JP2012188655A - Polysiloxane-based composition, sealant formed by using this composition, and optical device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polysiloxane-based composition that has high heat resistance and light resistance and also is excellent in gas barrier properties, thermal shock resistance, and light-extraction efficiency; a sealant formed by using this composition; and an optical device.SOLUTION: This polysiloxane-based composition includes (A) a polyhedron-structure polysiloxane modified product obtained by modifying (a) an alkenyl group-containing, polyhedron-structure polysiloxane-based compound with (b) a hydrosilyl group-containing compound; (B) an organopolysiloxane having two or more alkenyl groups in a molecule; and (C) a cyclic olefin compound having one carbon-carbon double bond in a molecule.

Description

The present invention relates to a polysiloxane composition having high heat resistance and light resistance, excellent gas barrier properties, cold shock resistance, and light extraction efficiency, a sealing agent using the composition, and an optical device.

  The polysiloxane composition is excellent in heat resistance, cold resistance, weather resistance, light resistance, chemical stability, electrical properties, flame resistance, water resistance, transparency, coloring, non-adhesiveness, and non-corrosion It is used in various industries. Among these, compositions composed of polysiloxanes having a polyhedral structure are known to exhibit even better heat resistance, light resistance, chemical stability, low dielectric properties, etc. due to their specific chemical structure. The application is expected.

  As an application example using a polysiloxane having a polyhedral structure, there is one intended to be used for an optical element sealing agent. For example, in Patent Document 1, a polysiloxane having a polyhedral structure containing two or more oxetanyl groups Disclosed is a polysiloxane composition having a polyhedral skeleton containing a resin, an aliphatic hydrocarbon containing one or more epoxy groups, and a cationic polymerization initiator. This material has high refraction and light extraction efficiency. high. However, since the polysiloxane composition described here has an oxetanyl group or an epoxy group, it has a problem of low heat resistance and light resistance.

  For such a problem, for example, in Patent Document 2, the problem of heat resistance and light resistance is improved by limiting the glass transition temperature of polyorganopolysiloxane having an epoxy group. Even after the impact test, cracks are unlikely to occur. However, it is still difficult to use in applications where high heat resistance and light resistance such as white LEDs are required, and the material is not satisfactory in crack resistance.

  In addition, the polysiloxane composition has excellent characteristics, but generally has a problem of low gas barrier properties. Therefore, when a polysiloxane composition having a low gas barrier property is used as a sealing material, there is a problem that the reflector is blackened by sulfides. For example, in Patent Document 3, a metal member is previously provided with a gas barrier property. The coating treatment is performed with a high acrylic resin, and then the sealing is performed with a silicone resin. However, the gas barrier property of the silicone resin itself used in the corresponding technology is low, and after coating with an acrylic resin, it takes a lot of work, such as sealing with a silicone resin, resulting in a problem in productivity.

  Patent Document 4 discloses a composition using a polysiloxane modified body having a polyhedral structure. This composition is excellent in molding processability, transparency, heat resistance / light resistance, and adhesiveness, and can be used as an optical sealant. However, there is still room for further improvement in gas barrier properties.

  As described above, disclosure of materials using polysiloxane is seen, but there are no examples of materials that maintain high heat resistance and light resistance and have excellent thermal shock resistance, gas barrier properties, and light extraction efficiency. The development of new materials was sought.

JP2008-163260 JP2007-169427 JP 2009-206124 A WO08 / 010545

  Provided are a polysiloxane-based composition having high heat resistance and light resistance, excellent in thermal shock resistance, gas barrier properties, and light extraction efficiency, a sealing agent using the composition, and an optical device.

As a result of intensive studies to solve the above problems, the present inventors have
Hereinafter, a polysiloxane composition comprising the components (A), (B), and (C).
(A) A modified polyhedral polysiloxane obtained by modifying a compound (b) having a hydrosilyl group with respect to an alkenyl group-containing polyhedral polysiloxane compound (a),
(B) an organopolysiloxane having two or more alkenyl groups in one molecule;
(C) The present inventors have found that the above problems can be solved by a cyclic olefin compound having one carbon-carbon double bond in one molecule, and have reached the present invention.

1). Hereinafter, a polysiloxane composition comprising the components (A), (B), and (C).
(A) A modified polyhedral polysiloxane obtained by modifying a compound (b) having a hydrosilyl group with respect to an alkenyl group-containing polyhedral polysiloxane compound (a),
(B) an organopolysiloxane having two or more alkenyl groups in one molecule;
(C) Cyclic olefin compound having one carbon-carbon double bond in one molecule 2). The polysiloxane composition according to 1), wherein the component (C) has a weight average molecular weight of less than 1000.

3). The component (C) is represented by the formula C _n H _{2 (nx)}
(N is an integer of 4-20, x is an integer of 1-5) The polysiloxane composition described in 1) or 2) above.

  4). The polysiloxane composition according to any one of 1) to 3), wherein the component (B) is an organopolysiloxane containing an aryl group.

  5). The polysiloxane composition according to any one of 1) to 4), wherein the modified polyhedral polysiloxane (A) is liquid at a temperature of 20 ° C.

  6). The polysiloxane composition according to any one of 1) to 5), wherein the compound (b) having a hydrosilyl group is a cyclic siloxane and / or a linear siloxane containing a hydrosilyl group. .

7). The alkenyl group-containing polyhedral polysiloxane compound (a) has the formula
[AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group , Aryl groups, or groups linked to other polyhedral skeleton polysiloxanes)
The polysiloxane composition according to any one of 1) to 6), which is an alkenyl group-containing polyhedral polysiloxane compound composed of a siloxane unit represented by formula (1):

  8). The modified polyhedral polysiloxane (A) is a hydrosilyl group in a range where 2.5 to 20 hydrogen atoms directly bonded to Si atoms per alkenyl group of the alkenyl group-containing polyhedral polysiloxane compound (a) are present. 8. The compound according to any one of 1) to 7), wherein the compound (b) is modified by adding an excess amount of the compound (b) and is obtained by distilling off the compound (b) having an unreacted hydrosilyl group. A polysiloxane composition.

  9). The polysiloxane composition according to any one of 1) to 8), wherein the modified polyhedral polysiloxane (A) has at least three hydrosilyl groups in the molecule.

10). The polyhedral polysiloxane modified (A) component is
[XR ³ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom, an alkyl group, or an aryl group Or a group linked to another polyhedral skeleton polysiloxane, X has a structure represented by the following general formula (1) or general formula (2), and when there are a plurality of X, the general formula (1 ) Or the structure of the general formula (2) may be different, or the structure of the general formula (1) or the general formula (2) may be mixed.

(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain Yes, and may be the same or different, provided that at least one of Y or Z is a hydrogen atom; R is an alkyl group or an aryl group, and may be the same or different. .) Is a structural unit. The polysiloxane composition according to any one of 1) to 9).

  11). The polysiloxane composition according to any one of 1) to 10), which contains a hydrosilylation catalyst.

  12). The polysiloxane composition according to any one of 1) to 11), further comprising a curing retarder.

  13). The polysiloxane composition according to any one of 1) to 12), further comprising an inorganic filler.

  14). Hardened | cured material formed using the polysiloxane type composition of any one of 1) -13).

  15). The cured product according to 14), wherein at least one maximum value of loss tangent measured at a frequency of 10 Hz is in a temperature range of −40 ° C. to 50 ° C., and a storage elastic modulus is 10 MPa or less at 50 ° C.

16). 40 ° C., the cured product according to 14) or 15), wherein the moisture permeability of 90% humidity is not more than ^30g / m 2 / 24h.

  17). The sealing agent which uses the polysiloxane type composition of any one of 1) -13).

  18). The sealant according to 17), wherein the sealant is a sealant for optical materials.

  19). The sealing agent according to 17) or 18), wherein the sealing agent is a high-luminance LED sealing agent.

  20). An optical device used as the sealant according to any one of 17) to 19).

A polysiloxane composition having high heat resistance and light resistance, excellent thermal shock resistance, gas barrier properties, and light extraction efficiency, a sealing agent using the composition, and an optical device can be provided. .

Hereinafter, the present invention will be described in detail.
<Alkenyl group-containing polyhedral polysiloxane compound (a)>
The alkenyl group-containing polyhedral polysiloxane compound (a) in the present invention is not particularly limited as long as it is a polysiloxane having an alkenyl group in the molecule and having a polyhedral skeleton. Specifically, for example, the following formula [R ⁵ SiO _3/2 ] _x [R ⁶ SiO _3/2 ] _y
(X + y is an integer of 6 to 24; x is an integer of 1 or more, y is 0 or an integer of 1 or more; R ⁵ is an alkenyl group or a group having an alkenyl group; R ⁶ is any organic group, or Groups linked to other polyhedral skeleton polysiloxanes)
An alkenyl group-containing polyhedral polysiloxane compound composed of a siloxane unit represented by the formula
[AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group , Aryl groups, or groups linked to other polyhedral skeleton polysiloxanes)
An alkenyl group-containing polyhedral polysiloxane compound composed of siloxane units represented by the formula:

  Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.

R ¹ is an alkyl group or an aryl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a cyclopentyl group. Examples of the aryl group include aryl groups such as a phenyl group and a tolyl group. Is done. R ¹ in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.
R ² is a hydrogen atom, an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and a cyclopentyl group. Examples of the aryl group include aryl groups such as a phenyl group and a tolyl group. Is done. R ² in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.
a is not particularly limited as long as it is an integer of 1 or more, but is preferably 2 or more, and more preferably 3 or more, from the handleability of the compound and the physical properties of the resulting cured product. Further, b is not particularly limited as long as it is 0 or an integer of 1 or more.

The sum of a and b (= a + b) is an integer from 6 to 24, but from the viewpoint of the stability of the compound and the stability of the resulting cured product, it should be 6 to 12, and more preferably 6 to 10. preferable.
The method for synthesizing the polyhedral polysiloxane compound (a) containing an alkenyl group is not particularly limited, and can be synthesized using a known method. As a synthesis method, for example, a silane of R ⁷ SiX ^a ₃ (wherein R ⁷ represents R ⁵ and R ⁶ described above, and X ^a represents a hydrolyzable functional group such as a halogen atom or an alkoxy group). It is obtained by the hydrolysis condensation reaction of the compound. Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by hydrolysis condensation reaction of R ⁷ SiX ^a _3, the ring is closed by reacting the same or different trifunctional silane compounds, and the polyhedron Methods for synthesizing structural polysiloxanes are also known.

  In addition, for example, there is a method of hydrolytic condensation of tetraalkoxysilane such as tetraethoxysilane in the presence of a base such as quaternary ammonium hydroxide. In this synthesis method, a silicate having a polyhedral structure is obtained by a hydrolytic condensation reaction of tetraalkoxysilane, and the obtained silicate is further reacted with a silylating agent such as an alkenyl group-containing silyl chloride. It is possible to obtain a polyhedral polysiloxane in which Si atoms and alkenyl groups forming a polyhedral structure are bonded through a siloxane bond. In the present invention, the same polyhedral polysiloxane can be obtained from a substance containing silica such as silica or rice husk instead of tetraalkoxylane.

<Compound (b) having hydrosilyl group>
The compound having a hydrosilyl group used in the present invention is not particularly limited as long as it has one or more hydrosilyl groups in the molecule, but the obtained polyhedral polysiloxane modified product has transparency, heat resistance, and light resistance. From the viewpoint, it is preferably a siloxane compound having a hydrosilyl group, and more preferably a cyclic siloxane or a linear polysiloxane having a hydrosilyl group. These compounds having a hydrosilyl group may be used alone or in combination of two or more.

Linear polysiloxanes containing hydrosilyl groups include copolymers of dimethylsiloxane units, methylhydrogensiloxane units, and terminal trimethylsiloxy units, and diphenylsiloxane units, methylhydrogensiloxane units, and terminal trimethylsiloxy units. Polymer, copolymer of methylphenylsiloxane unit, methylhydrogensiloxane unit and terminal trimethylsiloxy unit, polydimethylsiloxane blocked with dimethylhydrogensilyl group, terminal blocked with dimethylhydrogensilyl group Examples thereof include polydiphenylsiloxane and polymethylphenylsiloxane whose end is blocked with a dimethylhydrogensilyl group.
In particular, a linear polysiloxane containing a hydrosilyl group is a polysiloxane having a molecular end blocked with a dimethylhydrogensilyl group from the viewpoints of reactivity during modification, heat resistance and light resistance of the resulting cured product. Polysiloxane having a molecular end blocked with a dimethylhydrogensilyl group can be suitably used, and specific examples thereof include tetramethyldisiloxane and hexamethyltrisiloxane. .

  As cyclic siloxanes containing hydrosilyl groups, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen- 1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydro Gen-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9 , 11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane and the like. As the cyclic siloxane in the present invention, specifically from the viewpoint of industrial availability and reactivity when modified, or heat resistance, light resistance, strength, etc. of the obtained cured product, for example, 1, 3, 5, 7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane can be preferably used.

  In the present invention, from the viewpoint of heat resistance and light resistance, the Si atom is preferably composed of a hydrogen atom, a vinyl group and a methyl group.

<Hydrosilylation catalyst>
In the present invention, a hydrosilylation catalyst is used when the polyhedral polysiloxane modified product (A) is synthesized and the polysiloxane composition using the compound is cured.

  As the hydrosilylation catalyst used in the present invention, a known hydrosilylation catalyst can be used, and there is no particular limitation.

Specifically, for example, a platinum-olefin complex, chloroplatinic acid, a simple substance of platinum, a carrier (alumina, silica, carbon black, etc.) supported by solid platinum; a platinum-vinylsiloxane complex, for example, Pt _n (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ; platinum-phosphine complex, such as Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ; platinum-phosphite complex, such as Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer) , Pt (acac) _2, also platinum described in U.S. Patent 3,159,601 and in Pat 3159662 of Ashby et al - hydrocarbon complex, and Lamoreaux et al U.S. Patent Platinum is described in the 3220972 Pat Arcola - DOO catalysts may be mentioned.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable.

<Modified polyhedral polysiloxane (A)>
The modified polyhedral polysiloxane (A) can be synthesized by a hydrosilylation reaction between an alkenyl group-containing polyhedral compound (a) and a compound having a hydrosilyl group (b) in the presence of a hydrosilylation catalyst. . At this time, all the alkenyl groups of the modified polyhedral polysiloxane (A) do not need to react and may partially remain.

  The addition amount of the compound having a hydrosilyl group should be used so that the number of hydrogen atoms directly bonded to the Si atom is 2.5 to 20 per one alkenyl group of the polyhedral polysiloxane compound (A). Is preferred. If the addition amount is small, gelation proceeds due to a crosslinking reaction, so that the polyhedral polysiloxane modified product (A) has poor handling properties, and if too large, the physical properties of the cured product may be adversely affected.

  In addition, when synthesizing the polyhedral polysiloxane modified product (A), the compound (b) having an excessive amount of hydrosilyl group is present, so that the compound (b) having an unreacted hydrosilyl group under reduced pressure and heating conditions, for example, ) Is preferably removed.

There is no particular restriction on the amount of the hydrosilylation catalyst used during modified polyhedral polysiloxane (A) Synthesis, 10 ^-1 for the alkenyl group 1 mole of Arukenikeniru group-containing polyhedral polysiloxane compound (a) It is good to use in the range of ^10-10 mol. Preferably it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. If there are too many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light with a short wavelength, which may cause coloration or decrease the light resistance of the resulting cured product. May foam. Moreover, when there are too few hydrosilylation catalysts, reaction may not progress and there exists a possibility that a target object may not be obtained.

  As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC, More preferably, it is 45-140 degreeC. If the temperature is too low, the reaction does not proceed sufficiently, and if the temperature is too high, gelation may occur and handling properties may deteriorate.

  The modified polyhedral polysiloxane (A) thus obtained can ensure compatibility with various compounds, particularly siloxane compounds, and further, since a hydrosilyl group is introduced into the molecule, It becomes possible to react with a compound having alkenyl. Specifically, a cured product can be obtained by reacting with an organopolysiloxane (B) having two or more alkenyl groups in one molecule described later. At this time, it is preferable that at least three hydrosilyl groups in the modified polyhedral polysiloxane (A) are contained in the molecule. When the number of hydrosilyl groups is less than 3, the strength of the resulting cured product may be insufficient.

  In addition, the polyhedral polysiloxane modified body (A) in the present invention can be liquefied at a temperature of 20 ° C. Such a modified liquid polyhedral polysiloxane (A) is obtained, for example, by modifying an alkenyl group-containing polyhedral polysiloxane compound (a) with a cyclic siloxane having a hydrosilyl group or a linear polysiloxane. be able to. The polyhedral structure-resistant polysiloxane modified product (A) is preferably in a liquid form because of excellent handling properties.

As the polyhedral polysiloxane modified body (A) component in the present invention,
[XR ³ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom, an alkyl group, or an aryl group Or a group linked to another polyhedral skeleton polysiloxane, X has a structure represented by the following general formula (1) or general formula (2), and when there are a plurality of X, the general formula (1 ) Or the structure of the general formula (2) may be different, or the structure of the general formula (1) or the general formula (2) may be mixed.

(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain Yes, and may be the same or different, provided that at least one of Y or Z is a hydrogen atom; R is an alkyl group or an aryl group, and may be the same or different. .) Is a preferred example from the viewpoint of heat resistance, light resistance, or strength of the resulting cured product.

<(B) Organopolysiloxane having two or more alkenyl groups in one molecule>
The component (B) in the present invention preferably contains 2 or more alkenyl groups in one molecule, and more preferably 2 to 10 alkenyl groups. If the number of alkenyl groups in one molecule is too large, the heat and light resistance may be reduced.

  The number of siloxane units of the component (B) in the present invention is not particularly limited, but is preferably 2 or more, and more preferably 2 to 10. When the number of siloxane units in one molecule is small, volatilization tends to occur from within the polysiloxane composition, and desired physical properties may not be obtained. Moreover, when there are many siloxane units, gas barrier property may become low, such as the water vapor transmission rate of the obtained hardened | cured material becoming high.

  The component (B) in the present invention preferably contains an aryl group from the viewpoint of gas barrier properties. The component (B) containing an aryl group preferably has an aryl group bonded directly on the Si atom from the viewpoint of heat resistance and light resistance. The aryl group may be on either the side chain or the end of the molecule. Further, the molecular structure of the aryl group-containing organopolysiloxane is not limited, and for example, it may have a cyclic structure in addition to a straight chain, a branched chain, or a partially branched chain.

  Examples of such aryl groups include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, and 4-ethylphenyl. Group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 3-isobutylphenyl group, 4-isobutylphenyl group, 3-tbutylphenyl group, 4-tbutylphenyl group, 3-pentylphenyl group, 4-pentylphenyl group, 3-hexylphenyl group, 4-hexylphenyl group, 3-cyclohexylphenyl group, 4-cyclohexylphenyl group, 2,3-dimethylphenyl Group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,3-diethylphenyl group, 2,4-diethylphenyl group, 2,5-diethylphenyl group, 2,6-diethylphenyl group, 3,4-diethylphenyl group, 3,5-diethylphenyl group, cyclohexylphenyl group, biphenyl group, 2,3 2,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,4,5-trimethylphenyl group, 3-epoxyphenyl group, 4-epoxyphenyl group, 3-glycidylphenyl group, 4-glycidylphenyl group Etc. Among these, a phenyl group is a preferred example from the viewpoint of heat resistance and light resistance. These may be used alone or in combination of two or more.

  The component (B) in the present invention is a linear polysiloxane having two or more alkenyl groups, a polysiloxane having two or more alkenyl groups at the molecular end, and two or more alkenyl groups from the viewpoint of heat resistance and light resistance. Preferred examples include polysiloxanes having alkenyl groups such as cyclic siloxanes. These compounds having an alkenyl group may be used alone or in combination of two or more.

  Specific examples of the linear polysiloxane having two or more alkenyl groups include copolymers of dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units. Copolymer, methylphenylsiloxane unit, copolymer of methylvinylsiloxane unit and terminal trimethylsiloxy unit, polydimethylsiloxane blocked with dimethylvinylsilyl group, endblocked with dimethylvinylsilyl group Polydiphenylsiloxane, polymethylphenylsiloxane end-capped with dimethylvinylsilyl groups, copolymers of dimethylsiloxane units with methylvinylsiloxane units and terminal triethylsiloxy units, diphenylsiloxy Copolymers of emission units and methylvinylsiloxane units and end triethylsiloxy units, and a copolymer of methylphenylsiloxane units and methylvinylsiloxane units and end triethylsiloxy unit is exemplified. Among them, from the viewpoint of heat resistance and light resistance, a copolymer of a dimethylsiloxane unit, a methylvinylsiloxane unit and a terminal trimethylsiloxy unit, a copolymer of a diphenylsiloxane unit, a methylvinylsiloxane unit and a terminal trimethylsiloxy unit, methylphenyl Copolymers of siloxane units with methylvinylsiloxane units and terminal trimethylsiloxy units, polydimethylsiloxanes blocked with dimethylvinylsilyl groups, polydiphenylsiloxanes blocked with dimethylvinylsilyl groups, dimethylvinylsilyl groups A preferable example is polymethylphenylsiloxane whose end is blocked with a polymethylphenylsiloxane.

Specific examples of the polysiloxane having two or more alkenyl groups at the molecular ends include polysiloxanes whose ends are blocked with the dimethylalkenyl groups exemplified above, dimethylalkenylsiloxane units and SiO ₂ units, SiO _3/2 units, SiO 2 In a group consisting of at least one siloxane unit selected from the group consisting of units, a polysiloxane end-capped with a diethyl alkenyl group, a diethyl alkenyl siloxane unit and a SiO ₂ unit, a SiO _3/2 unit, a SiO unit Examples thereof include polysiloxane composed of at least one selected siloxane unit. Among them, from the viewpoint of heat resistance and light resistance, at least one siloxane unit selected from the group consisting of a polysiloxane blocked with a dimethylalkenyl group, a dimethylalkenylsiloxane unit, a SiO ₂ unit, a SiO _3/2 unit, and a SiO unit. A preferred example is polysiloxane consisting of:

Examples of the cyclic siloxane compound having two or more alkenyl groups include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetravinyl-1 -Phenyl-3,5,7-trimethylcyclotetrasiloxane, 1,3,5,7-tetravinyl-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-tetravinyl -1,5-diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-tetravinyl-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1-phenyl-3,5 , 7-trivinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-diphenyl-5,7-divinyl-1,3,5,7-tetramethylcycloteto Siloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3 , 5,7,9,11-hexavinyl-1,3,5,7,9,11-hexamethylcyclosiloxane, 1-propyl-3,5,7-trivinyl-1,3,5,7-tetramethyl Examples include cyclotetrasiloxane and 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane. Among these, from the viewpoint of heat resistance and light resistance, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetravinyl-1-phenyl- 3,5,7-trimethylcyclotetrasiloxane, 1,3,5,7-tetravinyl-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-tetravinyl-1, 5-diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-tetravinyl-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1-phenyl-3,5,7- Trivinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-diphenyl-5,7-divinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5- Livinyl-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11 -Hexavinyl-1,3,5,7,9,11-hexamethylcyclosiloxane is a preferred example.
These may be used alone or in combination of two or more.

  The amount of organopolysiloxane having two or more alkenyl groups in one molecule as component (B) can be variously set, but is included in the polyhedral polysiloxane modified material as component (A) per alkenyl group. It is desirable to add 0.3 to 5, preferably 0.5 to 3 hydrogen atoms directly connected to Si atoms. If the ratio of the alkenyl group is too small, appearance defects due to foaming and the like are likely to occur, and if too large, the physical properties of the cured product may be adversely affected.

<(C) Cyclic olefin compound having one carbon-carbon double bond in one molecule>
The cyclic olefin compound (C) having one carbon-carbon double bond in one molecule in the present invention reacts with the hydrosilyl group of the component (A). By using the component (C) in the present invention, the elastic modulus of the cured product can be reduced, and further, the thermal shock resistance, fracture strength, gas barrier properties, light extraction efficiency, and the like can be improved.
(C) component in this invention should just be a cyclic olefin compound which has one carbon-carbon double bond in 1 molecule, and this carbon-carbon double bond is any of a vinylene group, a vinylidene group, and an alkenyl group. It may be. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a hexenyl group, and a vinyl group is preferable from the viewpoint of heat resistance and light resistance.
(C) component in the present invention, the average molecular weight may be at 1000, as a more preferred example, the following formula _{C n H 2 (n-x} )
The cyclic olefin compound represented by (n is an integer of 4-20, x is an integer of 1-5) is mentioned as a preferable example from a reactive viewpoint with (b) component.

Examples of such cyclic olefin compounds include aliphatic cyclic olefin compounds and substituted aliphatic cyclic olefin compounds.
Specific examples of the aliphatic cyclic olefin compound include cyclohexene, cycloheptene, cyclooctene, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, allylcyclohexane, allylcycloheptane, allylcyclooctane, and methylenecyclohexane. It is done.

  Specific examples of the substituted aliphatic cyclic olefin compound include norbornene, 1-methylnorbornene, 2-methylnorbornene, 7-methylnorbornene, 2-vinylnorbornane, 7-vinylnorbornane, 2-allylnorbornane, 7-allylnorbornane, 2-methylene norbornane, 7-methylene norbornane, camphene, vinyl norcamphene, 6-methyl-5-vinyl-bicyclo [2,2,1] -heptane, 3-methyl-2-methylene-bicyclo [2,2,1 ] -Heptane, α-pinene, β-pinene, 6,6-dimethyl-bicyclo [3,1,1] -2-heptaene, longifolene, 2-vinyladamantane, 2-methyleneadamantane and the like.

  Among these, cyclohexene, vinylcyclohexane, norbornene, camphene, and pinene are preferable examples from the viewpoint of availability.

  These cyclic olefin compounds (C) having one carbon-carbon double bond in one molecule may be used alone or in combination of two or more.

  The addition amount of the cyclic olefin compound (C) having one carbon-carbon double bond in one molecule is the carbon-carbon of the component (C) per hydrosilyl group of the compound (b) having a hydrosilyl group described later. It is preferable to use so that the number of double bonds may be 0.01-0.5. When the addition amount is small, the thermal shock resistance of the resulting cured product may be lowered, and when the addition amount is large, a curing failure may occur in the resulting cured product.

<Hydrosilylation catalyst>
In the present invention, a hydrosilylation catalyst is used in synthesizing a polyhedral polysiloxane modified product and curing the composition containing the modified product.

  As the hydrosilylation catalyst used in the present invention, a known hydrosilylation catalyst can be used, and there is no particular limitation.

Specifically, for example, a platinum-olefin complex, chloroplatinic acid, a simple substance of platinum, a carrier (alumina, silica, carbon black, etc.) supported by solid platinum; a platinum-vinylsiloxane complex, for example, Pt _n (ViMe ₂ SiOSiMe ₂ Vi) _n , Pt [(MeViSiO) ₄ ] _m ; platinum-phosphine complex, such as Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ; platinum-phosphite complex, such as Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer) , Pt (acac) _2, also platinum described in U.S. Patent 3,159,601 and in Pat 3159662 of Ashby et al - hydrocarbon complex, and Lamoreaux et al U.S. Patent Platinum is described in the 3220972 Pat Arcola - DOO catalysts may be mentioned.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable.

<Curing retarder>
The curing retarder is a component for improving the storage stability of the polysiloxane composition of the present invention or adjusting the reactivity of the hydrosilylation reaction during the curing process. In the present invention, as the retarder, known compounds used in addition-type curable compositions with hydrosilylation catalysts can be used. Specifically, compounds containing aliphatic unsaturated bonds, organophosphorus compounds , Organic sulfur compounds, nitrogen-containing compounds, tin compounds, organic peroxides, and the like. These may be used alone or in combination of two or more.

  Specific examples of the compound containing an aliphatic unsaturated bond include 3-hydroxy-3-methyl-1-butyne, 3-hydroxy-3-phenyl-1-butyne, and 3,5-dimethyl-1- Examples thereof include propargyl alcohols such as hexyn-3-ol and 1-ethynyl-1-cyclohexanol, ene-yne compounds, maleic acid esters such as maleic anhydride and dimethyl maleate, and the like.

  Specific examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite.

  Specific examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide, and the like.

  Specific examples of nitrogen-containing compounds include N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, and N, N-dibutyl. -1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N-dibutyl-1,4-butanediamine, 2,2 Examples include '-bipyridine.

  Specific examples of tin compounds include stannous halide dihydrate, stannous carboxylate, and the like.

  Specific examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate. Of these, dimethyl maleate, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl-1-cyclohexanol can be exemplified as particularly preferred curing retarders.

The addition amount of the curing retarder is not particularly limited, but is preferably used in the range of 10 ⁻¹ to 10 ³ mol, more preferably in the range of 1 to 100 mol, per 1 mol of the hydrosilylation catalyst. preferable. Moreover, these hardening retarders may be used independently and may be used in combination of 2 or more types.

<Inorganic filler>
An inorganic filler can be added to the polysiloxane composition of the present invention as necessary.
By using an inorganic filler as the composition of the polysiloxane composition of the present invention, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical characteristics, light reflectance of the molded product obtained Various physical properties such as flame retardancy, fire resistance, and gas barrier properties can be improved.
The inorganic filler is not particularly limited as long as it is an inorganic substance or a compound containing an inorganic substance. Specifically, for example, quartz, fumed silica, precipitated silica, silicic anhydride, fused silica, crystalline silica, ultrafine powder amorphous silica, etc. Silica-based inorganic filler, alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass fiber, glass flake, alumina fiber, carbon fiber, mica, graphite, carbon black, Examples thereof include ferrite, graphite, diatomaceous earth, white clay, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloon, and silver powder. These may be used alone or in combination of two or more.

  The inorganic filler may be appropriately subjected to a surface treatment. Examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, treatment with a coupling agent, and the like, but are not particularly limited.

  An example of the coupling agent is a silane coupling agent. The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesiveness and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

  Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Alkoxysilanes which can be mentioned.

  By using the inorganic filler as a component of the polysiloxane composition, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical characteristics, light reflectance, and difficulty of the resulting molded body are obtained. Various physical properties such as flammability and fire resistance can be improved.

As the shape of the inorganic filler, various types such as a crushed shape, a piece shape, a spherical shape, and a rod shape can be used. The average particle size and particle size distribution of the inorganic filler are not particularly limited, but from the viewpoint of gas barrier properties, the average particle size is preferably 0.005 to 50 μm, more preferably 0.01 to 20 μm. More preferably. Similarly, the BET specific surface area, although not particularly limited, from the viewpoint of gas barrier properties, it is preferably ^70m 2 / g or more, more preferably 100 m ² / g or more, further 200 meters ² / It is especially preferable that it is g or more. Here, the BET specific surface area is the specific surface area of the particles calculated by the gas adsorption method, and the specific surface area of the particles by the gas adsorption method is calculated using a gas molecule whose adsorption occupation area is known like nitrogen gas. The specific surface area of the particles is calculated from the amount adsorbed on the particles. The BET specific surface area can accurately calculate the amount of gas molecules adsorbed directly on the solid surface (monomolecular layer adsorption amount). The BET specific surface area can be calculated using a mathematical formula called a BET formula shown below.

  As shown in the following formula (1), the BET formula shows the relationship between the adsorption equilibrium pressure P and the adsorption amount V at that pressure when the adsorption equilibrium state is maintained at a constant temperature, and is expressed as follows.

Formula (1): P / V (Po−P) = (1 / VmC) + ((C−1) / VmC) (P / Po) (Po: saturation vapor pressure, Vm: monomolecular layer adsorption amount, gas Adsorption amount when a molecule forms a monolayer on a solid surface, C: parameter related to heat of adsorption (> 0))
By calculating the monomolecular adsorption amount Vm from the above equation and multiplying this by the cross-sectional area occupied by one gas molecule, the surface area of the particles can be obtained.

  Although the addition amount of an inorganic filler is not specifically limited, It is 1-1000 weight part with respect to 100 weight part of the mixture of (A) component, (B) component, and (C) component, More preferably, it is 5-500 weight part. More preferably, it is 10 to 300 parts by weight. When the amount of the inorganic filler added is too large, the fluidity may be deteriorated, and when it is small, the physical properties of the obtained molded article may be insufficient.

  The order of mixing the inorganic filler is not particularly limited, but in the point that the storage stability tends to be good, after mixing with the component (B), there is a method of mixing with the component (A) and the component (C). desirable. In addition, (A) component, (B) component, (C) in that (A) component, (B) component, and (C) component which are reaction components are well mixed and a stable molded product is easily obtained. It is preferable to mix an inorganic filler with a mixture of components.

  The means for mixing these inorganic fillers is not particularly limited, but specifically, for example, a stirrer such as a two-roll or three-roll, a planetary stirring deaerator, a homogenizer, a dissolver, a planetary mixer, etc. And melt kneaders such as a plast mill. The mixing of the inorganic filler may be performed at normal temperature, may be performed by heating, may be performed under normal pressure, or may be performed under reduced pressure. If the temperature during mixing is high, the composition may be cured before molding.

<Polysiloxane composition and cured product>
The polysiloxane composition of the present invention comprises (A) a modified polyhedral polysiloxane, (B) an organopolysiloxane having two or more alkenyl groups in one molecule, and (C) carbon-carbon 2 in one molecule. Although it consists of a cyclic olefin compound having one heavy bond, it can be obtained by adding a hydrosilylation catalyst, a curing retarder, an inorganic filler, an adhesion-imparting agent, etc., if necessary.

  The adhesion-imparting agent is used for the purpose of improving the adhesion between the polysiloxane-based composition and the substrate in the present invention, and is not particularly limited as long as it has such an effect, but the silane coupling agent Can be illustrated as a preferred example.

  The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handling. From the viewpoints of adhesiveness and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

Specific preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldisilane. Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- Alkoxysilanes having an epoxy functional group such as (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysila Alkoxysilanes having a methacrylic group or an acrylic group such as 3-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Is mentioned. These may be used alone or in combination of two or more.
As addition amount of a silane coupling agent, it is preferable that it is 0.05-30 weight part with respect to 100 weight part of mixture of (A) component and (B) component, More preferably, it is 0.1-10. Parts by weight. If the addition amount is small, the effect of improving the adhesiveness does not appear, and if the addition amount is large, the physical properties of the cured product may be adversely affected.

  In the present invention, a known adhesion promoter can be used to enhance the effect of the adhesion promoter. Adhesion promoters include, but are not limited to, epoxy-containing compounds, epoxy resins, boronic ester compounds, organoaluminum compounds, and organotitanium compounds.

  The polysiloxane composition of the present invention can be handled as a liquid resin composition. By using a liquid composition, a molded body can be easily obtained by pouring into a mold, a package, a substrate, etc., and curing by heating. The molded body obtained by the polysiloxane composition of the present invention has high hardness and low thermal expansion coefficient, and is excellent in thermal dimensional stability.

  When adding temperature when making it harden | cure, Preferably it is 30-400 degreeC, More preferably, it is 50-250 degreeC. If the curing temperature is too high, the resulting cured product tends to have poor appearance, and if it is too low, curing is insufficient. Moreover, you may make it harden | cure combining the temperature conditions of two or more steps. Specifically, for example, by raising the curing temperature stepwise such as 70 ° C., 120 ° C., and 150 ° C., a preferable cured product can be obtained, which is preferable.

In the present invention, a hydrosilylation catalyst can be additionally used as necessary.
The curing time can be appropriately selected depending on the curing temperature, the amount of hydrosilylation catalyst used and the amount of hydrosilyl group, and other combinations of the composition of the present application. Preferably, a cured product can be obtained by performing the treatment for 10 minutes to 8 hours.

  Specifically, the polysiloxane composition in the present invention can be used by being injected or applied to, for example, a package or a substrate. After the injection or application, a molded body corresponding to the application can be easily obtained by curing under the above-mentioned curing conditions.

  The polysiloxane composition of the present invention may optionally contain various additives such as phosphors, colorants, heat resistance improvers, reaction control agents, mold release agents, and dispersants for fillers. Can be added. Examples of the filler dispersant include diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane, and the like. In addition, it is preferable to stop these arbitrary components to the minimum addition amount so that the effect of this invention may not be impaired.

  In the polysiloxane composition used in the present invention, the above-mentioned components are uniformly mixed using a kneader such as a roll, a Banbury mixer, a kneader, or a planetary stirring deaerator, and subjected to heat treatment as necessary. Or you may.

  The polysiloxane composition of the present invention can be used as a molded article. As a molding method, any method such as extrusion molding, compression molding, blow molding, calender molding, vacuum molding, foam molding, injection molding, liquid injection molding, and cast molding can be used.

  Specific uses of the molded product obtained in the present invention include, for example, substrate materials in the field of liquid crystal displays, light guide plates, prism sheets, deflection plates, retardation plates, viewing angle correction films, adhesives, color filters, polarizers. Examples of peripheral materials for liquid crystal display devices such as protective films and films for liquid crystals such as passivation films are exemplified. It is also used in PDP (plasma display) sealants, antireflection films, optical correction films, housing materials, front glass protective films, front glass substitute materials, adhesives, color filters, passivation films, and LED display devices. LED element mold material, front glass protective film, front glass substitute material, adhesive, color filter, passivation film, substrate material for plasma addressed liquid crystal display, light guide plate, prism sheet, deflector plate, retardation plate, field of view Corner correction film, adhesive, color filter, polarizer protective film, passivation film, front glass protective film, front glass substitute material, color filter, adhesive, passivation film, and field emission in organic EL displays Various film substrate in Isupurei (FED), front glass protective films, front glass substitute material, adhesive, a color filter, a passivation film is exemplified.

  In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Examples include rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, and glass substitutes. Moreover, the multilayer glass for rail vehicles is illustrated. Further, examples thereof include a toughness imparting agent for aircraft structural materials, engine peripheral members, wireness for protection and binding, and corrosion-resistant coating.

  In the construction field, interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials are exemplified. In agriculture, a house covering film is exemplified.

Next-generation DVDs, organic EL element peripheral materials, organic photorefractive elements, light-amplifying elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, etc. Examples thereof include fiber materials, element sealants, and adhesives.
In addition, the polysiloxane composition obtained in the present invention can be used in the optical device described below.

<Optical device>
The optical device of the present invention is an optical device using the polysiloxane composition of the present invention.
By using the polysiloxane composition of the present invention, the composition has low moisture permeability and is useful as an optical element sealant, and an optical device can be produced using the sealant.
As the optical device of the present invention, specifically, in the optical recording field, for example, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD ( Phase change disk), disk substrate materials for optical cards, pickup lenses, protective films, and sealants. More specifically, optical pickup members such as next-generation DVDs, such as pickup lenses, collimator lenses, objective lenses, sensor lenses, protective films, element sealants, sensor sealants, gratings, adhesives, prisms It can be suitably used for wave plates, correction plates, splitters, holograms, mirrors and the like.

  In the field of optical equipment, examples include still camera lens materials, viewfinder prisms, target prisms, viewfinder covers, and light receiving sensor sections. In addition, a photographing lens and a viewfinder of a video camera are exemplified. Moreover, the projection lens of a projection television, a protective film, a sealing agent, an adhesive agent, etc. are illustrated. Examples are materials for lenses of optical sensing devices, sealants, adhesives, and films.

  In the field of optical components, fiber materials, lenses, waveguides, element sealants, adhesives and the like around optical switches in optical communication systems are exemplified. Examples include optical fiber materials, ferrules, sealants, adhesives and the like around the optical connector. Examples of optical passive components and optical circuit components include lenses, waveguides, LED element sealants, adhesives, and the like. Examples include substrate materials, fiber materials, element sealants, adhesives, and the like around an optoelectronic integrated circuit (OEIC).

  In the field of optical fibers, examples include sensors for industrial use such as lighting and light guides for decorative displays, displays and signs, and optical fibers for communication infrastructure and for connecting digital devices in the home.

  Examples of the semiconductor integrated circuit peripheral material include an interlayer insulating film, a passivation film, an LSI, and a resist material for microlithography for an LSI material.

<Moisture permeability>
Moisture permeability after formed by using the polysiloxane composition curing of the present invention, the temperature 40 ° C., at a humidity of ^{90%, 30g / m 2 /} 24h although less, more ^20g / m 2 / 24h The following is preferable from the viewpoint of gas barrier properties.
The moisture permeability can be calculated according to the following method.

  A jig is prepared by fixing a 5 cm square polyisobutylene rubber sheet (3 mm thick, 3 cm square inside so as to be a square shape) on top of a 5 cm square plate glass (0.5 mm thick), 1 g of calcium chloride (for moisture measurement) manufactured by Wako Pure Chemical Industries, Ltd. is filled into a square shape and used as a test specimen. Further, a 5 cm square cured product for evaluation (2 mm thickness) is fixed on the upper part, and cured for 24 hours at a temperature of 40 ° C., humidity and 90% RH in a constant temperature and humidity machine (PR-2KP manufactured by ESPEC). The moisture permeability can be calculated according to the following formula (2).

Formula (2): Moisture permeability (g / m ² / 24h) = {(total weight of test specimen after moisture permeability test (g)) − (total weight of specimen before moisture permeability test (g))} × 10000 / 9cm ²
Upon curing the sealing agent using polysiloxane composition of the present invention, the moisture permeability becomes less 30g / m 2 / ^24h, for good low moisture permeability is particularly useful as a LED encapsulant. Moisture by is characteristic moisture permeability of the sealant of the present invention is less than 30g / m 2 / ^24h, further, oxygen, are suppressed gas permeability, such as hydrogen sulfide, and silver lead frame in LED, reflector As a result, it is possible to expect the effect of improving the durability of the LED.

<Viscoelastic behavior of sealing layer>
The cured product comprising the polysiloxane composition in the present invention exhibits a specific viscoelastic behavior.

  In general, when a sinusoidal vibration stress (strain) having an angular frequency ω is applied, the complex elastic modulus in the strain and the stress is expressed as E * = E ′ + iE ″. Rate. When the phase difference between stress and strain is δ, the loss tangent (tan δ) is represented by E ″ / E ′.

  The sealing layer in the present invention is a sealing layer having a maximum value of at least one loss tangent at −40 ° C. to 50 ° C. and a storage elastic modulus at 50 ° C. of 10 MPa or less. The maximum value of the loss tangent is more preferably in the range of −5 ° C. to 45 ° C., and further preferably in the range of 0 ° C. to 45 ° C. If it has a maximum value at low temperature, the gas barrier property of the sealing layer may decrease. If it has a maximum value at high temperature, the internal (residual) stress increases when the sealing layer is cured, and the heat resistance of the sealing layer is reduced. Impact properties may deteriorate. Furthermore, the storage elastic modulus at 50 ° C. is more preferably 8 MPa or less, and further preferably 5 MPa or less. If the storage elastic modulus at 50 ° C. is greater than 10 MPa, the thermal shock resistance of the sealing layer may deteriorate.

  When the viscoelastic behavior of the sealing layer is within the above range, there is no phenomenon such as cracking of the sealing layer that may occur in the manufacturing process of the optical device, and a good optical device can be obtained.

  Next, although the composition of this invention is demonstrated in detail based on an Example, this invention is not limited only to these Examples.

(Preparation of samples for heat resistance test and light resistance test)
A polysiloxane-based composition was filled into a mold and thermally cured in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 5 hours to prepare a sample having a thickness of 2 mm.

(Heat resistance test)
The sample prepared as described above was cured for 200 hours in a convection oven (in air) set at a temperature of 150 ° C. and visually observed. The case where no change in color due to coloring or the like was observed was evaluated as ◯, and the case where it was observed was evaluated as ×.

(Light resistance test)
A metering weather meter (model M6T) manufactured by Suga Test Instruments Co., Ltd. was used. The sample prepared as described above was irradiated with a black panel temperature of 120 ° C. and an irradiance of 0.53 kW / m ² to an integrated irradiance of 50 MJ / m ² and observed visually. The case where no change in color due to coloring or the like was observed was evaluated as ◯, and the case where it was observed was evaluated as ×.
(Crack test)
An LED package manufactured by Enomoto Co., Ltd. (product name: TOP LED 1-IN-1, outer dimensions 3528, 3.5 mm × 2.8 mm × 1.9 mm, inner diameter 2.4 mm), 0.4 mm × 0.4 mm × 0. Two 2 mm single crystal silicon chips were attached with an epoxy adhesive (product name: LOCTITE 348) manufactured by Henkel Japan, and placed in an oven at 150 ° C. for 30 minutes. A polysiloxane-based composition was injected into this LED package, and a sample was prepared by thermosetting in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 6 hours. The cured sample was observed with a microscope. If there was no change, it was rated as ○, and if it cracked or peeled off from the package, it was marked as x.

(Cool thermal shock test, heat cycle (H / C) test)
A polysiloxane-based composition was injected into the LED package, and a sample was prepared by thermosetting in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 6 hours. The sample was subjected to 100 cycles of a high temperature holding at 100 ° C. for 30 minutes and a low temperature holding at −40 ° C. for 30 minutes using a thermal shock tester (TSA-71H-W manufactured by Espec), and then the sample was observed with a microscope. If there was no change after the test, it was rated as ◯, and when cracks occurred or peeling occurred between the packages, it was marked as x.

(Moisture permeability test)
The mold was filled with the polysiloxane-based composition and thermally cured in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 6 hours to prepare a 5 cm square cured product for evaluation (2 mm thickness). . This cured product was cured at room temperature of 25 ° C. and humidity of 55% RH for 24 hours.
The moisture permeability in the present invention is calculated according to the following method.

A jig is prepared by fixing a 5 cm square polyisobutylene rubber sheet (3 mm thick, 3 cm square inside so as to be a square shape) on top of a 5 cm square plate glass (0.5 mm thick), 1 g of calcium chloride (for water measurement) manufactured by Wako Pure Chemical Industries, Ltd. was filled into a square shape and used as a test specimen. Further, a 5 cm square cured product for evaluation (2 mm thick) was fixed on the upper part, and was cured at a temperature of 40 ° C., a humidity of 90% RH for 24 hours in a constant temperature and humidity machine (PR-2KP manufactured by ESPEC).
The moisture permeability was calculated according to the following formula (2).

Formula (2): Moisture permeability (g / m ² / 24h) = {(total weight of test specimen after moisture permeability test (g)) − (total weight of specimen before moisture permeability test (g))} × 10000 / 9.0cm ²

(Hydrogen sulfide test, H ₂ S test)
A polysiloxane composition is injected into an LED package (product name: TOP LED 1-IN-1, external dimensions 3528, 3.5 mm x 2.8 mm x 1.9 mm, inner diameter 2.4 mm) manufactured by Enomoto Co., Ltd. Samples were prepared by thermosetting in an oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 6 hours. This sample was put in a flow type gas corrosion tester (KG130S manufactured by Fact Kei Co., Ltd.), and a hydrogen sulfide exposure test was conducted for 96 hours under the conditions of 40 ° C., 80% RH, and hydrogen sulfide 3 ppm. After the test, the case where the reflector of the package was not discolored was evaluated as ◯, when it was slightly discolored, and when it was blackened, it was evaluated as ×.

(Create sample for dynamic viscoelasticity measurement)
A polysiloxane-based composition is filled in a mold and thermally cured in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 6 hours, and a sample having a length of 35 mm, a width of 5 mm, and a thickness of 2 mm is obtained. Created.

(Dynamic viscoelasticity measurement)
The dynamic viscoelasticity of the sample prepared as described above was measured using a dynamic viscoelasticity measuring device Regel E4000 manufactured by UBM, measurement temperature −40 ° C. to 150 ° C., heating rate 4 ° C. per minute, strain 4 μm, frequency 10 Hz, Measurement was performed in a tensile mode with a chuck interval of 25 mm.

(Light extraction efficiency)
A 12 mil × 13 mil square blue LED chip (product number: B1213AAA0 S46B / C-19 / 20) manufactured by Genelites, a gold wire, and a die bond agent KER-3000 manufactured by Shin-Etsu Chemical Co., Ltd. -IN-1). Using the total luminous flux measurement (φ300mm) system (product number: HM-0930) manufactured by Otsuka Electronics Co., Ltd., the LED was energized to emit light under the conditions of a temperature of 25 ° C., a current of 30 mA, and a standby time of 30 seconds, and the total luminous flux was measured. Then, the average value of 100 measured samples was obtained.
After the measurement, 0.1 g of the sealant was injected into the LED, and was thermally cured in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 5 hours. Using the total luminous flux measurement (φ300mm) system (part number: HM-0930) manufactured by Otsuka Electronics Co., Ltd., the encapsulated LED was energized at a temperature of 25 ° C., a current of 30 mA, and a standby time of 30 seconds to emit light. The total luminous flux was measured, and the average value of 100 measured samples was obtained.
The following formula was used as a calculation method of light extraction efficiency.

(formula)
Light extraction efficiency (%) = (total luminous flux of LED after sealing / total luminous flux of LED before sealing) × 100
However, the total luminous flux of the LED after sealing and the total luminous flux of the LED before sealing are 100 average values.
The light extraction efficiency (%) of 120% or more was evaluated as ◯, 115% or more and less than 120% as Δ, and less than 115% as x.

(Production Example 1)
To 1262 g of a 48% choline aqueous solution (trimethyl-2hydroxyethylammonium hydroxide aqueous solution), 1083 g of tetraethoxysilane was added and stirred vigorously at room temperature for 2 hours. When the reaction system generated heat and became a homogeneous solution, the stirring was loosened and the reaction was further continued for 12 hours. Next, 1000 mL of methanol was added to the solid produced in the reaction system to obtain a uniform solution.

  While vigorously stirring a solution of 537 g of dimethylvinylchlorosilane, 645 g of trimethylsilyl chloride and 1942 mL of hexane, the methanol solution was slowly added dropwise. After completion of the dropwise addition, the mixture was reacted for 1 hour, and then the organic layer was extracted and concentrated to obtain a solid. Next, the produced solid is washed by vigorously stirring in methanol and filtered to obtain tris (16) Si atoms and an alkenyl group-containing polyhedral polysiloxane compound having 3 vinyl groups. 533 g of vinyldimethylsiloxy) pentakis (trimethylsiloxy) octasilsesquioxane was obtained as a white solid.

(Production Example 2)
20.0 g of tris (vinyldimethylsiloxy) pentakis (trimethylsiloxy) octasilsesquioxane, which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 1, was dissolved in 30.0 g of toluene, and platinum vinylsiloxane was further dissolved. 1.93 μL of a xylene solution of a complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) was dissolved. The solution thus obtained was slowly added dropwise to a solution of 30.94 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 30.94 g of toluene. , Reacted at 105 ° C. for 3 hours and cooled to room temperature.

  After completion of the reaction, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane added in excess with toluene is distilled off to obtain a modified liquid polyhedral polysiloxane. 21.7 g (SiH valence 4.70 mol / kg) was obtained.

(Production Example 3)
20.0 g of tris (vinyldimethylsiloxy) pentakis (trimethylsiloxy) octasilsesquioxane, which is an alkenyl group-containing polyhedral polysiloxane compound obtained in Production Example 1, is dissolved in 40.0 g of toluene, and further platinum vinylsiloxane. 1.93 μL of a xylene solution of a complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) was dissolved. The solution thus obtained was dissolved in 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane 20.62 g, 1,1,3,3-tetramethyldi- The solution was slowly added dropwise to a solution of 11.52 g of siloxane and 32.14 g of toluene, reacted at 95 ° C. for 3 hours, and cooled to room temperature.

  After completion of the reaction, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 1,1,3,3-tetramethyldisiloxane added in excess with toluene are retained. By leaving, 28.5 g (SiH valence 3.92 mol / kg) of a liquid polyhedral polysiloxane modified product was obtained.

Example 1
Phenylsiloxane containing a vinyl group at both ends to 5.00 g (SiH valence 4.70 mol / kg) of the modified polyhedral polysiloxane obtained in Production Example 2 (manufactured by Adeka, weight average molecular weight 385, Vi valence) 5.02 mol / kg) 1.73 g and camphene (weight average molecular weight 136, Vi valence 7.35 mol / kg) 1.25 g were added and stirred, then stirred and defoamed with a planetary stirring deaerator. A polysiloxane composition was obtained. Using the polysiloxane-based composition thus obtained, the evaluation was performed according to each test method described above. The results are shown in Table 1.

(Example 2)
Phenylsiloxane (Adeka, FX-T180, weight average molecular weight 490) containing vinyl groups at both ends to 5.00 g (SiH valence 4.70 mol / kg) modified polyhedral polysiloxane obtained in Production Example 2 , Vi valence 5.02 mol / kg) 1.73 g, β-pinene (weight average molecular weight 136, Vi valence 7.35 mol / kg) 1.09 g, Toray Dow Corning 3-glycidoxypropyltrimethoxysilane After adding 0.20 part by weight of SH6040 manufactured and stirred, stirring and defoaming were performed with a planetary stirring deaerator to obtain a polysiloxane composition. Using the polysiloxane-based composition thus obtained, the evaluation was performed according to each test method described above. The results are shown in Table 1.

(Example 3)
To the polyhedral polysiloxane modified 5.00 g (SiH valence 3.92 mol / kg) obtained in Production Example 3, 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltri 1.45 g of siloxane (weight average molecular weight 385, Vi valence 5.20 mol / kg) and camphene (weight average molecular weight 136, Vi valence 7.35 mol / kg) 0.94 g were added and stirred. Further, 0.21 μl of ethynylcyclohexanol, 0.11 μl of dimethyl maleate and 0.008 μl of N, N, N ′, N′-tetramethylethylenediamine were added and stirred, and then a xylene solution of platinum vinylsiloxane complex (platinum). 0.10 μl of platinum vinylsiloxane complex containing 3% by weight, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) and stirring, followed by stirring and defoaming with a planetary stirring deaerator, polysiloxane A composition was obtained. Using the polysiloxane-based composition thus obtained, the evaluation was performed according to each test method described above. The results are shown in Table 1.

Example 4
Linear polydimethylsiloxane (manufactured by Gelest, DMS-V03, weight) containing a vinyl group at its end on 5.00 g (SiH valence: 4.70 mol / kg) of the modified polyhedral polysiloxane obtained in Production Example 2 Toraydau, which has an average molecular weight of 500, Vi valence 4.00 mol / kg) 2.03 g, camphene (weight average molecular weight 136, Vi valence 7.35 mol / kg) 1.32 g, 3-glycidoxypropyltrimethoxysilane 0.21 part by weight of SH6040 manufactured by Corning was added and stirred. Furthermore, 0.42 g of fumed silica (manufactured by Nippon Aerosil Co., Ltd., R812, primary average particle size 7 nm, BET specific surface area 260 (m ^{2 /} g)) was added and stirred. Further, 0.21 μl of ethynylcyclohexanol and 0.10 μl of dimethyl maleate were added and stirred. To this, a xylene solution of a platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3% by weight of platinum, Umicore Precious Metals Japan) was added. (Product made, Pt-VTSC-3X) 0.14 μl was added and stirred, followed by stirring and defoaming with a planetary stirring deaerator to obtain a polysiloxane composition. Using the polysiloxane-based composition thus obtained, the evaluation was performed according to each test method described above. The results are shown in Table 1.

(Comparative Example 1)
Phenylsiloxane (Adeka, FX-T180, weight average molecular weight 490) containing vinyl groups at both ends to 5.00 g (SiH valence 4.70 mol / kg) modified polyhedral polysiloxane obtained in Production Example 2 , Vi valence 5.02 mol / kg) 2.71 g, 0.23 parts by weight of SH6040 manufactured by Toray Dow Corning, which is 3-glycidoxypropyltrimethoxysilane, was added and stirred. Further, 0.56 μl of ethynylcyclohexanol and 0.64 μl of dimethyl maleate were added and stirred. To this, a xylene solution of a platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3% by weight of platinum, Umicore Precious Metals Japan) was added. Manufactured, Pt-VTSC-3X) 0.10 μl was added and stirred, followed by stirring and defoaming with a planetary stirring deaerator to obtain a composition. Using the composition thus obtained, it was evaluated according to each test method described above. The results are shown in Table 1.

(Comparative Example 2)
Linear polydimethylsiloxane containing a vinyl group at the end (manufactured by Clariant, MVD8MV, weight average molecular weight) on 5.00 g (SiH valence 4.70 mol / kg) modified polyhedral polysiloxane obtained in Production Example 2 780, Vi valence 2.56 mol / kg) 5.45 g was added, and 0.31 part by weight of SH6040 manufactured by Toray Dow Corning, which is 3-glycidoxypropyltrimethoxysilane, was added and stirred. Further, 0.56 μl of ethynylcyclohexanol and 0.65 μl of dimethyl maleate were added and stirred. To this, a xylene solution of a platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3% by weight of platinum, Umicore Precious Metals Japan) was added. Manufactured, Pt-VTSC-3X) 0.10 μl was added and stirred, followed by stirring and defoaming with a planetary stirring deaerator to obtain a composition. Using the composition thus obtained, it was evaluated according to each test method described above. The results are shown in Table 1.

  As described above, it was found that the cured product obtained from the polysiloxane composition of the present invention has high heat resistance and light resistance, and is excellent in cold thermal shock resistance, gas barrier properties, and light extraction efficiency. By using the polysiloxane composition of the present invention, an optical device having low moisture permeability and excellent light extraction efficiency can be produced.

Claims (20)

Hereinafter, a polysiloxane composition comprising the components (A), (B), and (C).
(A) A modified polyhedral polysiloxane obtained by modifying a compound (b) having a hydrosilyl group with respect to an alkenyl group-containing polyhedral polysiloxane compound (a),
(B) an organopolysiloxane having two or more alkenyl groups in one molecule;
(C) Cyclic olefin compound having one carbon-carbon double bond in one molecule The polysiloxane composition according to claim 1, wherein the component (C) has a weight average molecular weight of less than 1,000. The component (C) is represented by the formula C _n H _{2 (nx)}
The polysiloxane composition according to claim 1 or 2, wherein n is an integer of 4 to 20, and x is an integer of 1 to 5. The polysiloxane composition according to any one of claims 1 to 3, wherein the component (B) is an organopolysiloxane containing an aryl group. 5. The polysiloxane composition according to claim 1, wherein the modified polyhedral polysiloxane (A) is liquid at a temperature of 20 ° C. 5. The polysiloxane composition according to any one of claims 1 to 5, wherein the compound (b) having a hydrosilyl group is a cyclic siloxane and / or a linear siloxane containing a hydrosilyl group. . The alkenyl group-containing polyhedral polysiloxane compound (a) has the formula
[AR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group; R ¹ is an alkyl group or an aryl group; R ² is a hydrogen atom or an alkyl group , Aryl groups, or groups linked to other polyhedral skeleton polysiloxanes)
The polysiloxane composition according to any one of claims 1 to 6, which is an alkenyl group-containing polyhedral polysiloxane compound composed of a siloxane unit represented by formula (1). The modified polyhedral polysiloxane (A) is a hydrosilyl group in a range where 2.5 to 20 hydrogen atoms directly bonded to Si atoms per alkenyl group of the alkenyl group-containing polyhedral polysiloxane compound (a) are present. The compound (b) having an excess is modified by adding an excess amount, and the compound (b) having an unreacted hydrosilyl group is distilled off to obtain the compound (b). A polysiloxane composition. The polyhedral composition according to any one of claims 1 to 8, wherein the modified polyhedral polysiloxane (A) has at least three hydrosilyl groups in the molecule. The polyhedral polysiloxane modified (A) component is
[XR ³ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ³ is an alkyl group or an aryl group; R ⁴ is an alkenyl group, a hydrogen atom, an alkyl group, or an aryl group Or a group linked to another polyhedral skeleton polysiloxane, X has a structure represented by the following general formula (1) or general formula (2), and when there are a plurality of X, the general formula (1 ) Or the structure of the general formula (2) may be different, or the structure of the general formula (1) or the general formula (2) may be mixed.

(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain Yes, and may be the same or different, provided that at least one of Y or Z is a hydrogen atom; R is an alkyl group or an aryl group, and may be the same or different. .) As a structural unit. The polysiloxane composition according to any one of claims 1 to 9. The polysiloxane composition according to claim 1, comprising a hydrosilylation catalyst. The polysiloxane composition according to any one of claims 1 to 11, further comprising a curing retarder. The polysiloxane composition according to claim 1, comprising an inorganic filler. Hardened | cured material formed using the polysiloxane type composition of any one of Claims 1-13. 15. The cured product according to claim 14, wherein there is at least one maximum value of loss tangent measured at a frequency of 10 Hz in a temperature range of −40 ° C. to 50 ° C., and a storage elastic modulus is 10 MPa or less at 50 ° C. . 40 ° C., the cured product of claim 14 or 15 moisture permeability of 90% humidity is equal to or less than ^30g / m 2 / 24h.   The sealing agent which uses the polysiloxane type composition of any one of Claims 1-13. The sealant according to claim 17, wherein the sealant is an optical material sealant.   The sealing agent according to claim 17 or 18, wherein the sealing agent is a high-luminance LED sealing agent. The optical device used as a sealing agent of any one of Claims 17-19.