
Q0: Total integrated value of signals derived from the Q0 structure represented by the following formula (20) in the polyorganosiloxane of the average composition formula (1).
Q1: Total integrated value of signals derived from the Q1 structure represented by the following formula (21) in the polyorganosiloxane of the average composition formula (1).
Q2: Total integrated value of signals derived from the Q2 structure represented by the following formula (21) in the polyorganosiloxane of the average composition formula (1).
Q3: Total integrated value of signals derived from the Q3 structure represented by the following formula (21) in the polyorganosiloxane of the average composition formula (1).
Q4: Total integrated value of signals derived from the Q4 structure represented by the following formula (21) in the polyorganosiloxane of the average composition formula (1).

In the formula (16), R ⁶ is an arbitrary organic group, Y is selected from a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, an unsubstituted or substituted structure group consisting of a chain, a branched, and a ring. It is a hydrolyzable group selected from the group consisting of monovalent alkoxy groups having an aliphatic hydrocarbon unit having a structure of at least a species and having 1 to 20 carbon atoms.

In the formula (17), R ⁶ is an arbitrary organic group, Y is selected from a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, an unsubstituted or substituted structure group consisting of a chain, a branch, and a ring. It is a hydrolyzable group selected from the group consisting of monovalent alkoxy groups having an aliphatic hydrocarbon unit having a structure of at least a species and having 1 to 20 carbon atoms.

In the formula (18), R ⁶ is an arbitrary organic group, Y is selected from a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, an unsubstituted or substituted structure group consisting of a chain, a branched, and a ring. It is a hydrolyzable group selected from the group consisting of monovalent alkoxy groups having an aliphatic hydrocarbon unit having a structure of at least a species and having 1 to 20 carbon atoms.

In the formula (19), R ⁶ is an arbitrary organic group, Y is selected from a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, an unsubstituted or substituted structure group consisting of a chain, a branched, and a ring. It is a hydrolyzable group selected from the group consisting of monovalent alkoxy groups having an aliphatic hydrocarbon unit having a structure of at least a species and having 1 to 20 carbon atoms.

In the formula (20), R ⁶ is an arbitrary organic group, Y is selected from a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, an unsubstituted or substituted structure group consisting of a chain, a branch, and a ring. It is a hydrolyzable group selected from the group consisting of monovalent alkoxy groups having an aliphatic hydrocarbon unit having a structure of at least a species and having 1 to 20 carbon atoms.

In the formula (21), R ⁶ is an arbitrary organic group, Y is selected from the group consisting of a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, an unsubstituted or substituted structure group consisting of a chain, a branch, and a ring. It is a hydrolyzable group selected from the group consisting of monovalent alkoxy groups having an aliphatic hydrocarbon unit having a structure of at least a species and having 1 to 20 carbon atoms.

<Calculation of component index β>
The component index β was determined by the following procedure using the ²⁹ Si-NMR measurement result of polyorganosiloxane.
In a dried sample bottle, 0.15 g of polyorganosiloxane is dissolved in 1 g of dehydrated chloroform. A solution obtained by adding 0.015 g of dried Cr (acac) ₃ to the solution and dissolving is used as an NMR measurement solution. The sample solution is transferred to a dried NMR measurement sample tube, and ²⁹ Si-NMR measurement under proton complete decoupling conditions is performed with 6,000 integrations (apparatus: α-400 manufactured by JASCO Corporation).

Based on the integral value of the obtained spectrum, the peak area value derived from the D structure, the peak area value derived from the Q structure, and the peak area value derived from the T structure with respect to the peak area value of all Si units constituting the polyorganosiloxane. The content (mol%) of the structure corresponding to each was calculated from the fraction, and calculated according to the following formula (3) using the above numerical values.
Component index β = {(βD) / (βQ + βT)} (3)
Here, βD, βQ, and βT represent the following.
βD: Content of D structural unit (mol%) with respect to the total amount of Si in the polyorganosiloxane represented by the average composition formula (1),
βQ: content of Q structural unit (mol%) with respect to the total amount of Si in the polyorganosiloxane represented by the average composition formula (1),
βT: Content of T structural unit (mol%) with respect to the total amount of Si in the polyorganosiloxane represented by the average composition formula (1).
However, 0 ≦ {βQ / (βQ + βT + βD)} ≦ 0.1.

<Calculation of mixing index γ>
The mixing index γ is calculated by the following general formula (5).
Mixing index γ = (γa) / (γb) (5)
Here, γa and γb represent the following.
γa: content (mol%) of the component (a) with respect to all reactive organosilicon compounds,
γb: Content (mol%) of the component (b) with respect to all reactive organosilicon compounds.

<Calculation of mixing index δ>
The mixing index δ is calculated by the following general formula (6).
Mixing index δ = {(δD) / (δQ + δT)} (6)
Here, δD, δQ, and δT represent the following.
δD: content (mol%) of a reactive organosilicon compound having a hydrolyzable group where n = 2 in the reactive organosilicon compound having a hydrolyzable group represented by the general formula (4),
δQ: content (mol%) of a reactive organosilicon compound having a hydrolyzable group where n = 0 in the reactive organosilicon compound having a hydrolyzable group represented by the general formula (4),
δT: content (mol%) of the reactive organosilicon compound having a hydrolyzable group where n = 1 in the reactive organosilicon compound having a hydrolyzable group represented by the general formula (4).
However, it is a value satisfying 0 ≦ {δQ / (δQ + δT + δD)} ≦ 0.1.

<Calculation of mixing index ε>
The mixing index ε is calculated by the following general formula (22).
Mixing index ε = (εw) / (εs) (22)
Here, εw and εs represent the following.
εw: amount of water added (in mol),
εs: X amount (mol number) in the general formula (4).

<Calculation method of condensation rate of intermediate condensation rate>
Condensation ratio is a value from ²⁹ Si-NMR measurement results of polyorganosiloxanes obtained by the following procedure.
0.15 g of polyorganosiloxane is dissolved in 1 g of deuterated chloroform. A solution obtained by adding 0.015 g of Cr (acac) ₃ to the solution and dissolving is used as an NMR measurement solution. Using this NMR measurement solution, ²⁹ Si-NMR measurement under proton complete decoupling conditions is performed with 6,000 integrations (apparatus: α-400 manufactured by JASCO Corporation).
Based on the obtained spectrum, as in the case of the component index α, the D0 structure, the D1 structure, and the D structure composed of the D2 structure, the T structure composed of the following T0 structure, T1 structure, T2 structure, and T3 structure, Based on the integrated value of each peak corresponding to the Q structure consisting of the Q0 structure, the Q1 structure, the Q2 structure, the Q3 structure, and the Q4 structure, the calculation is performed according to the following formula (15).
Condensation rate (%) = (D1 × 1 + D2 × 2 + T1 × 1 + T2 × 2 + T3 × 3 + Q1 × 1 + Q2 × 2 + Q3 × 3 + Q4 × 4) / {(D0 + D1 + D2) × 2 + (T0 + T1 + T2 + T3) × 3 + (Q0 + Q4 × 4 × 4 × 4) (15)

<Calculation of condensation rate of polyorganosiloxane>
The condensation rate of the polyorganosiloxane was also calculated from the ²⁹ Si-NMR measurement result of the sample collected after the polycondensation step by the same method as the method for calculating the condensation rate of the intermediate.
<Quantitative method of curable functional group contained in polyorganosiloxane-epoxy equivalent (WPE)>
When the curable functional group contained in the polyorganosiloxane is an epoxy group, the epoxy equivalent contained in the polyorganosiloxane is calculated by the following method, and the amount of the epoxy group contained in 100 g of the polyorganosiloxane. Converted into
The epoxy equivalent is the mass (g) of the modified silicone containing 1 equivalent of an epoxy unit, and was measured according to JIS K-7236.

<Method 2 for quantifying curable functional group contained in polyorganosiloxane>
When the curable functional group contained in the polyorganosiloxane was a functional group other than an epoxy group, it was quantified by a method such as ¹ H-NMR measurement in which the following internal standard substance coexisted.
The ¹ H-NMR measurement was performed according to the following procedure.
In a sample bottle, 10 mg of polyorganosiloxane and 20 mg of an internal standard substance (1,1,2,2-tetrabromoethane: a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) are weighed, and 970 mg of chloroform-d (Wako Pure Chemical Industries) is added to prepare for dissolution. . The solution is transferred to an NMR tube having a diameter of 5 mmφ, and ¹ H-NMR measurement is performed 600 times (apparatus: α-400 manufactured by JASCO Corporation).

From the above measurement results, the content (mol) of the curable functional group per unit weight of the polyorganosiloxane was calculated by the following procedure.
<1> The area value of the peak derived from the curable functional group is calculated from the ¹ H-NMR chart.
<2> From the ¹ H-NMR chart, the area value of the peak derived from the internal standard substance is calculated.
<3> The number of moles of protons per formula amount of 1,1,2,2-tetrabromoethane as an internal standard substance is 2 moles, and the weight of 1,1,2,2-tetrabromoethane added is used. Then, the number of protons (mol) per unit peak area of 1,1,2,2-tetrabromoethane is calculated.
<4> From the relationship between the peak area value derived from the curable functional group contained in the polyorganosiloxane and the number of protons (mol) per unit peak area obtained in the above <3>, ¹ H-NMR The content (mol) of the curable functional group contained in the polyorganosiloxane used for the measurement of the sample was calculated and converted to the content (mol) of the curable functional group contained in 100 g of the polyorganosiloxane. .

<Calculation of total content of siloxane units having hydrolyzable groups contained in polyorganosiloxane as substituents>
The total content of siloxane units having a hydrolyzable group contained in the polyorganosiloxane as a substituent is a value determined by the following procedure from the ²⁹ Si-NMR measurement result of the polyorganosiloxane.
In a dried sample bottle, 0.15 g of polyorganosiloxane is dissolved in 1 g of dehydrated chloroform. A solution obtained by adding 0.015 g of dried Cr (acac) ₃ to the solution and dissolving is used as an NMR measurement solution. The sample solution is transferred to a dried NMR measurement sample tube, and ²⁹ Si-NMR measurement under proton complete decoupling conditions is performed with 6,000 integrations (apparatus: α-400 manufactured by JASCO Corporation).
Based on the integral value of the obtained spectrum, the content of siloxane units having hydrolyzable groups as substituents for all Si units was calculated according to the following formula.
Total content (mol%) of siloxane units having hydrolyzable groups contained in polyorganosiloxane as substituents = (peak area of siloxane units having hydrolyzable groups as substituents) / (of all Si units) Peak area) x 100

<Storage stability of polyorganosiloxane>
The storage stability of the polyorganosiloxane was evaluated by a storage stability index θ represented by the following general formula (23).
Storage stability index θ = (storage viscosity) / (starting viscosity) (23)
The container containing the polyorganosiloxane immediately after production was sealed and the temperature was adjusted at 25 ° C. for 2 hours, and then the viscosity at 25 ° C. was measured, which was defined as “starting viscosity”. Further, the container containing the polyorganosiloxane was sealed and stored in a constant temperature incubator at 25 ° C. for 2 weeks. After storage for a predetermined period, the viscosity at 25 ° C. was measured, and this was designated as “storage viscosity”.
When the polyorganosiloxane has fluidity (viscosity is 1000 Pa · s or less) and the storage stability index θ is 4 or less, the storage stability index is judged to be ○, and the index θ is When exceeding 4, it was judged that there was no storage stability, and it was set as x.
The viscosity was measured by the following measurement method.
A 0.4 ml polyorganosiloxane sample was placed in a rotary E-type viscometer (manufactured by Toki Sangyo Co., Ltd., “TV-22”, rotor: 3 ° × R14), and the polyorganosiloxane was measured at a temperature of 25 ° C. did.

<Cold thermal shock test of cured product>
In the center of “Amodel A-4122NL WH 905” (15 mm × 15 mm × thickness 2 mm flat plate) manufactured by Solvay Advanced Polymers, a hollow with a diameter of 10 mm × depth of 1.2 mm was created, and then 5 mm × 5 mm × 0.2 mm. The silicon chip is placed, and the resin composition is cast and heated to obtain 10 cold shock samples for each test sample. The obtained sample was kept at −40 ° C. for 15 minutes in a thermal cycle tester (TSE-11-A manufactured by Espec Corp.), then heated to 120 ° C. in 3 minutes and then at 120 ° C. for 15 minutes. Hold and then subjected to a cycle test where the temperature is lowered to -40 ° C in 3 minutes.
During this test, the sample is taken out after 50 cycles and observed for any abnormalities such as peeling or cracking in the sample for thermal shock. Samples in which no abnormalities were confirmed were placed in the cooling / heating cycle tester again and evaluated by the same operation as described above, and then evaluated by the same method after 50 heat cycles. By repeating these operations, the evaluation was interrupted when abnormality was observed in 2 samples out of 10 samples, and “Cold thermal shock cycle number = (Number of interrupted heat cycles) − (50 times)” Asked. The case where the number of cycles of this thermal shock resistance test is less than 50 is D, the case of 50 or more and less than 150 is C, the case of 150 or more and less than 300 is B, and the case of 300 or more is A. .

<Light resistance test of cured product under heating conditions>
It is set so that UV light can be irradiated to a cured product having a thickness of 3 mm in a constant temperature dryer kept constant at 85 ° C. from a UV irradiation device (USHIO Corporation: SP-7) via an optical fiber. Using a 365 nm band pass filter, the light of 330-410 nm is irradiated so that it may become ² W / cm <2>.
Samples before UV irradiation and after UV irradiation under the above conditions were measured with a spectrocolorimeter (Nippon Denshoku Industries Co., Ltd., “SD5000”: integrating sphere opening diameter 10 mm), and the difference in yellowness (Δ YI) was calculated to evaluate the light resistance of the cured product under heating conditions.
When ΔYI is 6 or less, A is 10 or less, B is 10 or more and 15 or less, C is 15 or more and 20 or less is D, and 20 or more is E. .

<Heat-resistant discoloration test of cured product>
Using a cured product having a thickness of 3 mm, the light transmittance at 400 nm in the thickness direction is measured with JASCO V-550 manufactured by JASCO Corporation. Next, this hardened | cured material is put into the form made from SUS316, and after subjecting to heating conditions at 120 ° C. for 100 hours under air, it is allowed to cool at room temperature. Thereafter, the light transmittance at 400 nm in the thickness direction of the sample is measured again, and the value of the light transmittance at 400 nm in the sample after the heat treatment is calculated with respect to the light transmittance at 400 nm in the sample before the heat treatment. The ratio of the light transmittance of the sample after the heat treatment to the light transmittance of the sample before the heat treatment obtained above is calculated as the light transmittance retention.
The light transmission retention was 93% or more as A, 90% or more as B, 88% or more and less than 90% as C, 85% or more and less than 88% as D, and less than 85% as E.

[Example 1]
<Production 1a of polyorganosiloxane>
A 1 liter reactor with a reflux condenser, thermometer and stirrer is replaced with dry nitrogen. Under dry nitrogen conditions, 280 g of 3-glycidoxypropyltrimethoxysilane (hereinafter abbreviated as GPTMS) and 4-fluorophenyl-trimethoxysilane (hereinafter referred to as 4F-) were added to the apparatus under dry nitrogen. After charging 25.5 g of PTMS), 60 g of dimethyldimethoxysilane (hereinafter abbreviated as DMDMS), and 180 g of tetrahydrofuran (hereinafter abbreviated as THF), the mixture is stirred at room temperature. Subsequently, 100 g of water and 1.05 g of dibutyltin dilaurate (hereinafter abbreviated as DBTDL) were added, and the reactor was sealed with nitrogen and immersed in an oil bath at 80 ° C. with stirring. The reaction was carried out for 15 hours in a reflux state without distilling the solvent out of the reaction system (hydrolysis step). After completion of the reaction, the mixture was cooled to room temperature, and a sample solution (intermediate) was collected.

The solution after completion of the hydrolysis step was gradually reduced in pressure and heated using an evaporator and distilled off for 1 hour under conditions of 400 Pa and 50 ° C., and further reduced in pressure and heated to 80 ° C. and 1 Pa. The polycondensation reaction was performed by treating for 5 hours under the conditions. After completion of the reaction, the reaction mixture was cooled to room temperature to obtain polyorganosiloxane (1a).
The total content of siloxane units having hydrolyzable groups contained in this polyorganosiloxane was 0%, and the viscosity was 200 Pa · s or less.
Each index α, β, γ, δ, ε, condensation rate of intermediate (%), condensation rate of polyorganosiloxane (%), total content of siloxane having hydrolyzable groups contained in polyorganosiloxane Table 1 shows (mol%), the content (mol / 100 g) of an epoxy group that is a curable functional group, and determination of storage stability.

<Manufacture of cured product and characteristic evaluation 1a>
100 parts by mass of the polyorganosiloxane (1a) obtained above, as a curing agent (trade name) “Rikacid MH-700G” manufactured by Shin Nippon Chemical Co., Ltd. [70 of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride Mixture of 30% by mass] (hereinafter abbreviated as MH-700G) 51.3 parts by mass, “U-CAT 18X” (hereinafter referred to as U-CAT 18X) manufactured by San Apro Co., Ltd. as a curing accelerator Abbreviated.) 0.3 parts by mass were mixed under nitrogen, stirred until the whole became uniform, and then defoamed to obtain a curable composition. The curable composition obtained above was poured into a molding jig sandwiched between two stainless steel plates coated with a 3 mm thick U-shaped silicon rubber and a release agent under nitrogen, and the temperature was 1 at 120 ° C. Curing reaction was performed for 2 hours at 150 ° C. for a further time to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 2]
<Production 2a of polyorganosiloxane>
275 g of GPTMS was used, 27.5 g of 2,4-difluorophenyl-trimethoxysilane (hereinafter abbreviated as 2,4DF-PTMS) was used instead of 4F-PTMS, and 225 g of THF was used. A polyorganosiloxane (2a) was produced in the same manner as in Example 1 except that 135 g of water and 1.1 g of DBTDL were used.
The total content of siloxane units having hydrolyzable groups contained in this polyorganosiloxane was 0%, and the viscosity was 200 Pa · s or less.
Each index α, β, γ, δ, ε, condensation rate of intermediate (%), condensation rate of polyorganosiloxane (%), total content of siloxane having hydrolyzable groups contained in polyorganosiloxane Table 1 shows (mol%), the content (mol / 100 g) of an epoxy group that is a curable functional group, and determination of storage stability.

<Manufacture of cured product and characteristic evaluation 2a>
Except that 100 parts by mass of the polyorganosiloxane (2a) obtained above and 50.8 parts by mass of MH-700G were used, the same as Example 1 <Manufacture of cured product and property evaluation 1a> A curing reaction was performed to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 3]
<Production 3a of polyorganosiloxane>
Polyorganosiloxane (3a) was prepared in the same manner as in Example 1 except that 20 g of GPTMS, 330 g of 4F-PTMS, 10 g of DMDMS, and 1.1 g of DBTDL were used. Manufactured.
The total content of siloxane units having hydrolyzable groups contained in this polyorganosiloxane was 0%, and the viscosity was 200 Pa · s or less.
Each index α, β, γ, δ, ε, condensation rate of intermediate (%), condensation rate of polyorganosiloxane (%), total content of siloxane having hydrolyzable groups contained in polyorganosiloxane Table 1 shows (mol%), the content (mol / 100 g) of an epoxy group that is a curable functional group, and determination of storage stability.

<Manufacture of cured product and characteristic evaluation 3a>
Using 100 parts by mass of the polyorganosiloxane (3a) obtained above, using 3.7 parts by mass of MH-700G, curing reaction conditions at 100 ° C. for 1 hour, and further at 110 ° C. for 5 hours. Except for this, a curing reaction was carried out in the same manner as in Example 1 <Manufacture of cured product and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 4]
<Production 4a of polyorganosiloxane>
17 g of GPTMS was used, 327 g of 2,4,6-trifluorophenyl-trimethoxysilane (hereinafter abbreviated as 2,4,6TF-PTMS) was used instead of 4F-PTMS, and 10 g of DMDMS was used. A polyorganosiloxane (4a) was produced in the same manner as in Example 1 except that 80 g of water was used.
The total content of siloxane units having hydrolyzable groups contained in this polyorganosiloxane was 0%, and the viscosity was 200 Pa · s or less.
Each index α, β, γ, δ, ε, condensation rate of intermediate (%), condensation rate of polyorganosiloxane (%), total content of siloxane having hydrolyzable groups contained in polyorganosiloxane Table 1 shows (mol%), the content (mol / 100 g) of an epoxy group that is a curable functional group, and determination of storage stability.

<Manufacture of cured product and characteristic evaluation 4a>
Using 100 parts by mass of the polyorganosiloxane (4a) obtained above, using 3.3 parts by mass of MH-700G, and curing reaction conditions at 100 ° C. for 1 hour and further at 110 ° C. for 5 hours. Except for this, a curing reaction was carried out in the same manner as in Example 1 <Manufacture of cured product and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Comparative Example 1]
<Production 1b of polyorganosiloxane>
Instead of 4F-PTMS, 65.8 g of phenyltrimethylsilane, 30 g of DMDMS, 190 g of THF, 1.1 g of DBTDL, 75 hours of reaction in the hydrolysis step were 75. A modified resin composition (1b) was produced in the same manner as in Example 1 except that the immersion was carried out in an oil bath at 0 ° C.
The total content of siloxane units having hydrolyzable groups contained in this polyorganosiloxane was 0%, and the viscosity was 200 Pa · s or less.
Each index α, β, γ, δ, ε, condensation rate of intermediate (%), condensation rate of polyorganosiloxane (%), total content of siloxane having hydrolyzable groups contained in polyorganosiloxane Table 1 shows (mol%), the content (mol / 100 g) of an epoxy group that is a curable functional group, and determination of storage stability.

<Manufacture of cured product and characteristic evaluation 1b>
Except that 100 parts by mass of the polyorganosiloxane (1b) obtained above was used and 49.1 parts by mass of MH-700G were used, the same as Example 1 <Manufacture of cured product and property evaluation 1a> A curing reaction was performed to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Comparative Example 2]
<Production 2b of polyorganosiloxane>
Except for using 22 g of GPTMS, 422.8 g of 4F-PTMS, 24 g of DMDMS, 240 g of THF, 120 g of water, and 1.4 g of DBTDL. A modified resin composition (2b) was produced in the same manner as in Example 1.
The total content of siloxane units having hydrolyzable groups contained in this polyorganosiloxane was 0%, and the viscosity was 200 Pa · s or less.
Each index α, β, γ, δ, ε, condensation rate of intermediate (%), condensation rate of polyorganosiloxane (%), total content of siloxane having hydrolyzable groups contained in polyorganosiloxane Table 1 shows (mol%), the content (mol / 100 g) of an epoxy group that is a curable functional group, and determination of storage stability.

<Manufacture of cured product and characteristic evaluation 2b>
Using 100 parts by mass of the polyorganosiloxane (2b) obtained above, 3.1 parts by mass of MH-700G, curing reaction conditions at 100 ° C. for 1 hour, and further at 110 ° C. for 5 hours. Except for this, a curing reaction was carried out in the same manner as in Example 1 <Manufacture of cured product and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 5]
<Production 5a of polyorganosiloxane>
Except for using 283 g of GPTMS, using 70 g of 2,4DF-PTMS instead of 4F-PTMS, using 30 g of DMDMS, using 190 g of THF, and using 1.1 g of DBTDL. In the same manner as in Example 1, polyorganosiloxane (5a) was produced.
The total content of siloxane units having hydrolyzable groups contained in this polyorganosiloxane was 0%, and the viscosity was 200 Pa · s or less.
Each index α, β, γ, δ, ε, condensation rate of intermediate (%), condensation rate of polyorganosiloxane (%), total content of siloxane having hydrolyzable groups contained in polyorganosiloxane Table 1 shows (mol%), the content (mol / 100 g) of an epoxy group that is a curable functional group, and determination of storage stability.

<Manufacture of cured product and characteristic evaluation 5a>
Except that 100 parts by mass of the polyorganosiloxane (5a) obtained above and 49.5 parts by mass of MH-700G were used, the same as Example 1 <Manufacture of cured product and property evaluation 1a> A curing reaction was performed to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 6]
<Production 6a of polyorganosiloxane>
Example 1 except that 51.1 g of GPTMS was used, 228 g of 2,4DF-PTMS was used instead of 4F-PTMS, 70 g of DMDMS was used, and 1.0 g of DBTDL was used. In this way, polyorganosiloxane (6a) was produced.
The total content of siloxane units having hydrolyzable groups contained in this polyorganosiloxane was 0%, and the viscosity was 200 Pa · s or less.
Each index α, β, γ, δ, ε, condensation rate of intermediate (%), condensation rate of polyorganosiloxane (%), total content of siloxane having hydrolyzable groups contained in polyorganosiloxane Table 1 shows (mol%), the content (mol / 100 g) of an epoxy group that is a curable functional group, and determination of storage stability.

<Manufacture and characteristic evaluation 6a of cured product>
Using 100 parts by mass of the polyorganosiloxane (6a) obtained above, using 9.8 parts by mass of MH-700G, curing reaction conditions at 100 ° C. for 1 hour, and further at 110 ° C. for 5 hours. Except for this, a curing reaction was carried out in the same manner as in Example 1 <Manufacture of cured product and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 7]
<Production 7a of polyorganosiloxane>
For 51.1 g of GPTMS, 228 g of 2,4DF-PTMS instead of 4F-PTMS, 35 g of di (2,4-diphenyl) dimethoxysilane instead of DMDMS, 140 g of THF The polyorganosiloxane (7a) was produced in the same manner as in Example 1 except that 65 g of water and 0.85 g of DBTDL were used.
The total content of siloxane units having hydrolyzable groups contained in this polyorganosiloxane was 0%, and the viscosity was 200 Pa · s or less.
Each index α, β, γ, δ, ε, condensation rate of intermediate (%), condensation rate of polyorganosiloxane (%), total content of siloxane having hydrolyzable groups contained in polyorganosiloxane Table 1 shows (mol%), the content (mol / 100 g) of an epoxy group that is a curable functional group, and determination of storage stability.

<Manufacture of cured product and characteristic evaluation 7a>
100 parts by mass of the polyorganosiloxane (7a) obtained above, 12.3 parts by mass of MH-700G, curing reaction conditions at 100 ° C. for 1 hour, and further at 110 ° C. for 5 hours Except for this, a curing reaction was carried out in the same manner as in Example 1 <Manufacture of cured product and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 8]
<Production 8a of polyorganosiloxane>
274 g of GPTMS was used, 95 g of 2,4DF-PTMS was used instead of 4F-PTMS, 40 g of DDMMS was used, 210 g of THF was used, 105 g of water was used, and 1.2 g of DBTDL was used. A polyorganosiloxane (8a) was produced in the same manner as in Example 1 except that it was used.
The total content of siloxane units having hydrolyzable groups contained in this polyorganosiloxane was 0%, and the viscosity was 200 Pa · s or less.
Each index α, β, γ, δ, ε, condensation rate of intermediate (%), condensation rate of polyorganosiloxane (%), total content of siloxane having hydrolyzable groups contained in polyorganosiloxane Table 1 shows (mol%), the content (mol / 100 g) of an epoxy group that is a curable functional group, and determination of storage stability.

<Manufacture and characteristic evaluation 8a of cured product>
Except that 100 parts by mass of the polyorganosiloxane (8a) obtained above and 64.8 parts by mass of MH-700G were used, the same as Example 1 <Manufacture of cured product and property evaluation 1a> A curing reaction was performed to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 9]
<Production 9a of polyorganosiloxane>
120 g of GPTMS, 214 g of 2,4DF-PTMS instead of 4F-PTMS, 70 g of DMDMS, 200 g of THF, 110 g of water, 1.2 g of DBTDL A polyorganosiloxane (9a) was produced in the same manner as in Example 1 except that it was used.
The total content of siloxane units having hydrolyzable groups contained in this polyorganosiloxane was 0%, and the viscosity was 200 Pa · s or less.
Each index α, β, γ, δ, ε, condensation rate of intermediate (%), condensation rate of polyorganosiloxane (%), total content of siloxane having hydrolyzable groups contained in polyorganosiloxane Table 1 shows (mol%), the content (mol / 100 g) of an epoxy group that is a curable functional group, and determination of storage stability.

<Manufacture and characteristic evaluation 9a of cured product>
90 parts by mass of the polyorganosiloxane (9a) obtained above, trade name “Celoxide 2021P” manufactured by Daicel Chemical Industries, Ltd. [epoxy equivalent (WPE): 131 g / eq, viscosity (25 ° C.): 227 mPa · s] 10 parts by mass were mixed under nitrogen and stirred until the whole became uniform to obtain a modified resin composition (9a).
100 parts by mass of the modified resin composition (9a) obtained above, 15.8 parts by mass of MH-700G were used, and the curing reaction conditions were 1 hour at 120 ° C. and 5 hours at 140 ° C. Except for this, a curing reaction was carried out in the same manner as in Example 1 <Manufacture of cured product and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 10]
<Production 10a of polyorganosiloxane>
Except for using 164 g of GPTMS, using 180 g of 4F-PTMS, using 30 g of DMDMS, using 190 g of THF, and using 1.1 g of DBTDL, the same method as in Example 1, Polyorganosiloxane (10a) was produced.
The total content of siloxane units having hydrolyzable groups contained in this polyorganosiloxane was 0%, and the viscosity was 200 Pa · s or less.
Each index α, β, γ, δ, ε, condensation rate of intermediate (%), condensation rate of polyorganosiloxane (%), total content of siloxane having hydrolyzable groups contained in polyorganosiloxane Table 1 shows (mol%), the content (mol / 100 g) of an epoxy group that is a curable functional group, and determination of storage stability.

<Manufacture of cured product and characteristic evaluation 10a>
Using 100 parts by mass of the polyorganosiloxane (10a) obtained above, 29.3 parts by mass of MH-700G, curing reaction conditions at 110 ° C. for 1 hour, and further at 130 ° C. for 5 hours. Except for this, a curing reaction was carried out in the same manner as in Example 1 <Manufacture of cured product and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 11]
<Production 11a of polyorganosiloxane>
146 g of GPTMS, 187 g of 2,4,6TF-PTMS instead of 4F-PTMS, 105 g of DMDMS, 220 g of THF, 120 g of water, 1 DBTDL A polyorganosiloxane (11a) was produced in the same manner as in Example 1 except that .3 g was used.
The total content of siloxane units having hydrolyzable groups contained in this polyorganosiloxane was 0%, and the viscosity was 200 Pa · s or less.
Each index α, β, γ, δ, ε, condensation rate of intermediate (%), condensation rate of polyorganosiloxane (%), total content of siloxane having hydrolyzable groups contained in polyorganosiloxane Table 1 shows (mol%), the content (mol / 100 g) of an epoxy group that is a curable functional group, and determination of storage stability.

<Manufacture of cured product and characteristic evaluation 11a>
Using 100 parts by mass of the polyorganosiloxane (11a) obtained above, 22.1 parts by mass of MH-700G, curing reaction conditions at 110 ° C. for 1 hour, and further at 130 ° C. for 5 hours. Except for this, a curing reaction was carried out in the same manner as in Example 1 <Manufacture of cured product and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 12]
<Production 12a of polyorganosiloxane>
127.8 g of GPTMS was used, 187 g of 2,3,4,5,6-pentafluoro-trimethoxysilane was used instead of 4F-PTMS, 50 g of DMDMS was used, and 90 g of water was used Polyorganosiloxane (12a) was produced in the same manner as in Example 1 except that 1.1 g of DBTDL was used.
The total content of siloxane units having hydrolyzable groups contained in this polyorganosiloxane was 0%, and the viscosity was 200 Pa · s or less.
Each index α, β, γ, δ, ε, condensation rate of intermediate (%), condensation rate of polyorganosiloxane (%), total content of siloxane having hydrolyzable groups contained in polyorganosiloxane Table 1 shows (mol%), the content (mol / 100 g) of an epoxy group that is a curable functional group, and determination of storage stability.

<Manufacture of cured product and characteristic evaluation 12a>
Using 100 parts by mass of the polyorganosiloxane (12a) obtained above, 23.8 parts by mass of MH-700G, curing reaction conditions at 110 ° C. for 1 hour, and further at 130 ° C. for 5 hours. Except for this, a curing reaction was carried out in the same manner as in Example 1 <Manufacture of cured product and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 13]
<Production 13a of polyorganosiloxane>
100 g of 3- (trimethoxysilyl) propyl methacrylate was used instead of GPTMS, 215.5 g of 2,4,6TF-PTMS was used instead of 4F-PTMS, 30 g of DMDMS was used, 170 g of THF was used A polyorganosiloxane (13a) was produced in the same manner as in Example 1 except that 90 g of water was used.
The total content of siloxane units having hydrolyzable groups contained in this polyorganosiloxane was 0%, and the viscosity was 200 Pa · s or less.
Each index α, β, γ, δ, ε, condensation rate of intermediate (%), condensation rate of polyorganosiloxane (%), total content of siloxane having hydrolyzable groups contained in polyorganosiloxane Table 1 shows (mol%), the content (mol / 100 g) of an epoxy group that is a curable functional group, and determination of storage stability.

<Manufacture of cured product and characteristic evaluation 13a>
Use of 100 parts by mass of the polyorganosiloxane (12a) obtained above, no use of MH-700G, tert-amylperoxy-2-ethylhexanoate (chemicals) instead of U-CAT 18X Example 1 <Curing, except that 2.5 parts by mass of Trigonox 121-50E, 50 wt% solution manufactured by Akzo Corporation) was used, and the curing reaction conditions were 1 hour at 120 ° C. and 3 hours at 140 ° C. Curing reaction was carried out in the same manner as in the production and property evaluation 1a> to obtain a cured product. Table 1 shows the results of the thermal shock resistance test of the obtained cured product, the light resistance test result under the heating condition of the cured product, and the heat discoloration test result of the cured product.

[Example 14]
To 100 parts by mass of the polyorganosiloxane (2a) obtained in Example 2, 10 parts by mass of “YAG: Ce3 + phosphor” manufactured by Kasei Optonics Co., Ltd. was mixed under nitrogen. After adding 50.8 parts by mass of MH-700G and 0.3 parts by mass of U-CAT 18X to the obtained mixture, the mixture was mixed under nitrogen, stirred until the whole became uniform, then defoamed and cured. Sex composition (14a) was obtained.
The curable composition obtained above was poured into a bullet-shaped mold frame having a diameter of 4 mm, and a lead frame on which a light emitting element having an emission wavelength of 400 nm was fixed was immersed therein, and after degassing in vacuum, 120 A curing reaction was carried out at 1 ° C. for 1 hour and further at 150 ° C. for 2 hours to obtain a light emitting diode. Even when the light-emitting diode (14c) obtained by this operation was energized at room temperature at 20 mA for 200 hours, peeling between the element and the sealing portion and reduction in luminance were not observed.

Ten light-emitting diodes (14c) obtained by the above operation are used as test method 307 (thermal shock test) of “EIAJ ED-4701 / 300 (Semiconductor device environment and durability test method (strength test I)”). Accordingly, the evaluation was performed under the following conditions.
“-10 ° C. (5 minutes) to 100 ° C. (5 minutes)” was taken as one cycle. After 100 cycles of thermal shock, lighting of the light emitting diodes was confirmed.
Further, the ten light-emitting diodes (14c) obtained by the above-described operation are connected to test method 105 (temperature cycle test) of “EIAJ ED-4701 / 100 (Semiconductor device environment and durability test method (life test I)”). ) And evaluated under the following conditions.
“-40 ° C. (30 minutes) to 85 ° C. (5 minutes) to 100 ° C. (30 minutes) to 25 ° C. (5 minutes)” is taken as one cycle, and after 100 temperature cycles are applied, the light-emitting diodes are turned on. As a result, all 10 lights were turned on.

[Example 15]
100 parts by mass of the polyorganosiloxane (5a) obtained in Example 5 and 10 parts by mass of “YAG: Ce3 + phosphor” manufactured by Kasei Optonics Co., Ltd. were mixed under nitrogen. To the obtained mixture, 49.5 parts by mass of MH-700G and 0.3 part by mass of U-CAT 18X were added, mixed under nitrogen, stirred until the whole became uniform, then defoamed and cured. Sex composition (15a) was obtained.
The curable composition obtained above was poured into a bullet-shaped mold frame having a diameter of 4 mm, and a lead frame on which a light emitting element having an emission wavelength of 400 nm was fixed was immersed therein, and after degassing in vacuum, 120 A curing reaction was carried out at 1 ° C. for 1 hour and further at 150 ° C. for 2 hours to obtain a light emitting diode. Even when the light-emitting diode (15c) obtained by this operation was energized at 20 mA for 200 hours at room temperature, neither peeling of the element from the sealing portion nor reduction in luminance was observed.

Ten light-emitting diodes (15c) obtained by the above operation are used as test method 307 (thermal shock test) of “EIAJ ED-4701 / 300 (Semiconductor device environment and durability test method (strength test I)”). Accordingly, the evaluation was performed under the following conditions.
“-10 ° C. (5 minutes) to 100 ° C. (5 minutes)” was taken as one cycle. After 100 cycles of thermal shock, lighting of the light emitting diodes was confirmed.
Further, the ten light-emitting diodes (15c) obtained by the above-described operation are connected to Test Method 105 (Temperature Cycle Test) of “EIAJ ED-4701 / 100 (Semiconductor Device Environment and Durability Test Method (Life Test I)”). ) And evaluated under the following conditions.
“-40 ° C. (30 minutes) to 85 ° C. (5 minutes) to 100 ° C. (30 minutes) to 25 ° C. (5 minutes)” is taken as one cycle, and after 100 temperature cycles are applied, the light-emitting diodes are turned on. As a result, all 10 lights were turned on.

[Example 16]
100 parts by mass of the polyorganosiloxane (7a) obtained in Example 7 and 10 parts by mass of “YAG: Ce3 + phosphor” manufactured by Kasei Optonics Co., Ltd. were mixed under nitrogen. After adding 12.3 parts by mass of MH-700G and 0.3 parts by mass of U-CAT 18X to the obtained mixture, the mixture was mixed under nitrogen, stirred until the whole became uniform, then defoamed and cured. Sex composition (16a) was obtained.
The curable composition obtained above was poured into a bullet-shaped mold frame having a diameter of 4 mm, and a lead frame on which a light emitting element having an emission wavelength of 400 nm was fixed was immersed therein, and after degassing in vacuum, 100 A curing reaction was carried out at 1 ° C. for 1 hour and further at 110 ° C. for 5 hours to obtain a light emitting diode. Even when the light-emitting diode (16c) obtained by this operation was energized at room temperature for 20 hours at 20 mA, peeling between the element and the sealing portion and reduction in luminance were not observed.

Ten light-emitting diodes (16c) obtained by the above operation are used in the test method 307 (thermal shock test) of “EIAJ ED-4701 / 300 (Semiconductor device environment and durability test method (strength test I)”). Accordingly, the evaluation was performed under the following conditions.
“-10 ° C. (5 minutes) to 100 ° C. (5 minutes)” was taken as one cycle. After 100 cycles of thermal shock, lighting of the light emitting diodes was confirmed.
Further, the ten light-emitting diodes (16c) obtained by the above-described operation were subjected to test method 105 (temperature cycle test) of “EIAJ ED-4701 / 100 (Semiconductor device environment and durability test method (life test I)”). ) And evaluated under the following conditions.
“-40 ° C. (30 minutes) to 85 ° C. (5 minutes) to 100 ° C. (30 minutes) to 25 ° C. (5 minutes)” is taken as one cycle, and after 100 temperature cycles are applied, the light-emitting diodes are turned on. As a result, all 10 lights were turned on.

[Example 17]
100 parts by mass of the polyorganosiloxane (8a) obtained in Example 8 and 10 parts by mass of “YAG: Ce3 + phosphor” manufactured by Kasei Optonics Co., Ltd. were mixed under nitrogen. To the obtained mixture, 64.8 parts by mass of MH-700G and 0.3 part by mass of U-CAT 18X were added, mixed under nitrogen, stirred until the whole became uniform, defoamed and cured. Sex composition (17a) was obtained.
The curable composition obtained above was poured into a bullet-shaped mold frame having a diameter of 4 mm, and a lead frame on which a light emitting element having an emission wavelength of 400 nm was fixed was immersed therein, and after degassing in vacuum, 120 A curing reaction was carried out at 1 ° C. for 1 hour and further at 150 ° C. for 2 hours to obtain a light emitting diode. Even when the light-emitting diode (17c) obtained by this operation was energized at room temperature for 20 hours at 20 mA, peeling between the element and the sealing portion and reduction in luminance were not observed.

Ten light-emitting diodes (17c) obtained by the above operation are used as test method 307 (thermal shock test) of “EIAJ ED-4701 / 300 (Semiconductor device environment and durability test method (strength test I)”). Accordingly, the evaluation was performed under the following conditions.
“-10 ° C. (5 minutes) to 100 ° C. (5 minutes)” was taken as one cycle. After 100 cycles of thermal shock, lighting of the light emitting diodes was confirmed.
Further, the ten light-emitting diodes (17c) obtained by the above-described operation were subjected to test method 105 (temperature cycle test) of “EIAJ ED-4701 / 100 (Semiconductor device environment and durability test method (life test I)”). ) And evaluated under the following conditions.
“-40 ° C. (30 minutes) to 85 ° C. (5 minutes) to 100 ° C. (30 minutes) to 25 ° C. (5 minutes)” is taken as one cycle, and after 100 temperature cycles are applied, the light-emitting diodes are turned on. As a result, all 10 lights were turned on.

[Example 18]
100 parts by mass of the polyorganosiloxane (11a) obtained in Example 11 and 10 parts by mass of “YAG: Ce3 + phosphor” manufactured by Kasei Optonics Co., Ltd. were mixed under nitrogen. After adding 22.1 parts by mass of MH-700G and 0.3 parts by mass of U-CAT 18X to the obtained mixture, the mixture was mixed under nitrogen, stirred until the whole became uniform, then defoamed and cured. Sex composition (18a) was obtained.
The curable composition obtained above was poured into a bullet-shaped mold form having a diameter of 4 mm, and a lead frame on which a light emitting element having an emission wavelength of 400 nm was fixed was immersed therein, and after degassing in a vacuum, 110 A curing reaction was carried out at 1 ° C. for 1 hour and further at 130 ° C. for 5 hours to obtain a light emitting diode. Even when the light-emitting diode (18c) obtained by this operation was energized at 20 mA at room temperature for 200 hours, peeling between the element and the sealing portion and a decrease in luminance were not observed.

Ten light-emitting diodes (18c) obtained by the above operation are used as test method 307 (thermal shock test) of “EIAJ ED-4701 / 300 (Semiconductor device environment and durability test method (strength test I)”). Accordingly, the evaluation was performed under the following conditions.
“-10 ° C. (5 minutes) to 100 ° C. (5 minutes)” was taken as one cycle. After 100 cycles of thermal shock, lighting of the light emitting diodes was confirmed.
Further, the ten light-emitting diodes (18c) obtained by the above-described operation were subjected to test method 105 (temperature cycle test) of “EIAJ ED-4701 / 100 (Semiconductor device environment and durability test method (life test I)”). ) And evaluated under the following conditions.
“-40 ° C. (30 minutes) to 85 ° C. (5 minutes) to 100 ° C. (30 minutes) to 25 ° C. (5 minutes)” is taken as one cycle, and after 100 temperature cycles are applied, the light-emitting diodes are turned on. As a result, all 10 lights were turned on.

[Example 19]
100 parts by mass of the polyorganosiloxane (13a) obtained in Example 13 and 10 parts by mass of “YAG: Ce3 + phosphor” manufactured by Kasei Optonics Co., Ltd. were mixed under nitrogen. After adding 2.5 parts by mass of tert-amylperoxy-2-ethylhexanoate (Kagoya Akzo Trigonox 121-50E, 50 wt% solution) to the obtained mixture, the mixture was mixed under nitrogen, After stirring until the whole became uniform, defoaming was performed to obtain a curable composition (19a).
The curable composition obtained above was poured into a bullet-shaped mold frame having a diameter of 4 mm, and a lead frame on which a light emitting element having an emission wavelength of 400 nm was fixed was immersed therein, and after degassing in vacuum, 120 A curing reaction was performed at 1 ° C. for 1 hour and further at 140 ° C. for 3 hours to obtain a light emitting diode. Even if the light-emitting diode (19c) obtained by this operation was energized at 20 mA for 200 hours at room temperature, neither peeling of the element from the sealing portion nor reduction in luminance was observed.

Ten light-emitting diodes (19c) obtained by the above operation are used as test method 307 (thermal shock test) of “EIAJ ED-4701 / 300 (Semiconductor device environment and durability test method (strength test I)”). Accordingly, the evaluation was performed under the following conditions.
“-10 ° C. (5 minutes) to 100 ° C. (5 minutes)” was taken as one cycle. After 100 cycles of thermal shock, lighting of the light emitting diodes was confirmed.
Further, the ten light-emitting diodes (19c) obtained by the above operation were tested using the test method 105 (temperature cycle test) of “EIAJ ED-4701 / 100 (Semiconductor device environment and durability test method (life test I)”). ) And evaluated under the following conditions.
“-40 ° C. (30 minutes) to 85 ° C. (5 minutes) to 100 ° C. (30 minutes) to 25 ° C. (5 minutes)” is taken as one cycle, and after 100 temperature cycles are applied, the light-emitting diodes are turned on. As a result, all 10 lights were turned on.

  A curable polymer that has good transparency and excellent light resistance under heating conditions, heat yellowing resistance, cold shock resistance in thermal cycle, and can form a cured product without tackiness. Organosiloxane, and a curable resin composition, a light-emitting component, and an optical semiconductor device using the same can be provided.

Claims (18)

The polyorganosiloxane represented by the following average composition formula (1), which contains at least the siloxane units of the following (A) and (B), and is represented by the following general formula (2): B) Polyorganosiloxane, wherein the component index α of the siloxane unit is 0.001 or more and 19 or less.
(Wherein R ¹ is each independently a monovalent structure composed of one or more structures selected from the group consisting of hydrogen, halogen atoms, hydroxyl groups, unsubstituted or substituted, chain, branched and cyclic structures. Represents an organic group, and n is a positive number satisfying 1 ≦ n <2.)
(A) A siloxane unit having, as a substituent, at least a phenyl group having a fluorine atom as a substituent as R ¹ in the average composition formula (1).
(B) A group consisting of an organic group, an epoxy group, an episulfide group, a thiocarbonate group, a dithiocarbonate group and a trithiocarbonate group containing a carbon-carbon double bond in one molecule as R ¹ in the average composition formula (1) A siloxane unit having at least one curable functional group selected from as a substituent.
Component index α = (αa) / (αb) (2)
(Here, in the general formula (2), αa is the content (mol%) of the component (A) with respect to the total Si amount in the polyorganosiloxane represented by the average composition formula (1), and αb is the average composition formula. (The content (mol%) of the component (B) with respect to the total amount of Si in the polyorganosiloxane represented by (1) is shown.) 2. The polyorganosiloxane according to claim 1, wherein all of the aromatic hydrocarbon units contained as R ¹ are phenyl groups substituted with fluorine atoms. 3. The polyorganosiloxane according to claim 1, wherein all of the aromatic hydrocarbon units contained as R ¹ are phenyl groups substituted with 2 or more and 3 or less fluorine atoms.   The total content of siloxane units having a hydrolyzable group contained in the polyorganosiloxane as a substituent is 5 mol% or less with respect to the total Si amount. The polyorganosiloxane described in 1.   The curable functional group contained in the polyorganosiloxane is at least one selected from the group consisting of a vinyl group, a methacryl group, an epoxy group, an episulfide group, a dithiocarbonate group, and a trithiocarbonate group. Item 5. The polyorganosiloxane according to any one of Items 1 to 4. The component index β of the D structural unit, the T structural unit, and the Q structural unit constituting the polyorganosiloxane is in the range of 0.01 to 1.4. The polyorganosiloxane according to item 1.
Component index β = {(βD) / (βQ + βT)} (3)
(In the formula (3), βD is the content (mol%) of the D structural unit with respect to the total Si amount in the polyorganosiloxane represented by the average composition formula (1), and βQ is the average composition formula (1). The content (mol%) of the Q structural unit with respect to the total Si amount in the polyorganosiloxane represented by the formula, βT is the content of the T structural unit with respect to the total Si amount in the polyorganosiloxane represented by the average composition formula (1) The amount (mol%) is shown, and 0 ≦ {βQ / (βQ + βT + βD)} ≦ 0.1.)   The polyorganosiloxane according to any one of claims 1 to 6, wherein the content of the curable functional group contained in the polyorganosiloxane is 0.001 mol / 100 g or more and 1 mol / 100 g or less.   The polyorganosiloxane according to any one of claims 1 to 7, wherein the condensation rate is 80% or more.   The polyorganosiloxane according to any one of claims 1 to 8, wherein the viscosity of the polyorganosiloxane at 25 ° C is 1,000 Pa · s or less. Hydrolysis obtained by hydrolyzing a reactive organosilicon compound having a hydrolyzable group represented by the following general formula (4) containing at least the following components (a) and (b) in the presence of water: In producing polyorganosiloxane by polycondensation of the subsequent intermediate, the mixing index γ of the component (a) and the component (b) represented by the following general formula (5) is 0.001 or more and 19 or less. The method for producing a polyorganosiloxane according to claim 1, wherein the range is satisfied.
(Wherein R ¹ is each independently a monovalent consisting of one or more structures selected from the group consisting of hydrogen, halogen atoms, hydroxyl groups, unsubstituted or substituted, chain, branched and cyclic structures. X represents independently a monovalent hydrolyzable group, and q and r satisfy the conditions of q ≧ 0, r> 0, 2 ≦ q + r ≦ 4. Is a positive number.)
(A) In the general formula (4), a reactive organosilicon compound having, as R ¹ , at least a phenyl group having a fluorine atom as a substituent as R ¹ .
(B) In the general formula (4), a group consisting of an organic group containing a carbon-carbon double bond, an epoxy group, an episulfide group, a thiocarbonate group, a dithiocarbonate group and a trithiocarbonate group as R ¹ in one molecule. A reactive organosilicon compound having at least one curable functional group selected from as a substituent.
Mixing index γ = (γa) / (γb) (5)
(In the formula (5), γa is the content (mol%) of the component (a) with respect to all reactive organosilicon compounds, and γb is the content of the component (b) with respect to all reactive organosilicon compounds. Amount (mol%) is indicated.) The mixing index δ of the reactive organosilicon compound having the hydrolyzable group represented by the general formula (6) is in a range of 0.01 or more and 1.4 or less. Production method of polyorganosiloxane;
Mixing index δ = {(δD) / (δQ + δT)} (6)
Here, in formula (6), δD is a reactive organosilicon having a hydrolyzable group where q = 2 in a reactive organosilicon compound having a hydrolyzable group represented by general formula (4) Compound content (mol%), δQ is a reactive organosilicon compound having a hydrolyzable group where q = 0 in the reactive organosilicon compound having a hydrolyzable group represented by the general formula (4) Content (mol%), δT of the reactive organosilicon compound having a hydrolyzable group of q = 1 in the reactive organosilicon compound having a hydrolyzable group represented by the general formula (4) The content (mol%) is shown, and 0 ≦ {δQ / (δQ + δT + δD)} ≦ 0.1.)   The method for producing a polyorganosiloxane according to claim 10 or 11, wherein the hydrolyzable group is an alkoxy group.   The alkoxide-based organotin is used as a catalyst in the production of polyorganosiloxane by hydrolysis in the presence of water and polycondensation of the obtained hydrolysis product. 2. A method for producing a polyorganosiloxane according to item 1.   The step of hydrolyzing the reactive organosilicon compound having a hydrolyzable group represented by the general formula (4) in the presence of water is performed by a reflux step that does not involve distillation of water or a solvent out of the reaction system. The method for producing a polyorganosiloxane according to any one of claims 10 to 13, wherein:   The method for producing a polyorganosiloxane according to any one of claims 10 to 14, wherein the condensation ratio of the intermediate after completion of the hydrolysis step is 70% or more.   A curable resin composition comprising the polyorganosiloxane according to any one of claims 1 to 9 and a curing catalyst.   The light emitting component manufactured using the curable resin composition of Claim 16.   A semiconductor device comprising the light emitting component according to claim 17.