JP2009280768A - Siloxane derivative and cured product, and optical semiconductor encapsulant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new siloxane derivative, a cured product, and an optical semiconductor encapsulant. <P>SOLUTION: The siloxane derivative has: a partial cleavage cage type silsesquioxane structure; a constitutional unit represented by a general formula (1), wherein R<SP>1</SP>and R<SP>2</SP>each independently represents a hydrogen atom, a halogen atom, a hydrocarbon, or a partial substitution product thereof, respectively, and may be same or different when two or more R<SP>1</SP>and R<SP>2</SP>are present in one molecule; and an epoxy group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel siloxane derivative, a cured product obtained by polymerizing the siloxane derivative, and an optical semiconductor sealing material comprising the cured product. The cured product obtained by polymerizing the siloxane derivative of the present invention has high transparency, and further has excellent curability and heat resistance. In particular, adhesives, coating materials, photo materials for optical parts and electronic parts are used. It is useful for applications such as resists, sealing materials, sealing materials, insulating materials, lens materials, and substrate materials. In particular, the present invention relates to a novel siloxane derivative and a cured product obtained by polymerizing the siloxane derivative, which are suitable for an optical semiconductor sealing material.

  Conventionally, as a sealing material for an optical semiconductor such as a light emitting diode (LED), an epoxy resin, a silicone resin, or the like is used depending on the use environment, application, or the like. However, when epoxy resin is used, it is excellent in curability, but there is a problem that heat resistance is insufficient and yellowing occurs. On the other hand, when silicone resin is used, heat resistance is excellent, but soft There is a problem that dust or the like adheres when used as a material, and a problem that adhesion and thermal shock resistance are insufficient when a hard material is used, causing peeling from the base material and cracking of the sealing material. In addition, in a silicone resin, a high refractive index is desired from the viewpoint of improving light extraction efficiency.

  In order to achieve both the curing characteristics of the epoxy resin and the heat resistance of the silicone resin, siloxane derivatives having an epoxy group have also been studied (see Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4). However, since these siloxane derivatives have a large amount of epoxy groups introduced, with recent increase in brightness and power of LEDs, heat resistance has become insufficient, having high transparency, curability, Development of a new material capable of forming a cured product having excellent heat resistance is desired.

JP 2005-171021 A JP 2004-238589 A JP 2004-359933 A JP 2006-104248 A

  The present invention is capable of forming a cured product having high transparency and excellent curability and heat resistance, and particularly a siloxane derivative suitable for an optical semiconductor sealing material and a cured product obtained by polymerizing the siloxane derivative. The purpose is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by a specific siloxane derivative and a cured product obtained by polymerizing the siloxane derivative, thereby completing the present invention. It came to.

  That is, the present invention provides a siloxane derivative described below, a cured product obtained by polymerizing the siloxane derivative, and an optical semiconductor sealing material comprising the cured product. Specifically, the present invention includes the following [1] to [14].

  [1] Partially cleaved cage silsesquioxane structure and the following general formula (1):

(Wherein R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon, or a partial substituent thereof, and R ¹ and R ² may be the same when a plurality of R ¹ and R ² exist in one molecule) May be different.)
And a siloxane derivative having an epoxy group.

  [2] The partially cleaved cage silsesquioxane structure has the following general formula (2):

(In the formula, R ³ represents a hydrogen atom, a halogen atom, a hydrocarbon, or a partially substituted product thereof, and a plurality of R ³ may be the same or different.)
The siloxane derivative according to [1] represented by

  [3] At least the following general formula (3):

(In the formula, R ⁴ and R ⁵ each independently represent a hydrocarbon or a partially substituted product thereof, R ⁶ represents an epoxy group-containing group, and R ⁴ , R ⁵ and R ⁶ are present in the molecule. If there are multiple, they may be the same or different.)
The siloxane derivative according to [1] or [2], which is contained in the structural unit represented by

  [4] The following general formula (4):

(In the formula, R ⁷ , R ⁸ and R ⁹ each independently represent a hydrocarbon or a partial substituent thereof, and when there are a plurality of R ⁷ , R ⁸ and R ⁹ in the molecule, they are the same or different. May be.)
The siloxane derivative according to any one of [1] to [3], further having a structural unit represented by:

[5] The siloxane derivative according to [2], wherein R ³ is a phenyl group.

[6] R ¹ and R ² are methyl groups, and those cases where ^{R 4, R 5, R 7} , R 8 and R ⁹ present is either a methyl group, [1] to [5] The siloxane derivative according to any one of the above.

[7] The following general formula (5):
{(C ₆ H ₅ SiO _3/2 ) _a ((CH ₃ ) ₂ SiO _1/2 CH ₂ CH ₂ ) _{2c + d + e} (H (CH ₃ ) ₂ SiO _1/2 ) _{b- (2c + d + e)} } (((CH ₃ ) ₂ SiO) _n (CH ₃ ) ₂ Si) _c (R ⁶ ) _d ((CH ₃ ) ₃ Si) _e (5)
(Wherein R ⁶ is an epoxy group-containing group, a, b, c, d, e and n are real numbers, a> 0, b> 0, c> 0, d> 0, e ≧ 0, n > 0 and b ≧ 2c + d + e.)
The siloxane derivative in any one of [1]-[6] containing the structural unit represented by these.

  [8] A cured product obtained by polymerizing the siloxane derivative according to any one of [1] to [7].

  [9] The cured product according to [8], which is polymerized using an acid anhydride as a curing agent.

  [10] The cured product according to [9], which is polymerized by further using a curing accelerator.

  [11] The acid anhydride present in the curing agent is polymerized so that the acid anhydride / epoxy group = 0.01 to 0.8 in an equivalent ratio to the epoxy group, [9] or [10 ] The hardened | cured material as described in.

  [12] The cured product according to [8], which is polymerized using a cationic polymerization initiator as a polymerization initiator.

  [13] The cured product according to any one of [8] to [12], which is polymerized by heat.

  [14] An optical semiconductor sealing material comprising the cured product according to any one of [8] to [13].

  Hereinafter, the present invention will be described in detail.

  The siloxane derivative of the present invention has a partially cleaved cage silsesquioxane structure and the following general formula (1):

(Wherein R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon, or a partial substituent thereof, and R ¹ and R ² may be the same when a plurality of R ¹ and R ² exist in one molecule) May be different.)
And a siloxane derivative having an epoxy group.

  The partially-cleavage cage silsesquioxane structure in the present invention is a cage structure in which a part of Si—O bond in a polysiloxane whose basic structural unit is a T unit is cleaved. Is the following general formula (6):

(Wherein R ³ is a hydrogen atom, a halogen atom, a hydrocarbon, or a partially substituted product thereof, and a plurality of R ³ may be the same or different, i and j are positive numbers, and 6 ≦ i + j ≦ 40, i ≧ 1, and j ≧ 4.)
There are some which have a structure represented by

  Examples of the structure represented by the general formula (6): General formula (2), general formula (7), general formula (8):

Shown in

  By having a partially cleaved cage silsesquioxane structure, more typically a structural unit represented by the general formula (6), the siloxane derivative of the present invention is excellent in curability and has a Tg of Gives a cured product with high heat resistance. The structure represented by the general formula (2) is preferable because it can be three-dimensionally bonded and has particularly high Tg and excellent heat resistance. Specific examples include trisilanol-type silsesquioxane, which can be suitably used from the viewpoint of availability. Moreover, by having a structural unit represented by the general formula (1), the siloxane derivative of the present invention gives an appropriate viscosity and is excellent in workability.

The substituent R ^{3 in} the general formula (6) represents a hydrogen atom, a halogen atom, a hydrocarbon, or a partial substituent thereof, and a plurality of R ³ may be the same or different. Examples of the hydrocarbon group that can be employed as the substituent R ³ include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aromatic structure-containing alkenyl group, a polyene hydrocarbon group, an aryl group, an araalkyl group, and an alkylene group. Etc. Examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl and the like. Examples of the cycloalkyl group include cyclopentyl, cyclohexyl, cyclohexylethyl, cycloheptyl, cyclooctyl, cyclononyl, methylcyclopentyl, methylcyclohexyl and the like. Examples of alkenyl groups include vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl and the like. Examples of cycloalkenyl groups include cyclopentenyl, cyclohexenyl, cyclohexenylethyl, norbornenyl, norbornenylethyl and the like. Examples of the aromatic structure-containing alkenyl group, a cinnamyl _{(C 6 H 5 -CH = CH} -CH 2 -), styryl _{(C 6 H 5 -CH = CH} -), 4- Binirusuchiriru (CH ₂ = CH- C ₆ H ₄ —CH═CH—), alkyl-substituted styryl, alkoxy-substituted styryl groups and the like. Examples of polyene hydrocarbon groups include 1,5-hexadienyl, 2,4-pentadienyl, cyclooctadienyl groups, and the like. Examples of araalkyl groups include benzyl, phenethyl, 2-methylbenzyl, 4-methylbenzyl, α-methylbenzyl, 2-vinylphenethyl, 4-vinylphenethyl groups and the like. Examples of the alkylene group include an ethylene group, a propylene group, and a butylene group. Examples of the aryl group include a phenyl group, a phenylene group, a naphthyl group, a naphthylene group, or an aromatic group that is mono-substituted or substituted with an alkyl group or an alkenyl group having 1 to 14, more preferably 1 to 8 carbon atoms. Etc. Examples of substituted aromatic groups are tolyl, 4-methylphenyl, 2,4-dimethylphenyl, 4-t-butylphenyl, 4-vinylphenyl, 2-allylphenyl, 4-allylphenyl. Group, vinyl naphthyl group and the like.

In the general formula (6), the total number of carbon atoms of R ³ is preferably 10 or less, more preferably 6 or less, in view of high heat resistance. For the same reason, it is preferable not to include a carbon-carbon double bond. In the present invention, the “carbon-carbon double bond” includes a conjugated double bond but does not include an aromatic ring structure. Particularly preferably, R ³ is a methyl group or an ethyl group. Further, the refractive index can be increased by introducing a phenyl group as R ³ . Throughout this specification, heat resistance means that yellowing due to heat hardly occurs.

Examples of R ¹ and R ² in the general formula (1) are each independently at least one selected from the examples of R ³ in the general formula (6). Among these, when R ¹ and / or R ² is a linear or branched alkyl group, there is an advantage of excellent heat resistance, and a siloxane derivative having good viscosity and good workability is obtained. easy. The total number of carbon atoms, including substituents, of each of R ¹ and R ² is preferably 10 or less, more preferably 6 or less from the viewpoint of high heat resistance, and R ¹ and R from the same viewpoint. ² are each preferably an unsubstituted linear or branched alkyl group. Similarly, R ¹ and R ² are each more preferably a linear alkyl group from the viewpoint of high heat resistance. Based on the above, R ¹ and R ² in the general formula (1) are particularly preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group, Preferably, they are a methyl group and an ethyl group. In addition, the refractive index can be increased by introducing a phenyl group as at least one of R ¹ and R ² . The structural unit represented by the general formula (1) may be ^one type or two or more types in which at least one of R ¹ and R ² is different.

  The siloxane derivative of the present invention has an epoxy group at least represented by the general formula (3):

(In the formula, R ⁴ and R ⁵ each independently represent a hydrocarbon or a partially substituted product thereof, R ⁶ represents an epoxy group-containing group, and R ⁴ , R ⁵ and R ⁶ are present in the molecule. If there are multiple, they may be the same or different.)
It is preferable to contain in the structural unit represented by these. Thereby, the molecular weight and the epoxy value can be easily adjusted, the workability is good with an appropriate viscosity, and a siloxane derivative having a predetermined epoxy value can be easily obtained.

Examples of R ⁴ and R ⁵ in general formula (3) are each independently at least one selected from the examples of R ³ in general formula (6). Among these, when R ⁴ and R ⁵ are each a linear or branched alkyl group, there is an advantage of excellent heat resistance, and it is easy to obtain a siloxane derivative having an appropriate viscosity and good workability. . The total number of carbon atoms including substituents in R ⁴ and R ⁵ is preferably 10 or less, more preferably 6 or less in view of high heat resistance. From the same viewpoint, R ⁴ and R ⁵ Each is preferably an unsubstituted linear or branched alkyl group. Similarly, R ⁴ and R ⁵ are each preferably a linear alkyl group in view of high heat resistance. Based on the above, R ⁴ and R ⁵ in the general formula (3) are particularly preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group, Preferably, they are a methyl group and an ethyl group. In addition, the refractive index can be increased by introducing a phenyl group as at least one of R ⁴ and R ⁵ . The structural unit represented by the general formula (3) may be one type or two or more types in which at least one of R ⁴ and R ⁵ is different.

R ⁶ in the general formula (3) is an epoxy group-containing group, and the general formula (9):

(Wherein R ¹⁰ represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms.)
General formula (10):

(Wherein R ¹¹ represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms.)
General formula (11):

(In the formula, R ¹² represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms.)
Or general formula (12):

(In the formula, R ¹³ represents a methylene group, a divalent linear alkylene group having 2 to 10 carbon atoms, or a branched alkylene group having 3 to 10 carbon atoms.)
Is preferable in terms of curability, heat resistance, and the like.

The number of carbon atoms of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ is preferably 10 or less from the viewpoint of heat resistance. From the above viewpoint, preferred structures of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are exemplified by — (CH ₂ ) —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH _2). ) ₄ -,-(CH ₂ ) ₅ -,-(CH ₂ ) ₆ -,-(CH ₂ ) ₈ -,-(CH ₂ ) _10- , -CH (CH ₃ ) CH _2- , -C (CH _{3) 2} - and the _{like, - (CH 2) 2 -} , - (CH 2) 3 -, - CH (CH 3) CH 2 - are more preferable, more preferably - (CH _{2) 2} -, - (CH ₂ ) ₃ —. Moreover, when an epoxy group containing group is represented by General formula (9) or General formula (11), it is preferable from a viewpoint of availability, and when represented by General formula (9), it is still more preferable from a sclerosing | hardenable viewpoint. In summary, the epoxy group-containing groups in the siloxane derivative of the present invention are particularly preferable as 3-glycidoxypropyl group, 2- (3 ′, 4′-epoxycyclohexyl) ethyl group, 3- (2 '-Hydroxyethoxy) propyl group and the like can be mentioned. Among them, 2- (3 ′, 4′-epoxycyclohexyl) ethyl group is most preferable in terms of excellent curability.

  The number average molecular weight of the siloxane derivative of the present invention is not particularly limited, but is preferably 500 to 100,000. If the number average molecular weight is 500 or more, the curability is excellent, the Tg of the cured product is high, and if the number average molecular weight is 100,000 or less, the workability of the siloxane derivative and the curable resin composition containing the siloxane derivative is excellent. . From such a viewpoint, the more preferable range of the number average molecular weight is 700 to 50000, more preferably 800 to 10000, particularly preferably 900 to 8000, and most preferably 1000 to 7000. The number average molecular weight is defined by the number average molecular weight in GPC measurement.

  The epoxy value of the siloxane derivative is preferably 0.001 to 0.25 (equivalent / 100 g), more preferably 0.001 to 0.15 (equivalent / 100 g) from the viewpoints of curability and heat resistance. More preferably, it is 0.005-0.12 (equivalent / 100 g), and most preferably 0.01-0.10 (equivalent / 100 g). Here, the epoxy value means the number of moles of epoxy groups in 100 g of the siloxane derivative.

  The siloxane derivative of the present invention has the general formula (4):

(In the formula, R ⁷ , R ⁸ and R ⁹ each independently represent a hydrocarbon or a partial substituent thereof, and when there are a plurality of R ⁷ , R ⁸ and R ⁹ in the molecule, they are the same or different. May be.)
It is more preferable to further have a structural unit represented by Thereby, the molecular weight and the epoxy value can be easily adjusted, the workability is good with an appropriate viscosity, and a siloxane derivative having a predetermined epoxy value can be easily obtained.

Examples of R ⁷ , R ⁸ and R ⁹ in the general formula (4) each independently include at least one selected from the examples of R ³ in the general formula (6). In these, when R <^7> , R < ⁸ > and R < ⁹ > are each linear or branched alkyl groups, there exists an advantage that it is excellent in heat resistance. The total number of carbon atoms including substituents in R ⁷ , R ⁸ and R ⁹ is preferably 10 or less, more preferably 6 or less in view of high heat resistance, and R ⁷ , R ⁸ and R ⁹ are each preferably an unsubstituted linear or branched alkyl group. Similarly, R ⁷ , R ⁸ and R ⁹ are each preferably a linear alkyl group in view of high heat resistance. Based on the above, R ⁷ , R ⁸ and R ⁹ in the general formula are particularly preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group, Preferably, they are a methyl group and an ethyl group. Further, the refractive index can be increased by introducing a phenyl group as at least one of R ⁷ , R ⁸ and R ⁹ . The structural unit represented by the general formula (4) may be one type or two or more types in which at least one of R ⁷ , R ⁸ and R ⁹ is different.

In the siloxane derivative of the present invention, R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ , R ⁸ and R ⁹ may be methyl groups in that a cured product having particularly excellent heat resistance can be provided. Particularly preferred.

The siloxane derivative of the present invention has a general formula (5):
{(C ₆ H ₅ SiO _3/2 ) _a ((CH ₃ ) ₂ SiO _1/2 CH ₂ CH ₂ ) _{2c + d + e} (H (CH ₃ ) ₂ SiO _1/2 ) _{b- (2c + d + e)} } (((CH ₃ ) ₂ SiO) _n (CH ₃ ) ₂ Si) _c (R ⁶ ) _d ((CH ₃ ) ₃ Si) _e (5)
(Wherein R ⁶ is an epoxy group-containing group, a, b, c, d, e and n are real numbers, a> 0, b> 0, c> 0, d> 0, e ≧ 0, n > 0 and b ≧ 2c + d + e.)
It is preferable that the structural unit represented by these is included. Thereby, the hardened | cured material which is excellent in heat resistance especially can be given.

In the general formula (5), when 2a ≦ c, the siloxane derivative of the present invention is preferable in terms of excellent workability with an appropriate viscosity, and when e> 0, it is excellent in adjusting the molecular weight and epoxy value. Is preferable. The values of a, b, c, d, e and n can be determined by ²⁹ Si-NMR.

  Although it does not specifically limit as a synthesis method of the siloxane derivative shown by above-mentioned [1]-[7], For example, the synthesis method by hydrosilylation can be mentioned. In this case, it is more preferable to synthesize so as not to include an unreacted vinyl group from the viewpoint of heat resistance.

  The cured product of the present invention can be obtained by polymerizing the siloxane derivative of the present invention. Examples of the method for polymerizing and curing the siloxane derivative include thermal curing, curing with energy rays, and curing with a combination thereof. Curing with an energy beam is preferable for curing in a short time, and thermal curing is more preferable for obtaining a cured product with better heat resistance.

  When the siloxane derivative of the present invention is cured by energy rays, a cationic photopolymerization initiator or a photobase generator may be added as a compound that promotes curing.

The cationic photopolymerization initiator is a compound capable of releasing a substance that initiates cationic polymerization by irradiation with energy rays, and particularly preferred is an onium salt that releases a Lewis acid by irradiation. Examples of the onium salt include a diazonium salt of a Lewis acid, an iodonium salt of a Lewis acid, a sulfonium salt of a Lewis acid, and the cation portion is aromatic diazonium, aromatic iodonium, and aromatic sulfonium, respectively, and the anion portion is An onium salt composed of BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , [BX ₄ ] ⁻ (wherein X is a phenyl group substituted with two or more fluorine or trifluoromethyl groups) and the like.

  Specifically, boron difluoride phenyldiazonium salt, phosphorus hexafluoride diphenyliodonium salt, antimony hexafluoride diphenyliodonium salt, arsenic hexafluoride tri-4-methylphenylsulfonium salt, antimony tetrafluoride Tri-4-methylphenylsulfonium salt, tetrakis (pentafluorophenyl) boron diphenyliodonium salt, acetylacetone aluminum salt and orthonitrobenzylsilyl ether mixture, phenylthiopyridium salt, phosphorus hexafluoride allene-iron complex, etc. be able to. More specifically, CD-1012 (trade name: manufactured by SARTOMER), PCI-019, PCI-021 (trade name: manufactured by Nippon Kayaku Co., Ltd.), Optmer SP-150, Optomer SP-170 (trade name: Asahi) Denki Co., Ltd.), UVI-6990 (trade name: manufactured by Dow Chemical Co., Ltd.), CPI-100P, CPI-100A (trade name: manufactured by San Apro), TEPBI-S (trade name: manufactured by Nippon Shokubai Co., Ltd.), etc. These can be used alone or in combination of two or more.

  In addition, a photosensitizer such as benzophenone, benzoin isopropyl ether, thioxanthone, and anthracene can be used in combination with the photocationic polymerization initiator. Specifically, 4,4′-bis (diethylamino) benzophenone, 2,4 Examples include '-diethylthioxanthone, isopropylthioxanthone, 9,10-diethoxyanthracene, and 9,10-dibutoxyanthracene.

  Examples of the photobase generator include benzyl carbamate compounds, benzoin carbamate compounds, o-carbamoyl hydroxyamines, o-carbamoyl oximes, aromatic sulfonamides, N- (2-arylethenyl) amides, aryl azides , N-arylformamides, acyloxyimino compounds, and N-substituted-4- (orthonitrophenyl) dihydropyrrolidines.

  The blending amount of these photopolymerization initiators is preferably 0.001 to 20 parts by mass, and 0.1 to 15 parts by mass with respect to 100 parts by mass of the siloxane derivative of the present invention from the viewpoint of curability and heat resistance of the cured product. Is more preferable, and 0.2-10 mass parts is still more preferable.

  When the siloxane derivative of the present invention is photocured, the light source that can be used for curing the siloxane derivative is not particularly limited as long as it can be cured within a predetermined working time. For example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, or an electrodeless discharge lamp can be used. In addition, in order to accelerate | stimulate hardening, you may heat the hardened | cured material obtained by the said method with a thermostat, an infrared heater, etc.

  When the siloxane derivative of the present invention is thermally cured, acid anhydride curing or curing by cationic polymerization is preferable from the viewpoint of excellent heat resistance.

  When the siloxane derivative of the present invention is thermally cured with an acid anhydride, the acid anhydride is added to the siloxane derivative. Acid anhydrides that can be used in the present invention include hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, phthalic anhydride, trimellitic anhydride Colorless to pale yellow acid anhydrides such as acid, pyromellitic anhydride, succinic anhydride, and acid anhydride-terminated polydimethylsiloxane can be used, and these can be used alone or in combination of two or more thereof. Methyl hexahydrophthalic anhydride, hexahydrophthalic anhydride, and methyl nadic anhydride are more preferred from the viewpoint of heat resistance.

  The acid anhydride may be used alone or as a mixture of two or more, and the blending amount is 0.01 to 5 equivalents relative to the epoxy group of the siloxane derivative of the present invention from the viewpoint of heat resistance and the like. Is preferably added so as to be 0.05 to 2 equivalents, more preferably 0.1 to 1.5 equivalents, and more preferably 0.15 to 1.0. It is particularly preferable to add so as to be equivalent, and most preferable to add so as to be 0.2 to 0.8 equivalent.

  When the siloxane derivative of the present invention is cured with an acid anhydride, a curing accelerator may be further added. Examples of the curing accelerator include imidazole compounds, quaternary ammonium salts, phosphonium salts, amine compounds, aluminum chelate compounds, and organic phosphine compounds. Among these, imidazole compounds, quaternary ammonium salts, phosphonium salts, organic phosphine compounds, and the like are preferable because they give a cured product with little coloration. Specifically, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1,8-diaza-bicyclo (5,4,0) undecene-7, trimethylamine, benzyldimethylamine, triethylamine, dimethylbenzylamine, 2 , 4,6-trisdimethylaminomethylphenol and other amine compounds and salts thereof, quaternary ammonium salts such as tetramethylammonium chloride, benzyltrimethylammonium bromide, tetrabutylammonium bromide, aluminum chelates, tetra-n-butylphosphonium benzotri Organic phosphine compounds such as azolate, tetra-n-butylphosphonium-0,0-diethyl phosphorodithioate, chromium (III) tricarboxylate, tin octylate, acetylacetonate Cr, etc. It is below. Among these, tetramethylammonium chloride, tetra-n-butylphosphonium-0,0-diethyl phosphorodithioate and the like give a cured product with little coloration. Moreover, as a commercial item, U-CAT SA1, U-CAT 2026, U-CAT 18X etc. can be used suitably from a San Apro company.

  These curing accelerators may be used alone or as a mixture of two or more thereof, and the blending amount thereof is more than 0 parts by mass with respect to 100 parts by mass of the siloxane derivative of the present invention, and 0.001 mass from the viewpoint of reactivity. It is preferably 10 parts by mass or less from the viewpoint of heat resistance. From the above viewpoint, it is more preferably 0.01 to 5 parts by mass, still more preferably 0.01 to 2 parts by mass, and particularly preferably 0.05 to 1 part by mass.

  When the siloxane derivative of the present invention is thermally cured by cationic polymerization, a thermal cationic polymerization initiator is added to the siloxane derivative.

  The thermal cationic polymerization initiator is a compound that initiates polymerization by generating cationic species by heat, and examples thereof include various onium salts such as quaternary ammonium salts, phosphonium salts, and sulfonium salts. Specifically, as the quaternary ammonium salt, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, N, N -Dimethyl-N-benzylanilinium hexafluoroantimonate, N, N-dimethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl-N -Benzyltrifluoromethanesulfonate, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimonate, N, N-diethyl -N- (4- methoxybenzyl) preparative Luigi hexafluoroantimonate and the like. Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate. Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsinate, tris (4-methoxyphenyl) sulfonium hexafluoroarsinate, diphenyl (4-phenylthiophenyl) sulfonium. Hexafluoroalcinate and the like can be mentioned.

  These onium salts are commercially available, for example, Adeka Opton CP-66, CP-77 (all manufactured by Asahi Denka Kogyo Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI-80L and Sun-Aid SI-100L (all Product names: manufactured by Sanshin Chemical Industry Co., Ltd.), CI-2855, CI-2624 (all product names: manufactured by Nippon Soda Co., Ltd.), CAT EX-1 (product name: manufactured by Daicel Chemical Industries, Ltd.), and the like.

  Examples of other thermal cationic polymerization initiators include organometallic complexes, such as aluminum compounds containing aluminum complexes such as aluminum trisacetylacetonate, zirconium compounds containing zirconium complexes such as tetrakis (ethylacetoacetate) zirconium. And titanium compounds containing a titanium complex such as diisopropoxybis (acetylacetonate) titanate. In these, an aluminum compound is preferable.

  These thermal cationic polymerization initiators may be used alone or as a mixture of two or more thereof, and the blending amount thereof is based on 100 parts by mass of the siloxane derivative of the present invention from the viewpoint of curability and heat resistance of the cured product. 0.001-20 mass parts is preferable, 0.001-10 mass parts is more preferable, 0.002-1 mass parts is still more preferable, 0.002-0.5 mass parts is especially preferable, 0.005-0 .1 part by mass is most preferred.

  When the siloxane derivative of the present invention is thermally cured, curing with an acid anhydride and curing by cationic polymerization may be combined. That is, an acid anhydride and a thermal cationic polymerization initiator may be used in combination, or an acid anhydride, a curing accelerator, and a thermal cationic polymerization initiator may be used in combination.

  Further, the resin composition containing the siloxane derivative of the present invention (hereinafter referred to as curable resin composition) is not limited to this, but usually has a liquid form, and in the case of thermosetting, the curing The resin composition can be cured by heating to 80 to 250 ° C. The thermosetting molding method is not particularly limited, and can be molded by casting, low-pressure transfer molding, potting, dipping, pressure molding, injection molding, or the like. When the curable resin composition is solid, it can be molded by being heated and cured under pressure using a press, a low-pressure transfer molding machine or the like.

  Moreover, you may harden the composition which made the curable resin composition containing the siloxane derivative of this invention contain the organic solvent. Then, the curable resin composition or a composition containing an organic solvent in the curable resin composition is impregnated in a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, A cured product can also be obtained by hot press molding a prepreg obtained by photocuring or thermosetting, or heat drying.

  An organic resin can be blended with the curable resin composition containing the siloxane derivative of the present invention for the purpose of imparting adhesiveness and flexibility. Examples of the organic resin include an epoxy resin, an acrylic resin, a polyester resin, and a polyimide resin. In particular, those having groups capable of reacting with other components are preferred, and epoxy resins are preferred. Examples of the epoxy resin include bis A type epoxy resin, bis F type epoxy resin, hydrogenated epoxy resin, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and the like. The organic resin can be used as long as the object of the present invention is not impaired, and the blending amount is usually 0 to 80 parts by mass, preferably 0 to 30 parts by mass with respect to 100 parts by mass of the siloxane derivative of the present invention. is there.

  In addition, when a curable resin composition containing the siloxane derivative of the present invention is cationically polymerized by light or heat to obtain a cured product, another cationically polymerizable compound may be blended. Examples of the cationic polymerizable compound include compounds having an epoxy group, compounds having an oxetane ring, vinyl ether compounds, other cyclic ether compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, and spiro orthoester compounds. it can. Moreover, the above compound may have a hydroxyl group, and when it has a hydroxyl group, curability and adhesiveness can be improved. Among these, it is preferable to use a compound having an epoxy group and / or a compound having an oxetane ring from the viewpoints of curability and transparency. In order to improve photocurability, particularly in a long wavelength region lamp such as a xenon lamp, it is preferable to use a compound having an epoxy group and a compound having an oxetane ring in combination.

  The curable resin composition containing the siloxane derivative of the present invention includes a dye, a deterioration inhibitor, a mold release agent, a diluent, a viscosity modifier, and an antioxidant within a quantitative and qualitative range that does not depart from the scope of the present invention. , Light stabilizer, ultraviolet absorber, silane coupling agent, heat stabilizer, antistatic agent, antifoaming agent, leveling agent, polymerization inhibitor, waxes, slip agent, corrosion inhibitor, flame retardant, plasticizer, Additives such as surfactants can be blended. Further, the curable resin composition of the present invention includes an inorganic oxide as necessary for the purposes of heat resistance, hardness, conductivity, thermal conductivity, thixotropy, low thermal expansion, refractive index improvement and adjustment, and the like. The filler represented by can be mix | blended.

  As the antioxidant, all conventionally known antioxidants can be used. For example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone, 4,4′-butylidenebis (3-methyl- 6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2,2′-methylenebis (4-ethyl-6-t-butylphenol) and the like.

  When this antioxidant is used, its blending amount is not particularly limited, but is usually preferably 5 to 20000 mass ppm, more preferably 10 to 10000 mass ppm, and more preferably 100 to 1000 ppm by mass with respect to the siloxane derivative of the present invention. Is particularly preferred. When it mix | blends in this range, the antioxidant effect will fully be exhibited, there is no coloring and cloudiness, and it is excellent also in heat resistance.

  In order to improve light resistance, a light stabilizer can be blended. As the light stabilizer, a hindered amine stabilizer that captures radicals generated when the cured product deteriorates is suitable. You may use together with the said antioxidant, and, thereby, an antioxidant effect can be improved more. Specific examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyl-2,2,6,6-tetramethylpiperidine and the like. Here, the light resistance means that yellowing due to light hardly occurs.

  Examples of the corrosion inhibitor include ion exchangers, polyvalent carboxylic acids, hydroxycarboxylic acids, organic tin compounds, and sulfide compounds.

  Fillers include silica (fumed silica, colloidal silica, precipitated silica, etc.), silicon nitride, boron nitride, alumina, titania, zirconia and other inorganic oxides or inorganic nitrides, glass, glass fiber, talc, clay, ceramics , Silver powder, gold powder, copper powder and the like. These fillers can be used with or without a surface treatment. When the surface treatment is performed, the dispersibility of the filler is increased, the fluidity of the composition is increased, and the filling rate is increased. This is preferable in that it can be performed. The average particle size of these fillers is preferably 500 nanometers or less because the cured product has high transparency, more preferably 200 nanometers or less, still more preferably 100 nanometers or less, and most preferably 20 nanometers. It is below nanometer.

  The siloxane derivative of the present invention and a cured product obtained by polymerizing the siloxane derivative have high transparency and are excellent in curability and heat resistance. Adhesives, paints, mechanical component materials, automotive component materials, civil engineering It is useful for applications such as adhesives, coating materials, photoresists, sealing materials, sealing materials, insulating materials, lens materials, and substrate materials for building materials, molding materials, etc., especially for optical components and electronic components. Specifically, eyeglass lenses, optical equipment lenses, CD and DVD pickup lenses, automotive headlamp lenses, projector lens and other lens materials, optical filters such as optical fibers, optical waveguides and color filters, and optical adhesives Agents, optical disk substrates, optical transmission layers of optical disks, interlayer insulation layers, printed wiring boards, laminates such as copper-clad laminates, display substrates, light guide plates, antireflection films, etc., and sealing of semiconductors, liquid crystals, organic EL, etc. Examples thereof include a stopping material. In particular, it can be suitably used for optical semiconductor device applications such as a sealing material for an optical semiconductor device, a die bonding paste and a die bond material obtained by curing the same, or a chip coating material or a lens material that covers the periphery of a chip. . Examples of optical semiconductors include LED lamps, chip LEDs, semiconductor lasers, photocouplers, and photodiodes.

  The emission wavelength of the optical semiconductor using the cured product obtained by polymerizing the siloxane derivative of the present invention can be widely used from infrared to red, green, blue, purple and ultraviolet. By using a cured product obtained by polymerizing the siloxane derivative of the present invention as an optical semiconductor encapsulant, an optical semiconductor device such as a light emitting diode with little deterioration in luminance over a long period of time without causing yellowing or peeling of the encapsulant. can get.

  When producing an optical semiconductor using a cured product obtained by polymerizing the siloxane derivative of the present invention, the optical semiconductor is produced by sealing the light emitting element with a curable resin composition containing the siloxane derivative of the present invention. Can do. At the time of sealing, it may be sealed only with the curable resin composition containing the siloxane derivative of the present invention, but may be used in combination with other sealing materials. When using together, after sealing with curable resin composition containing the siloxane derivative of this invention, you may seal with another sealing material, and after sealing with another sealing material, the siloxane derivative of this invention You may seal with the curable resin composition containing this. Examples of other sealing materials include epoxy resins, silicone resins, epoxy silicone resins, acrylic resins, urethane resins, urea resins, imide resins, and glass. Examples of the shape of the sealing portion include a bullet-shaped lens shape, a plate shape, and a thin film shape.

  The performance of the optical semiconductor using the cured product obtained by polymerizing the siloxane derivative of the present invention can be improved by a conventionally known method. As a method for improving the performance, for example, a method of providing a light reflecting layer or a condensing layer on the back surface of the light emitting device, a method of forming a complementary colored portion on the bottom, a layer that absorbs light having a wavelength shorter than the main light emitting peak is used. A method of sealing the light-emitting element and sealing with a hard material; a method of inserting and fixing an optical semiconductor into a through hole; and a substrate by connecting the optical semiconductor to a lead member by flip chip connection or the like Examples thereof include a method of extracting light from the direction, a method of performing a shaping process on each interface such as an interface between the light emitting element and the sealing material and an interface between the sealing material and the air.

  The optical semiconductor using the cured product obtained by polymerizing the siloxane derivative of the present invention includes, for example, a backlight such as a liquid crystal display or a mobile phone, illumination, an automobile headlamp, a vehicle instrument light source, various sensors, a printer, and a copying machine. It is useful as a light source such as a light source, a signal lamp, an indicator lamp, a display device, a light source of a surface light emitter, a display, a decoration, various lights, and the like.

The present invention will be described based on examples.
In this example, the epoxy value (equivalent / 100 g) was determined according to JIS K-7236. For gel permeation chromatography (GPC) measurement, which is a method for measuring the number average molecular weight, Shodex KF-804L (made by Showa Denko) as a column, LC-10AT (made by Shimadzu Corporation) as a pump, and RID- as a detector. 6A (RI: differential refractometer, manufactured by Shimadzu Corporation), tetrahydrofuran was used as the mobile phase. Moreover, JEOL GSX-400 was used for the measurement of a NMR spectrum. The amount of platinum contained was measured using a quadrupole ICP mass spectrometer (manufactured by Thermo Elemental: X7-ICP-MS).
Moreover, the various physical property evaluation in a present Example was implemented with the following method.

(1) Curability The cured product was observed by finger touch, and it was rated as ◎ if it was hard, ○ when it was soft but not sticky, and × when stickiness remained.

(2) Transparency When the cured product was visually observed, it was evaluated as ◎ for colorless and transparent, ◯ for slightly colored, and × for colored.

(3) Heat resistance A curable resin composition containing a siloxane derivative was applied to a glass plate and cured to obtain a cured film having a thickness of 105 μm. The obtained sample was heat-treated at 260 ° C. for 30 minutes. And the change of the transmittance | permeability in 400 nm before and behind heat processing was measured with the ultraviolet visible spectrophotometer V-550 (made by JASCO Corporation), and the transmittance | permeability retention rate (%) was calculated | required. A sample having a retention rate of 90% or more was evaluated as ◎, a sample having a retention rate of less than 90% and 80% or more was evaluated as ○, and a sample having a retention rate of less than 80% was evaluated as ×.

(4) Refractive Index Measurement A curable resin composition containing a siloxane derivative was applied to a glass plate and cured to obtain a cured film having a thickness of 105 μm. The refractive index at 589 nm of the cured film was measured with a reflection spectral film thickness meter FE-3000 (manufactured by Otsuka Electronics Co., Ltd.).

[Synthesis Example 1]
A reactor having a stirrer was charged with 50 g of trisilanol phenyl-POSS (manufactured by Hybrid Plastics) and 245 g of dehydrated tetrahydrofuran. To the dropping funnel, 18.06 g of dimethylchlorosilane and 20 g of dehydrated tetrahydrofuran were added and dropped into the reactor while stirring. After completion of dropping, the mixture was stirred at room temperature for 1.5 hours. To the dropping funnel, 16.39 g of triethylamine and 90 g of dehydrated tetrahydrofuran were added, and the mixture was added dropwise to a reactor placed in an ice bath with stirring to neutralize the reaction solution. After completion of the dropwise addition, the mixture was stirred for 1 hour while being placed in an ice bath. To the dropping funnel, 4.05 g of triethylamine and 0.96 g of methanol were added and dropped into the reactor while stirring to crush unreacted dimethylchlorosilane. After completion of dropping, the mixture was stirred at room temperature for 1 hour.

  Triethylamine hydrochloride precipitated in the reaction vessel was removed by filtration under reduced pressure. The solvent in the filtrate was distilled off under reduced pressure. The obtained solid was dissolved in a small amount of tetrahydrofuran and then dropped into a large amount of methanol to precipitate white crystals. White crystals were collected by filtration and then vacuum-dried to obtain white powder.

The obtained white powder has a partially cleaved cage silsesquioxane structure by ¹ H-NMR, ²⁹ Si-NMR (deuterated chloroform, tetramethylsilane internal standard) (C ₆ H ₅ SiO _3/2 ). It was found to be a compound represented by ₇ ((CH ₃ ) ₂ HSiO _1/2 ) ₃ .

[Synthesis Example 2]
In a reactor having a reflux condenser, a thermometer, and a stirrer, 15 g of the white powder synthesized in Synthesis Example 1 and 4.06 g of both terminal vinyl polydimethylsiloxane DMS-V03 (product name: Gelest Co., Ltd.), 2.49 g of 4-vinylcyclohexene oxide and 86.2 g of 1,4-dioxane were added. A 2.2% platinum-divinyltetramethyldisiloxane complex xylene solution diluted with 1,4-dioxane so that the Pt content was 1000 ppm was placed in a 0.356 g reactor. After stirring at 60 ° C. for 4 hours, the mixture was cooled to room temperature, and 1.42 g of vinyltrimethylsilane and 3 g of 1,4-dioxane were placed in the reactor. After stirring at 50 ° C. for 3 hours, the mixture was cooled to room temperature, and 15 g of Shirakaba A (product name: Takeda Pharmaceutical Company Limited) and 7 g of Celite (Wako Pure Chemical Industries, Ltd.) were placed in the reactor as activated carbon. Stir for 20 hours to remove the Pt catalyst. Thereafter, activated carbon and celite were removed by vacuum filtration. The filtrate was heated under reduced pressure and the solvent was distilled off to obtain a colorless and transparent siloxane derivative having fluidity.

The epoxy value of the obtained siloxane derivative was 0.079 eq / 100 g. Three peaks were detected from the GPC measurement, and the number average molecular weights were 6500, 3000, and 1400, respectively. In addition, ²⁹ Si-NMR (deuterated chloroform, tetramethylsilane internal standard) confirmed that 91% of SiH groups had reacted. The reacted SiH groups reacted with DMS-V03 at 30%, 4-vinylcyclohexene oxide at 58%, and vinyltrimethylsilane at 12%. ^{From 1} H-NMR, an unreacted vinyl group could not be confirmed. Moreover, the residual Pt catalyst was 1 ppm or less in terms of Pt. The appearance did not change even after 1 month at room temperature.

[Example 1]
100 parts by mass of the siloxane derivative obtained in Synthesis Example 2, 8.2 parts by mass of Ricacid MH-700G (product name: Shin Nippon Rika Co., Ltd.) mainly composed of 4-methylhexahydrophthalic anhydride as an acid anhydride, As a curing accelerator, 0.25 part by mass of U-CAT 18X (product name: manufactured by San Apro) was stirred until the whole became uniform, and then defoamed to obtain a curable resin composition. The equivalent ratio of acid anhydride to epoxy group of the siloxane derivative is 0.63. This curable resin composition was cast into a mold and a sample coated on a glass substrate was cured at 105 ° C. for 30 minutes, 120 ° C. for 2 hours, 150 ° C. for 2 hours, and further at 170 ° C. for 30 minutes. I did. Table 1 shows the performance of the obtained cured product.

[Example 2]
The same procedure as in Example 1 was performed except that ricacid MH-700G (product name: manufactured by Shin Nippon Rika Co., Ltd.) containing 4-methylhexahydrophthalic anhydride as a main component was changed to 8.8 parts by mass. The equivalent ratio of acid anhydride to epoxy group of the siloxane derivative is 0.68. Table 1 shows the performance of the obtained cured product.

[Example 3]
The same procedure as in Example 1 was conducted except that 9.5 parts by mass of Ricacid MH-700G (product name: manufactured by Shin Nippon Rika Co., Ltd.) containing 4-methylhexahydrophthalic anhydride as a main component was used. The equivalent ratio of acid anhydride to epoxy group of the siloxane derivative is 0.73. Table 1 shows the performance of the obtained cured product.

[Example 4]
The same procedure as in Example 1 was carried out except that 16.4 parts by mass of Ricacid MH-700G (product name: manufactured by Shin Nippon Rika Co., Ltd.) containing 4-methylhexahydrophthalic anhydride as a main component was used. The equivalent ratio of acid anhydride to epoxy group of the siloxane derivative is 1.27. Table 1 shows the performance of the obtained cured product.

[Example 5]
100 parts by mass of the siloxane derivative obtained in Synthesis Example 2 and 0.01 part by mass of Adeka Opton CP-66 (product name: manufactured by Asahi Denka Kogyo Co., Ltd.) as a thermal cationic polymerization initiator were stirred until the whole became uniform, and then removed. Foaming was performed to obtain a curable resin composition. This curable resin composition was cast into a mold and a sample coated on a glass substrate was cured at 105 ° C. for 30 minutes, 120 ° C. for 2 hours, 150 ° C. for 2 hours, and further at 170 ° C. for 30 minutes. I did. Table 1 shows the performance of the obtained cured product.

[Comparative Example 1]
100 parts by mass of ECMS-924 (product name: manufactured by Gelest, epoxy value 0.091) as a chain siloxane derivative having an alicyclic epoxy group, and Adeka Opton CP-66 (product name: Asahi Denka) as a thermal cationic polymerization initiator A curable resin composition was obtained by stirring and defoaming 0.015 parts by mass (produced by Kogyo Co., Ltd.) until the whole became uniform. The performance evaluation was performed in the same manner as in Example 1. Table 1 shows the performance of the obtained cured product.

[Comparative Example 2]
1,3,5,7-tetramethyl-tetrakis (3,4-epoxycyclohexylethyl) cyclotetrasiloxane (epoxy value 0.50) 100 parts by weight, ethylene glycol 10 parts, 4-methylhexahydro anhydride as acid anhydride 79 parts by mass of Ricacid MH-700G (product name: Shin Nippon Rika Co., Ltd.) mainly composed of phthalic acid and 0.25 parts by mass of U-CAT 18X (product name: San Apro Co., Ltd.) as a curing accelerator After stirring until uniform, defoaming was performed to obtain a curable resin composition. The equivalent ratio of acid anhydride to epoxy group of the siloxane derivative is 0.96. The performance evaluation was performed in the same manner as in Example 1. Table 1 shows the performance of the obtained cured product.

  From the above results, in the optical semiconductor used as the sealing material using the siloxane derivative according to the present invention and the cured product obtained by polymerizing the siloxane derivative, the balance between the curability and heat resistance of the cured product is higher than the conventional one. Since it is excellent, it can be expected to greatly improve the product life, and it becomes possible to provide an optical semiconductor with higher reliability than ever.

  The siloxane derivative of the present invention and a cured product obtained by polymerizing the siloxane derivative are excellent in transparency, curability, and heat resistance, and can be suitably used particularly for sealing materials in the field of optical semiconductors.

Claims (14)

Partially cleaved cage silsesquioxane structure and the following general formula (1):

(Wherein R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon, or a partial substituent thereof, and R ¹ and R ² may be the same when a plurality of R ¹ and R ² exist in one molecule) May be different.)
And a siloxane derivative characterized by having an epoxy group. The partially cleaved cage silsesquioxane structure has the following general formula (2):

(In the formula, R ³ represents a hydrogen atom, a halogen atom, a hydrocarbon, or a partially substituted product thereof, and a plurality of R ³ may be the same or different.)
The siloxane derivative of Claim 1 represented by these. The epoxy group has at least the following general formula (3):

(In the formula, R ⁴ and R ⁵ each independently represent a hydrocarbon or a partially substituted product thereof, R ⁶ represents an epoxy group-containing group, and R ⁴ , R ⁵ and R ⁶ are present in the molecule. If there are multiple, they may be the same or different.)
The siloxane derivative according to claim 1, which is contained in a structural unit represented by The following general formula (4):

(In the formula, R ⁷ , R ⁸ and R ⁹ each independently represent a hydrocarbon or a partial substituent thereof, and when there are a plurality of R ⁷ , R ⁸ and R ⁹ in the molecule, they are the same or different. May be.)
The siloxane derivative according to claim 1, further comprising a structural unit represented by: The siloxane derivative according to claim 2, wherein R ³ is a phenyl group. The R ¹ and R ² are methyl groups, and when R ⁴ , R ⁵ , R ⁷ , R ⁸ and R ⁹ are present, these are all methyl groups. The siloxane derivative described. The following general formula (5):
{(C ₆ H ₅ SiO _3/2 ) _a ((CH ₃ ) ₂ SiO _1/2 CH ₂ CH ₂ ) _{2c + d + e} (H (CH ₃ ) ₂ SiO _1/2 ) _{b- (2c + d + e)} } (((CH ₃ ) ₂ SiO) _n (CH ₃ ) ₂ Si) _c (R ⁶ ) _d ((CH ₃ ) ₃ Si) _e (5)
(Wherein R ⁶ represents an epoxy group-containing group, a, b, c, d, e and n are real numbers, a> 0, b> 0, c> 0, d> 0, e ≧ 0, n > 0 and b ≧ 2c + d + e.)
The siloxane derivative of any one of Claims 1-6 containing the structural unit represented by these.   Hardened | cured material formed by superposing | polymerizing the siloxane derivative of any one of Claims 1-7.   The hardened | cured material of Claim 8 formed by superposing | polymerizing using an acid anhydride as a hardening | curing agent.   The hardened | cured material of Claim 9 formed by superposing | polymerizing further using a hardening accelerator.   The curing according to claim 9 or 10, wherein the acid anhydride present in the cured product is polymerized so that the acid anhydride / epoxy group = 0.01 to 0.8 in an equivalent ratio to the epoxy group. object.   The hardened | cured material of Claim 8 formed by superposing | polymerizing using a cationic polymerization initiator as a polymerization initiator.   The hardened | cured material of any one of Claims 8-12 formed by superposing | polymerizing with a heat | fever.   The optical-semiconductor sealing material which consists of hardened | cured material of any one of Claims 8-13.