JP2012224743A - Polysiloxane modified compound with polyhedral structure, composition containing the same, and cured product obtained by curing the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polysiloxane-based composition having high heat resistance and light resistance, and excelling in gas barrier property and thermal shock resistance and good handleability in sealing an optical semiconductor device.SOLUTION: The polysiloxane modified compound with a polyhedral structure is obtained by hydrosilylating a polysiloxane compound (b) obtained by mutually hydrosilylating polysiloxane-based compounds (a) with polyhedral structure having an alkenyl group and a hydrosilyl group, a compound (c) having not less than two hydrosilyl groups or alkenyl groups in one molecule, and a cyclic olefin compound (d) having one carbon-carbon double bond in one molecule.

Description

  The present invention relates to a polysiloxane composition having high heat resistance and light resistance, excellent gas barrier properties and thermal shock resistance, and good handling properties when sealing an optical semiconductor element.

  Polysiloxane composition is excellent in heat resistance, cold resistance, weather resistance, light resistance, chemical stability, electrical properties, flame resistance, water resistance, transparency, colorability, non-adhesiveness, non-corrosion It is used in various industries. Among them, a composition composed of polysiloxane having a polyhedral structure is known to exhibit further excellent heat resistance, light resistance, chemical stability, low dielectric property, etc. from its specific chemical structure. .

  As an application example using a polysiloxane having a polyhedral structure, there is one intended to be used for an optical semiconductor element sealant. For example, in Patent Document 1, a polysiloxane having a polyhedral structure having two or more oxetanyl groups A polysiloxane-based composition having a polyhedral structure containing a resin, an aliphatic hydrocarbon containing one or more epoxy groups, and a cationic polymerization initiator is disclosed. This material has high refraction and light extraction efficiency. high. However, since it has an oxetanyl group or an epoxy group, there is a problem that heat resistance and light resistance are low.

  In addition, the polysiloxane composition has excellent characteristics, but generally has a problem of low gas barrier properties. Therefore, when used in an optical semiconductor element sealant application, there is a problem that the reflector is blackened by sulfide. For example, in Patent Document 2, a metal member is previously made of an acrylic resin having a high gas barrier property. The coating process is performed. However, after performing the coating treatment with an acrylic resin, it takes time and labor, such as sealing with a silicone resin separately, and there is a problem in productivity.

  In the optical semiconductor element sealant application, in order to obtain white light, a sealant containing a yellow phosphor with respect to a blue light emitting element is used, or in order to further enhance color rendering, A means such as using a sealant containing a green phosphor and a red phosphor for a blue light emitting element is used, but when the sealant has a low viscosity, There was a problem that the phosphors settled and the emission colors varied.

  In addition, the thermal and thermal shock resistance is an element required for the sealant. If the thermal and thermal shock resistance is low, there is a problem that cracks and peeling occur from the sealant due to a rapid temperature difference. For example, Patent Document 3 discloses a composition using a polysiloxane modified body having a polyhedral structure, and this material is excellent in transparency, heat resistance, light resistance, workability including dicing properties, and gas barrier properties. However, there remains room for further improvement in the viscosity of the composition and the thermal shock resistance.

  As described above, it has been desired to develop a material having high heat resistance and light resistance, excellent thermal shock resistance and gas barrier properties, and good handling properties when sealing an optical semiconductor element.

JP2008-163260 JP 2009-206124 A JP2011-52093A

  Disclosed is a polysiloxane composition having high heat resistance and light resistance, excellent gas barrier properties and thermal shock resistance, and good handling properties when sealing an optical semiconductor element.

As a result of intensive studies to solve the above problems, the present inventors have
A polysiloxane compound (b) obtained by hydrosilylating polyhedral polysiloxane compounds (a) containing an alkenyl group and a hydrosilyl group (b), a compound (c) having two or more hydrosilyl groups or alkenyl groups in one molecule; The present inventors have found that the above problems can be solved by a modified polyhedral polysiloxane obtained by hydrosilylation reaction of a cyclic olefin compound (d) having one carbon-carbon double bond in one molecule. .

  That is, the present invention has the following configuration.

  1) Polysiloxane compound (b) obtained by hydrosilylating polyhedral polysiloxane compounds (a) containing alkenyl groups and hydrosilyl groups (b) Compound having two or more hydrosilyl groups or alkenyl groups in one molecule (c) ) A modified polyhedral polysiloxane obtained by hydrosilylation reaction of a cyclic olefin compound (d) having one carbon-carbon double bond in one molecule.

  2) The modified polyhedral polysiloxane according to 1), wherein the component (d) has a weight average molecular weight of less than 1000.

  3) In the polysiloxane compound (b), one of the alkenyl group and hydrosilyl group derived from the polyhedral polysiloxane compound (a) containing an alkenyl group and a hydrosilyl group remains 1) Or modified polyhedral polysiloxane according to 2).

  4) The modified polyhedral polysiloxane according to any one of 1) to 3), wherein the modified polyhedral polysiloxane is liquid at a temperature of 20 ° C.

  5) The modified polyhedral polysiloxane according to any one of 1) to 4), wherein the modified polyhedral polysiloxane has at least three hydrosilyl groups in the molecule.

  6) The polyhedral polyhedral polymer according to any one of 1) to 5), wherein the polyhedral polysiloxane compound (a) containing an alkenyl group and a hydrosilyl group is a vinyl group. Modified siloxane.

  7) The compound (c) component having two or more hydrosilyl groups or alkenyl groups in one molecule is a cyclic siloxane having a hydrosilyl group or alkenyl group and / or a linear siloxane. The modified polyhedral polysiloxane according to any one of -6).

  8) After obtaining a polysiloxane compound (b) obtained by hydrosilylating polyhedral polysiloxane compounds (a) containing an alkenyl group and a hydrosilyl group, 2 hydrosilyl groups or alkenyl groups are added in one molecule. Any one of 1) to 7), which is obtained by hydrosilylating a compound (c) having at least one compound and a cyclic olefin compound (d) having one carbon-carbon double bond in one molecule. The modified polyhedral polysiloxane according to claim 1.

  9) A polysiloxane composition containing the modified polyhedral polysiloxane according to any one of 1) to 8).

  10) A polysiloxane composition comprising the modified polyhedral polysiloxane according to any one of 1) to 8) and a polysiloxane having two or more alkenyl groups in one molecule.

  11) The polysiloxane composition according to 10), wherein the polysiloxane having two or more alkenyl groups in one molecule has one or more aryl groups.

  12) The polysiloxane composition according to any one of 9) to 11), which has a viscosity of 1 Pa · s or more at a temperature of 23 ° C.

  13) The polysiloxane composition according to any one of 9) to 12), comprising a hydrosilylation catalyst.

  14) The polysiloxane composition according to any one of 9) to 13), comprising a curing retarder.

  15) The polysiloxane composition according to any one of 9) to 14), which contains an adhesion-imparting agent.

  16) A cured product obtained by curing the polysiloxane composition according to any one of 9) to 15).

  It is possible to provide a polysiloxane composition having high heat resistance and light resistance, excellent gas barrier properties and thermal shock resistance, and good handling properties when sealing an optical semiconductor element.

  Hereinafter, the present invention will be described in detail.

<Polyhedral polysiloxane compound (a) containing alkenyl group and hydroxyl group>
The component (a) in the present invention is not particularly limited as long as it is a polysiloxane compound in which an alkenyl group and a hydrosilyl group are bonded directly or indirectly to Si atoms forming a polyhedral structure.
In a polysiloxane compound in which an alkenyl group and a hydrosilyl group are bonded directly or indirectly on Si atoms forming a polyhedral structure used in the present invention, the number of Si atoms contained in the polyhedral structure is 6 to 24 Specifically, for example, silsesquioxane having a polyhedral structure represented by the following structure is exemplified (here, the number of Si atoms = 8 is exemplified as a representative example).

In the above formulas, R ^{1 to} R ⁸ represent an alkenyl group, an organic group having an amino group, an alkyl group, a cycloalkyl group, an aryl group, a hydrosilyl group, or a part or all of hydrogen atoms bonded to carbon atoms of these groups. A chloromethyl group, a trifluoropropyl group, a cyanoethyl group, a (meth) acryloyl group, an epoxy group, a mercapto group or the like substituted with a halogen atom, a cyano group or the like, preferably 1 to 20 carbon atoms, More preferably, it is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group, butenyl group, hexenyl group and the like. Examples of the organic group having an amino group include a methylamino group, a dimethylamino group, and a trimethylamino group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the cycloalkyl group include a cyclohexyl group, and examples of the aryl group include a phenyl group and a tolyl group.

However, on average, at least one of R ^{1 to} R ⁸ is an alkenyl group, and at least one is a hydrosilyl group. The alkenyl group is preferably a vinyl group from the viewpoint of heat resistance, and when a group other than the alkenyl group is selected, a methyl group is preferable from the viewpoint of heat resistance.

The above-mentioned silsesquioxane having a polyhedral structure is, for example, RSiX ₃ (wherein R represents R ^{1 to} R ⁸ described above, and X represents a hydrolyzable functional group such as a halogen atom or an alkoxy group). The silane compound can be obtained by hydrolysis condensation reaction. In addition, after synthesizing a trisilanol compound having three silanol groups in the molecule by the hydrolysis condensation reaction of RSiX ₃ , the ring is closed by reacting the same or different trifunctional silane compounds to form a polyhedral structure. A method for synthesizing silsesquioxane is also known. Furthermore, silsesquioxane having a partially-cleavable polyhedral structure can be synthesized by reacting the trisilanol compound with a monofunctional silane and / or a bifunctional silane.

  In the polyhedral polysiloxane compound (a) in the present invention, a more preferred example is a silylated silicic acid having a polyhedral structure as shown by the following structure (here, the number of Si atoms = 8). As a representative example). When the Si atom forming the polyhedral skeleton and the alkenyl group and the hydrosilyl group are bonded via a siloxane bond, the obtained cured product is not too rigid, and a good molded body can be obtained.

In the above formula, R ^{9 to} R ³² represent an alkenyl group, an organic group having an amino group, an alkyl group, a cycloalkyl group, an aryl group, a hydrosilyl group, or a part or all of hydrogen atoms bonded to carbon atoms of these groups. A chloromethyl group, a trifluoropropyl group, a cyanoethyl group, a (meth) acryloyl group, an epoxy group, a mercapto group or the like substituted with a halogen atom, a cyano group or the like, preferably 1 to 20 carbon atoms, More preferably, it is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of alkenyl groups include vinyl, allyl, butenyl, hexenyl and the like. Examples of the organic group having an amino group include a methylamino group, a dimethylamino group, and a trimethylamino group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the cycloalkyl group include a cyclohexyl group, and examples of the aryl group include a phenyl group and a tolyl group. Of these R ^{9 to} R ³² , at least one is an alkenyl group, and at least one is a hydrosilyl group. The alkenyl group is preferably a vinyl group from the viewpoint of heat resistance, and even when a group other than the alkenyl group is selected, a methyl group is preferable from the viewpoint of heat resistance and light resistance.

  The method for synthesizing the silylated silicic acid having a polyhedral structure is not particularly limited, and is synthesized using a known method. Specific examples of the synthesis method include a method in which a tetraalkoxysilane such as tetraethoxysilane is hydrolytically condensed in the presence of a base such as quaternary ammonium hydroxide.

  In this synthesis method, a silicate having a polyhedral structure is obtained by hydrolytic condensation reaction of tetraalkoxysilane, and the resulting silicate is further silylated such as alkenyl group-containing silyl chloride, hydrosilyl group-containing silyl chloride, etc. By reacting with an agent, it is possible to obtain a polyhedral polysiloxane compound in which Si atoms forming a polyhedral structure are bonded to alkenyl groups and hydrosilyl groups via siloxane bonds. In the present invention, silylated silicic acid having the same polyhedral structure can be obtained from a silica-containing substance such as silica or rice husk instead of tetraalkoxysilane.

  In the present invention, the number of Si atoms contained in the polyhedral structure can be suitably 6 to 24, more preferably 6 to 10. Further, it may be a mixture of polyhedral polysiloxane compounds having different numbers of Si atoms.

Regarding the alkenyl group and hydrosilyl group present on the Si atom forming the polyhedral structure in (a) of the present invention, the resulting polyhedral polysiloxane modified product (A) or polyhedral polysiloxane modified product (A) is used. From the viewpoint of the strength and gas barrier properties, handling properties, and moldability of the resulting cured product,
(I) [number of alkenyl groups]-[number of hydrosilyl groups]> 2, or
(Ii) [number of hydrosilyl groups]-[number of alkenyl groups]> 2,
It is preferable that

  Further, in the alkenyl group or hydrosilyl group present on the Si atom forming the polyhedral structure in (a) of the present invention, when the number of alkenyl groups is larger than the number of hydrosilyl groups, the number of hydrosilyl groups on average is 2. It is preferably 5 or less, more preferably 1.5 or less. When the number exceeds 2.5, gelation occurs in the polysiloxane compound (b) described later or the polyhedral polysiloxane modified body (A), and there is a risk that handling properties, molding processability, and the like are lowered. From the viewpoint of gas barrier properties, the average number of alkenyl groups is preferably 0.5 or more, and more preferably 1.0 or more.

  In the alkenyl group or hydrosilyl group present on the Si atom forming the polyhedral structure in (a) of the present invention, when the number of hydrosilyl groups is larger than the number of alkenyl groups, the number of alkenyl groups is 2. It is preferably 5 or less, more preferably 1.5 or less. When the number exceeds 2.5, gelation occurs in the polysiloxane compound (b) described later or the polyhedral polysiloxane modified body (A), and there is a risk that handling properties, molding processability, and the like are lowered. Further, from the viewpoint of gas barrier properties, the average number of hydrosilyl groups is preferably 0.5 or more, and more preferably 1.0 or more.

<Polysiloxane compound (b)>
The polysiloxane compound (b) in the present invention can be obtained by bonding polyhedral polysiloxane compounds (a) containing an alkenyl group and a hydrosilyl group directly by a hydrosilylation reaction. In the polysiloxane compound (b) in the present invention, the molecules of the polyhedral polysiloxane compound (a) containing an alkenyl group and a hydrosilyl group are directly bonded to each other by the reaction of the alkenyl group and the hydrosilyl group derived from (a). Thus, for example, the strength, gas barrier properties, and dicing properties (cutting properties) of a cured product obtained using the modified polyhedral polysiloxane can be improved. Here, in the hydrosilylation reaction of the alkenyl group and the hydrosilyl group derived from the polyhedral polysiloxane compound (a) containing an alkenyl group and a hydrosilyl group, either one of the alkenyl group or the hydrosilyl group remains, It is preferable from the viewpoints of hardness and strength, gas barrier properties and dicing properties (cutting workability) of a cured product obtained by using the polyhedral polysiloxane modified product. Here, the state in which either one of the alkenyl group or the hydrosilyl group remains means that one of the alkenyl group or the hydrosilyl group substantially disappears and is averaged in one molecule of the polysiloxane compound (b). 0.5 or less, preferably 0.2 or less, and more preferably 0. On the other hand, the number of remaining substituents on average per molecule of the polysiloxane compound (b) is 1. This means that the number is 5, preferably 2, and more preferably 2.5 or more. At this time, from the viewpoint of gas barrier properties, it is more preferable that the number of remaining substituents is further increased.

  Further, for example, from the viewpoint of heat resistance and light resistance of a cured product obtained by curing a polyhedral polysiloxane modified product or a polyhedral polysiloxane modified product finally obtained, an alkenyl group Preferably only the residue remains.

Moreover, when the polyhedral polysiloxane compound (a) containing an alkenyl group and a hydrosilyl group is subjected to a hydrosilylation reaction to obtain a polysiloxane compound (b), a hydrosilylation catalyst can be used. The hydrosilylation catalyst is not particularly limited and any catalyst can be used. Specifically, 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 ] _n }; platinum-phosphine complex {eg Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ }; platinum-phosphite complex {eg 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 La oreaux et al., U.S. Patent No. 3220972 No. platinum Arcola described in the specification - 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.

  As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC. When the hydrosilylation catalyst remains in the polysiloxane compound (b), the remaining hydrosilylation catalyst can be used as a hydrosilylation catalyst for hydrosilylation with the next (c).

<Compound (c) having two or more hydrosilyl groups or alkenyl groups in one molecule>
The compound (c) having two or more hydrosilyl groups or alkenyl groups in one molecule in the present invention is not particularly limited as long as it contains two or more hydrosilyl groups or alkenyl groups on average in the molecule. From the viewpoints of handling properties, molding processability, transparency of polyhedral polysiloxane modified products, or transparency, heat resistance, and light resistance of cured products obtained using polyhedral polysiloxane modified products, hydrosilyl groups or alkenyl groups. And / or linear siloxanes are preferred, and in particular, cyclic siloxanes having a hydrosilyl group or alkenyl group are preferred from the viewpoints of blue laser resistance and gas barrier properties.

  In the present invention, the compound (c) having two or more hydrosilyl groups or alkenyl groups in one molecule may be used alone or in combination of two or more.

  As the linear siloxane having an alkenyl group, 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, Copolymer of methylphenylsiloxane unit, methylvinylsiloxane unit and terminal trimethylsiloxy unit, polysiloxane blocked with dimethylvinylsilyl group, 1,3-divinyl-1,1,3,3-tetramethyldi Examples include siloxane, 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, and the like.

  Examples of the cyclic siloxane having an alkenyl group include 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1,3. , 5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-trimethylcyclosiloxane, , 3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1,3,5,7,9, Examples thereof include 11-hexamethylcyclosiloxane.

  Specific examples of the linear siloxane having a hydrosilyl group include a copolymer of a dimethylsiloxane unit, a methylhydrogensiloxane unit, and a terminal trimethylsiloxy unit, a diphenylsiloxane unit, a methylhydrogensiloxane unit, and a terminal trimethylsiloxy unit. Copolymer of methylphenylsiloxane unit, methylhydrogensiloxane unit and terminal trimethylsiloxy unit, polysiloxane end-capped with dimethylhydrogensilyl group, 1,1,3,3-tetramethyl Examples include disiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, 1,1,3,3-tetraphenyldisiloxane, and the like.

  Specific examples of the cyclic siloxane having a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trimethyl. Hydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 -Trihydrogen-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 are exemplified.

  In the present invention, the compound (c) having two or more hydrosilyl groups or alkenyl groups in one molecule is composed of a hydrogen atom, a vinyl group, and a methyl group on the Si atom from the viewpoint of heat resistance and light resistance. Furthermore, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 1,1,3,3-tetramethyldisiloxane are excellent in availability. Therefore, it is preferable. In particular, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane is preferable from the viewpoint of blue laser resistance and gas barrier properties.

  The amount of the compound (c) having two or more hydrosilyl groups or alkenyl groups in one molecule is such that when the alkenyl groups remain in the polysiloxane compound (b), (c) The number of hydrogen atoms directly bonded to the component Si atom is preferably more than one, and more preferably 2.5 to 20, but it depends on the compound. If the amount added is small, gelation occurs due to a crosslinking reaction, resulting in a modified polyhedral polysiloxane with poor handling properties. If too large, the physical properties of a cured product obtained using the modified polyhedral polysiloxane may be adversely affected. There is. Furthermore, when an excessive amount of the component (c) is present, it is preferable to remove the unreacted component (c), for example, under reduced pressure and heating conditions.

  Further, when a hydrosilyl group remains in the polysiloxane compound (b), it is preferable that the number of alkenyl groups directly connected to Si atoms of the component (c) is less than one per remaining hydrosilyl group, It is preferably used so as to be 0.05 to 0.4, but it depends on the compound. When the addition amount is small, the physical properties of the cured product may be adversely affected. When the addition amount is too large, gelation occurs due to a crosslinking reaction, resulting in a modified polyhedral polysiloxane having poor handling properties.

<Cyclic olefin compound (d) having one carbon-carbon double bond in one molecule>
The cyclic olefin compound (d) having one carbon-carbon double bond in one molecule in the present invention undergoes a hydrosilylation reaction with the hydrosilyl group of the component (b) when the component (b) has a hydrosilyl group. . In addition, when the component (c) has a hydrosilyl group, the hydrosilyl group of the component (c) also undergoes a hydrosilylation reaction. By using the component (d), the elastic modulus of the obtained cured product can be reduced, and further, the thermal shock resistance, fracture strength, gas barrier properties and the like can be improved.

  (D) 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.

In addition, from the viewpoint of reactivity with the component (b), the component (d) in the present invention preferably has an average molecular weight of 1000 or less. As a more preferable example, the following formula C _n H _{2 (nx) )}
The cyclic olefin compound represented by (n is an integer of 4-20, x is an integer of 1-5) is mentioned.

  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, 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 (d) 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 (d) having one carbon-carbon double bond in one molecule is the carbon-carbon of the component (d) 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.

<Modified polyhedral polysiloxane>
The modified polyhedral polysiloxane of the present invention is a polysiloxane compound (b) obtained by hydrosilylating polyhedral polysiloxane compounds (a) containing an alkenyl group and a hydrosilyl group in the presence of a hydrosilylation catalyst described later. It is obtained by subjecting a compound (c) having two or more hydrosilyl groups or alkenyl groups in one molecule to a hydrosilylation reaction with a cyclic olefin compound (d) having one carbon-carbon double bond in one molecule. .

  The method for obtaining the modified polyhedral polysiloxane of the present invention is not particularly limited and can be variously set. For example, after reacting the component (b) and the component (c) in advance, the component (d) is reacted. Alternatively, after reacting the component (c) and the component (d) in advance, the component (b) may be reacted, or the component (b), the component (c), and the component (d) are allowed to coexist. You may make it react. After completion of each reaction, for example, volatile unreacted components may be distilled off under reduced pressure and heating conditions, and used as a target product or an intermediate for the next step. In order to suppress the formation of a compound containing only the component (d) and the component (b) but not including the component (b), the component (b) and the component (c) are reacted, and the unreacted (c) A method in which the component (d) is reacted after the component is distilled off is preferred.

  In the polyhedral polysiloxane modified product thus obtained, a part of the alkenyl group of the component (b) used in the reaction may remain.

Polyhedral polysiloxane is not particularly limited as amount of a hydrosilylation catalyst used in the synthesis of the modified product, used for the reaction component (b) and (c) component of the alkenyl group 1 mol per 10 ^-1 to 10 ^{- It} is good to use in the range of ¹⁰ mol. Preferably it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. If there are 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. There is also a risk of foaming. Moreover, when there are 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 polyhedral polysiloxane modified product thus obtained can ensure compatibility with various compounds, particularly siloxane compounds, and further, since hydrosilyl groups are introduced into the molecule, It becomes possible to make it react with the compound which has. Specifically, a cured product can be obtained by reacting with a polysiloxane having two or more alkenyl groups in one molecule described later.

The modified polyhedral polysiloxane in the present invention can be liquid at a temperature of 20 ° C. It is preferable that the polyhedral polysiloxane modified is in a liquid form because of excellent handling properties.
In addition, the modified polyhedral polysiloxane preferably has at least three hydrosilyl groups in the molecule from the viewpoint of the strength and hardness of the resulting cured product, as well as heat resistance and light resistance.

  The polyhedral polysiloxane modified product thus obtained is controlled by controlling the addition amount of components (a) to (d), reaction sequence, reaction time, reaction temperature, etc., and the viscosity of the polyhedral polysiloxane modified product. Control is possible. It is also possible to adjust the viscosity of the polysiloxane composition described later by controlling the viscosity of the modified polyhedral polysiloxane. The viscosity of the modified polyhedral polysiloxane is not particularly limited, but when the modified polyhedral polysiloxane is liquid at a temperature of 20 ° C., the viscosity at 20 ° C. is 0.01 Pa · s to 300 Pa · s. It is preferably 1 Pa · s to 100 Pa · s. If the modified polyhedral polysiloxane is too low in viscosity, the polysiloxane composition described later will have low viscosity, and additives such as phosphors may settle without being dispersed. If the viscosity is too high, the handling property may be deteriorated.

  In addition, the modified polyhedral polysiloxane preferably has at least three hydrosilyl groups in the molecule from the viewpoint of the strength and hardness of the resulting cured product, as well as heat resistance and light resistance.

<Polysiloxane having two or more alkenyl groups in one molecule>
In the present invention, the number of polysiloxane siloxane units having two or more alkenyl groups in one molecule 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, the composition tends to volatilize, and desired physical properties may not be obtained after curing. Moreover, when there are many siloxane units, the gas barrier property of the obtained hardened | cured material may fall.

  In the present invention, the polysiloxane having two or more alkenyl groups in one molecule preferably has an aryl group from the viewpoint of gas barrier properties. In addition, in the polysiloxane having two or more alkenyl groups in one molecule having an aryl group, the aryl group is preferably bonded directly to the Si atom from the viewpoint of heat resistance and light resistance. In addition, the aryl group may be present at either the side chain or the terminal of the molecule, and the molecular structure of such an aryl group-containing polysiloxane is not limited. In addition to the chain shape, it may have a cyclic structure.

  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, biphenyl group, 2,3,4-trimethyl Examples include phenyl group, 2,3,5-trimethylphenyl group, 2,4,5-trimethylphenyl group, 3-epoxyphenyl group, 4-epoxyphenyl group, 3-glycidylphenyl group, 4-glycidylphenyl group and the like. . 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 polysiloxane having two or more alkenyl groups in one molecule in the present invention is a linear polysiloxane having two or more alkenyl groups from the viewpoint of heat resistance and light resistance, and two or more alkenyl groups at the molecular ends. Preferred examples include polysiloxanes having a cyclic structure and cyclic siloxanes having two or more alkenyl groups.

  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 Examples thereof include polydiphenylsiloxane and polymethylphenylsiloxane whose ends are blocked with dimethylvinylsilyl groups.

Specific examples of the polysiloxane having two or more alkenyl groups at the molecular terminals include polysiloxanes whose ends are blocked with the dimethylvinylsilyl group exemplified above, two or more dimethylvinylsiloxane units and SiO ₂ units, SiO _{3 /} Examples thereof include polysiloxane composed of at least one siloxane unit selected from the group consisting of ₂ units and SiO units.

  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 and the like.

  These polysiloxanes having two or more alkenyl groups in one molecule may be used alone or in combination of two or more.

  The amount of polysiloxane having two or more alkenyl groups per molecule can be variously set, but per alkenyl group is directly linked to Si atoms contained in the polyhedral polysiloxane-based modified polyhedral polysiloxane. It is desirable that the added hydrogen atoms be added at a rate of 0.3 to 5, preferably 0.5 to 3. When the proportion of alkenyl groups is small, appearance defects due to foaming or the like are likely to occur, and when the proportion of alkenyl groups is large, physical properties after curing may be adversely affected.

  A cured product can be obtained by hydrosilylating the hydrosilyl group of the modified polyhedral polysiloxane of the present invention and the alkenyl group of a polysiloxane having two or more alkenyl groups in one molecule. In the hydrosilylation reaction, it is preferable to use a hydrosilylation catalyst. As the hydrosilylation catalyst that can be used in this reaction, those described below can be used. In the hydrosilylation reaction between a polyhedral polysiloxane modified and a polysiloxane having two or more alkenyl groups in one molecule, the hydrosilylation catalyst used in the synthesis of the polyhedral polysiloxane modified is the polyhedral polysiloxane. Since it is brought together with the modified body, it is not necessary to use a hydrosilylation catalyst separately.

<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, a platinum-olefin complex, chloroplatinic acid, platinum alone, a carrier (alumina, silica, carbon black, etc.) supported by solid platinum, a platinum-vinylsiloxane complex, such as 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 polyhedral 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.

<Adhesive agent>
The adhesion-imparting agent is used for the purpose of improving the adhesion between the polyhedral polysiloxane composition and the substrate in the present invention, and is not particularly limited as long as it has such an effect. A ring agent can be exemplified 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.

<Polysiloxane composition>
The polysiloxane composition of the present invention can be obtained by adding polysiloxane having two or more alkenyl groups in one molecule, a hydrosilylation catalyst, and a curing retarder to the modified polyhedral polysiloxane as necessary. Can do. The polyhedral polysiloxane composition of the present invention can be handled as a liquid resin composition. By using a liquid resin composition, it is possible to easily obtain a molded body according to the application by injecting or applying to a mold, package, substrate or the like and curing.

  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.

  The curing time can be appropriately selected depending on the curing temperature, the amount of the hydrosilylation catalyst to be used and the amount of the reactive 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.

  The viscosity of the polysiloxane composition of the present invention is not particularly limited, but the viscosity at a temperature of 23 ° C. is preferably 1 Pa · s to 300 Pa · s, more preferably 2 Pa · s to 100 Pa · s. . If the viscosity of the polysiloxane composition is too low, additives such as phosphors may settle without being dispersed. Further, when the viscosity of the polysiloxane composition is too high, the handling property may be deteriorated.

  An inorganic filler can be added to the polysiloxane composition of the present invention as necessary. By adding an inorganic filler to the polysiloxane composition of the present invention, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical characteristics, light reflectance, and difficulty of the resulting molded product are obtained. Various physical properties such as flammability, 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 silane coupling agent, and the like, but are not particularly limited.

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.

  The addition amount of the inorganic filler is not particularly limited, but it is preferably 1 to 1000 parts by weight, more preferably 100 parts by weight, based on 100 parts by weight of the polyhedral polysiloxane modified body and polysiloxane having two or more alkenyl groups in one molecule. 3 to 500 parts by weight, more preferably 5 to 300 parts by weight. When the amount of the inorganic filler added is large, the fluidity may be deteriorated, and when the amount of the inorganic filler added is small, desired physical properties may not be obtained.

  The order of mixing the inorganic fillers is not particularly limited, but in terms that storage stability tends to be good, the polyhedral polysiloxane modification is performed after mixing with polysiloxane having two or more alkenyl groups in one molecule. A method of mixing the body is desirable. In addition, a polyhedral polysiloxane modified body that is a reaction component, and a polysiloxane having two or more alkenyl groups in one molecule are well mixed and a stable molded product is easily obtained. It is preferable to mix an inorganic filler with a mixture of polysiloxane having two or more alkenyl groups in one molecule.

  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.

  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 of the present invention, the above-described components are uniformly mixed using a kneader such as a roll, a Banbury mixer, a kneader, or a planetary stirring deaerator, and heat-treated 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 the peripheral material of the liquid crystal display device such as a protective film and a film for liquid crystal such as a passivation film 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 optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Examples include pickup lenses, protective films, sealants, and adhesives. 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 And a wave plate, a correction plate, a splitter, a hologram, a mirror, 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.

  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.

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

(viscosity)
An E-type viscometer manufactured by Tokyo Keiki was used. The measurement was performed at a measurement temperature of 23.0 ° C., a rotation speed of 1 rpm, and an EHD type 48φ 1-fold cone.

(SiH value)
400 MHz NMR manufactured by Varian Technologies Japan Limited was used. The SiH value of the modified polyhedral polysiloxane is obtained by calculating the following formula (1) by making a mixture of the modified polyhedral polysiloxane and dibromoethane and measuring the NMR.
Formula (1): SiH value (mol / kg) = [integral value of peak attributed to SiH group of modified polyhedral polysiloxane] / [integral value of peak attributed to methyl group of dibromoethane] × 4 X [Weight of dibromoethane in mixture] / [Molecular weight of dibromoethane] / [Weight of polyhedral polysiloxane in mixture]
Calculated using

(Preparation of samples for heat resistance test and light resistance test)
The polyhedral polysiloxane 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 ×.

(Creation of sample for cold thermal shock test)
Enomoto Co., Ltd. LED package (product name: TOP LED 1-IN-1), two 0.4mm x 0.4mm x 0.2mm single-crystal silicon chips, Henkel Japan Co., Ltd. epoxy adhesive (product name) : LOCITE 348) and fixed by heating in a convection oven set at 150 ° C. for 30 minutes. A polyhedral polysiloxane-based composition was injected here, and a sample was prepared by thermosetting in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 5 hours.

(Cold thermal shock resistance test)
The sample prepared as described above was subjected to 100 cycles of high temperature holding 100 ° C., 30 minutes, low temperature holding −40 ° C., 30 minutes using a thermal shock tester (TSA-71H-W manufactured by Espec). A sample was observed. After the test, if there was no change visually, it was rated as “C”, and if it cracked or peeled off or colored with the package, it was marked “X”.

(Making samples for moisture permeability test)
(In the present invention, the moisture permeability of the cured product was used as an index of gas barrier properties of the obtained cured product. That is, a low moisture permeability is synonymous with a high gas barrier property.) Polyhedral polysiloxane system The composition was filled in 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 of 5 cm square and 2 mm thickness. This sample was cured for 24 hours in an environment of room temperature 25 ° C. and humidity 55% RH.

(Moisture permeability test)
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. Furthermore, the above 5 cm square sample with a thickness of 2 mm is fixed to the upper part, and this is used as a test specimen. The test specimen is cured for 24 hours at a temperature of 40 ° C. and a humidity of 90% RH in a thermo-hygrostat (PR-2KP manufactured by ESPEC).
Formula (2): Moisture permeability (g / m ² / day) = {(total weight of specimen after moisture permeability test (g)) − (total weight of specimen before moisture permeability test (g))} × 10000 / 9
The moisture permeability (water vapor transmission rate) was calculated according to

(Hydrogen sulfide test)
A polysiloxane-based composition is injected into an LED package (product name: TOP LED 1-IN-1) manufactured by Enomoto Co., Ltd., and heat-cured in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 5 hours. To make a sample. This sample was put in a flow type gas corrosion tester and subjected to a hydrogen sulfide exposure test for 96 hours under the conditions of 40 ° C., 80% RH, and 3 ppm of hydrogen sulfide. After the test, if the package reflector was not discolored, it was rated as ◯, if slightly discolored, Δ, and if discolored, ×.

(Phosphor sedimentation test)
To 5 g of the polysiloxane composition, 0.05 g of a phosphor (Y3957 manufactured by Intematics) was added, and the mixture was thoroughly stirred and allowed to stand. The observation was made after 1 hour, and when the phosphor remained dispersed, it was marked as ◯, and when sedimentation was observed, it was marked as x.

(Production Example 1)
As a synthesis method of polysiloxane (a) having a polyhedral structure, 1042 g of tetraalkoxysilane was added to 1288 g of 48% trimethyl-2hydroxyethylammonium hydroxide aqueous solution (choline aqueous solution), and the mixture was vigorously stirred at room temperature for 3 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, 750 mL of methanol was added to the solid produced in the reaction system to obtain a uniform solution. While stirring a solution of 588 g of dimethylvinylchlorosilane, 554 g of trimethylchlorosilane, 132 g of dimethylchlorosilane, and 750 mL of hexane, the obtained uniform 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 was stirred and washed in acetonitrile, followed by filtration to obtain 601 g of a polyhedral polysiloxane compound containing an alkenyl group and a hydrosilyl group. ^{From 1} H-NMR, it was confirmed that a vinyl group, a trimethylsilyl group, and a hydrosilyl group were introduced at a ratio of 3.1: 3.9: 1.0.

(Production Example 2)
As a synthesis method of the polyhedral polysiloxane compound (a), 417 g of tetraalkoxysilane was added to 515 g of 48% trimethyl-2hydroxyethylammonium hydroxide aqueous solution (choline aqueous solution), and the mixture was vigorously stirred at room temperature for 3 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, 265 mL of methanol was added to the solid matter generated in the reaction system to obtain a uniform solution. While stirring a solution of 25 g of dimethylvinylchlorosilane, 105 g of trimethylchlorosilane, 80 g of dimethylchlorosilane, and 225 mL of hexane, the obtained uniform 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 was stirred and washed in methanol, and then filtered to obtain 224 g of a polyhedral polysiloxane compound containing an alkenyl group and a hydrosilyl group. ^{From 1} H-NMR, it was confirmed that a vinyl group, a trimethylsilyl group, and a hydrosilyl group were introduced at a ratio of 0.6: 3.8: 3.6.

Example 1
A mixed solution of 10 g of the polyhedral polysiloxane compound containing alkenyl groups and hydrosilyl groups obtained in Production Example 1 and 30 g of toluene is mixed with 1.4 μL of a platinum vinylsiloxane complex (3% platinum / xylene solution) and 10 g of toluene. The solution was added dropwise, heated at 105 ° C. for 1 hour, and then cooled to room temperature. ^{From 1} H-NMR, it was confirmed that the hydrosilyl group derived from polysiloxane disappeared and an alkenyl group was present. The solution containing the alkenyl group-containing polysiloxane compound thus obtained was used in an amount of 5.2 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (used. The alkenyl group-containing polysiloxane compound was added dropwise to a mixed solution of 20 g of toluene and an amount of 3.2 hydrosilyl groups per alkenyl group, and heated at 105 ° C. for 2 hours. When this solution was subjected to ¹ H-NMR measurement, it was confirmed that an alkenyl group derived from polysiloxane had disappeared. Toluene and unreacted components were distilled off from this solution, 10 g of toluene was added again to dissolve the product, and 1.5 g of camphene prepared separately (1,3,5,7-tetrahydrogen-used) was prepared. 1) 3,3,5,7-tetramethylcyclotetrasiloxane hydrosilyl group is slowly added dropwise in a solution of 10 g of toluene in an amount of 0.13 carbon-carbon double bond groups). And reacted at 105 ° C. for 5 hours. When this solution was subjected to ¹ H-NMR measurement, it was confirmed that the carbon-carbon double bond group derived from camphene had disappeared. After cooling to room temperature, toluene was distilled off to obtain 16.1 g of a liquid polyhedral polysiloxane modified product (SiH value 2.32 mol / kg). 1.49 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane was added to 5.00 g of the resulting modified product and stirred to obtain a polysiloxane composition. . Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Example 2)
A mixed solution of 10 g of polyhedral polysiloxane compound containing alkenyl group and hydrosilyl group obtained in Production Example 1 and 30 g of toluene is mixed with 1.6 μL of platinum vinylsiloxane complex (3% platinum, xylene solution) and 10 g of toluene. The solution was added dropwise, heated at 105 ° C. for 1 hour, and then cooled to room temperature. ^{From 1} H-NMR, it was confirmed that the hydrosilyl group derived from polysiloxane disappeared and an alkenyl group was present. To the solution containing the alkenyl group-containing polysiloxane compound thus obtained, 1.5 g of camphene (1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetra used) was used. After adding 1) the amount of carbon-carbon double bond groups to one hydrosilyl group of siloxane, this solution is added to 1,3,5,7-tetrahydrogen-1, Dropped in a mixed solution of 5.2 g of 3,5,7-tetramethylcyclotetrasiloxane (amount of 3.2 silyl silyl groups with respect to one alkenyl group of the alkenyl group-containing polysiloxane compound) and 20 g of toluene. , And heated at 105 ° C. for 5 hours. When this solution was subjected to ¹ H-NMR measurement, it was confirmed that the alkenyl group derived from the polysiloxane compound and the carbon-carbon double bond group derived from camphene disappeared. After cooling to room temperature, 2.67 μl of ethynylcyclohexanol and 0.62 μl of dimethyl maleate were added, and toluene was distilled off to obtain 16.3 g of a liquid polyhedral polysiloxane modified product (SiH value 2.50 mol / kg) Got. 1.60 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane was added to 5.00 g of the resulting modified product and stirred to obtain a polysiloxane composition. . Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Example 3)
A mixed solution of 10 g of polyhedral polysiloxane compound containing alkenyl group and hydrosilyl group obtained in Production Example 1 and 30 g of toluene is mixed with 1.6 μL of platinum vinylsiloxane complex (3% platinum, xylene solution) and 10 g of toluene. The solution was added dropwise, heated at 105 ° C. for 1 hour, and then cooled to room temperature. ^{From 1} H-NMR, it was confirmed that the hydrosilyl group derived from polysiloxane disappeared and an alkenyl group was present. The solution containing the alkenyl group-containing polysiloxane compound thus obtained was used in an amount of 5.2 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (used. An amount of 3.2 hydrosilyl groups per alkenyl group of the alkenyl group-containing polysiloxane compound) and 1.6 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (used) The solution was added dropwise to a mixed solution of 20 g of toluene with an alkenyl group-containing polysiloxane compound having an amount of 0.9 hydrosilyl group and heated at 105 ° C. for 2 hours. When this solution was subjected to ¹ H-NMR measurement, it was confirmed that the alkenyl group derived from the polysiloxane compound had disappeared. After completion of the reaction, toluene and unreacted components were distilled off from this solution, 10 g of toluene was added again to dissolve the product, and 1.5 g of camphene prepared separately (1,3,5,7- The amount of carbon-carbon double bond groups is 0.13 per 1 hydrosilyl group of tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane was dissolved in 10 g of toluene. The solution was slowly added dropwise and reacted at 105 ° C. for 5 hours. When this solution was subjected to ¹ H-NMR measurement, it was confirmed that the carbon-carbon double bond group derived from camphene had disappeared. After cooling to room temperature, 2.6 μl of ethynylcyclohexanol and 0.62 μl of dimethyl maleate were added, and toluene was distilled off to obtain 16.8 g of a modified polyhedral polysiloxane having a polyhedral structure (SiH value 2.01 mol / kg). Got. 1.29 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane was added to 5.00 g of the resulting modified product and stirred to obtain a polysiloxane composition. . Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

Example 4
1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyl was added to 5.00 g (SiH value 2.50 mol / kg) of the modified liquid polyhedral polysiloxane obtained in Example 2. 1.60 g of trisiloxane and 0.16 g of 3-glycidoxypropyltrimethoxysilane were added and stirred to obtain a polysiloxane composition. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Example 5)
A mixed solution of 10 g of polyhedral polysiloxane compound containing alkenyl group and hydrosilyl group obtained in Production Example 2 and 30 g of toluene is mixed with 0.6 μL of platinum vinylsiloxane complex (3% platinum / xylene solution) and 10 g of toluene. The solution was added dropwise, heated at 105 ° C. for 1 hour, and then cooled to room temperature. ^{From 1} H-NMR, it was confirmed that an alkenyl group derived from polysiloxane disappeared and a hydrosilyl group was present, and a solution of a hydrosilyl group-containing polysiloxane compound was obtained.

  Separately, 0.8 g of vinylcyclohexane (amount of 0.22 alkenyl groups relative to one hydrosilyl group of the used hydrosilyl group-containing polysiloxane compound) and 1,7-divinyl-3, 3, 5, 5 -1.2 g of tetraphenyl-1,1,7,7-tetramethyltetrasiloxane (amount of 0.12 alkenyl groups relative to one hydrosilyl group of the hydrosilyl group-containing polysiloxane compound used) in 10 g of toluene Dissolved. This solution was made to react with the solution of the hydrosilyl group-containing polysiloxane compound prepared earlier and reacted at 105 ° C. for 2 hours.

^{As a result of 1} H-NMR measurement, it was confirmed that vinylcyclohexane and alkenyl groups derived from 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane disappeared. After cooling to room temperature, toluene was distilled off to obtain 10.5 g (SiH value 1.34 mol / kg) of a modified liquid polyhedral polysiloxane. 0.86 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane was added to 5.00 g of the resulting modified product and stirred to obtain a polysiloxane composition. . Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Comparative Example 1)
The polyhedral polysiloxane compound containing alkenyl groups and hydrosilyl groups obtained in Production Example 1 was dissolved in 15 g of toluene, and a xylene solution of platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, Umicore). A mixed solution of 0.8 μL of Pt-VTSC-3X) manufactured by Precious Metals Japan and 5 g of toluene was added dropwise, heated at 105 ° C. for 1 hour, and then cooled to room temperature. ^{From 1} H-NMR, it was confirmed that the hydrosilyl group derived from the polyhedral polysiloxane compound disappeared and the alkenyl group was present. 2.6 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane was used for the solution containing the alkenyl group-containing polysiloxane compound thus obtained (used. The alkenyl group-containing polyhedral polysiloxane compound was slowly dropped into a solution of 4.7 g of hydrosilyl groups per 1 alkenyl group and 10 g of toluene, and reacted at 105 ° C. for 2 hours. When this solution was subjected to ¹ H-NMR measurement, it was confirmed that the alkenyl group derived from the polysiloxane compound had disappeared. 1.99 μl of ethynylcyclohexanol and 0.46 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off to obtain 6.6 g of a liquid modified product (SiH value 3.66 mol / kg). To 5,0 g of the obtained modified product, 2.4 g of 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane was added and stirred to obtain a composition. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

(Comparative Example 2)
The polyhedral polysiloxane compound containing alkenyl groups and hydrosilyl groups obtained in Production Example 1 was dissolved in 15 g of toluene, and a xylene solution of platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, Umicore). A mixed solution of 0.8 μL of Pt-VTSC-3X) manufactured by Precious Metals Japan and 5 g of toluene was added dropwise, heated at 105 ° C. for 1 hour, and then cooled to room temperature. ^{From 1} H-NMR, it was confirmed that the hydrosilyl group derived from the polyhedral polysiloxane compound disappeared and the alkenyl group was present. 2.6 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane was used for the solution containing the alkenyl group-containing polysiloxane compound thus obtained (used. The alkenyl group-containing polysiloxane compound was slowly dropped into a solution of 4.7 g of hydrosilyl groups per 1 alkenyl group and 10 g of toluene, and reacted at 105 ° C. for 2 hours. When this solution was subjected to ¹ H-NMR measurement, it was confirmed that the alkenyl group derived from the polysiloxane compound had disappeared. 1.99 μl of ethynylcyclohexanol and 0.46 μl of dimethyl maleate were added, and toluene and unreacted components were distilled off to obtain 6.7 g of a liquid modified product (SiH value 3.66 mol / kg). To 5.0 g of the obtained modified product, 4.6 g of linear polydimethylsiloxane containing a vinyl group at the end (MVD8MV, manufactured by Clariant) was added and stirred to obtain a composition. Various evaluations described above were performed using the composition thus obtained, and the results are shown in Table 1.

  As shown in Table 1, the polyhedral siloxane composition of the present invention has high heat resistance and light resistance, excellent thermal shock resistance and gas barrier properties, and handling when sealing an optical semiconductor element. It has a good viscosity.

Claims (16)

A polysiloxane compound (b) obtained by hydrosilylating polyhedral polysiloxane compounds (a) containing an alkenyl group and a hydrosilyl group, a compound (c) having two or more hydrosilyl groups or alkenyl groups in one molecule, A modified polyhedral polysiloxane obtained by hydrosilylation reaction of a cyclic olefin compound (d) having one carbon-carbon double bond in one molecule. The polyhedral polysiloxane modified product according to claim 1, wherein the component (d) has a weight average molecular weight of less than 1000. In the polysiloxane compound (b), either the alkenyl group or hydrosilyl group derived from the polyhedral polysiloxane compound (a) containing an alkenyl group and a hydrosilyl group remains. 3. A modified polyhedral polysiloxane according to 2. The modified polyhedral polysiloxane according to any one of claims 1 to 3, wherein the modified polyhedral polysiloxane is liquid at a temperature of 20 ° C. 5. The modified polyhedral polysiloxane according to claim 1, wherein the modified polyhedral polysiloxane has at least three hydrosilyl groups in the molecule. The polyhedral polysiloxane modification according to any one of claims 1 to 5, wherein the alkenyl group of the polyhedral polysiloxane compound (a) containing an alkenyl group and a hydrosilyl group is a vinyl group. body. The compound (c) component having two or more hydrosilyl groups or alkenyl groups in one molecule is a cyclic siloxane having a hydrosilyl group or an alkenyl group, and / or a linear siloxane. 7. The modified polyhedral polysiloxane according to any one of 6 above. After obtaining a polysiloxane compound (b) obtained by hydrosilylating polyhedral polysiloxane compounds (a) containing an alkenyl group and a hydrosilyl group, two or more hydrosilyl groups or alkenyl groups are contained in one molecule. The compound (c) having a carbon olefin compound (d) having one carbon-carbon double bond in one molecule is obtained by a hydrosilylation reaction. The modified polyhedral polysiloxane according to Item. The polysiloxane type composition containing the polyhedral polysiloxane modified body of any one of Claims 1-8. A polysiloxane composition comprising the modified polyhedral polysiloxane according to any one of claims 1 to 8, and a polysiloxane having two or more alkenyl groups in one molecule. The polysiloxane composition according to claim 10, wherein the polysiloxane having two or more alkenyl groups in one molecule has one or more aryl groups. The polysiloxane composition according to any one of claims 9 to 11, which has a viscosity of 1 Pa · s or more at a temperature of 23 ° C.   The polysiloxane composition according to any one of claims 9 to 12, comprising a hydrosilylation catalyst.   The polysiloxane composition according to any one of claims 9 to 13, further comprising a curing retarder.   The polysiloxane composition according to any one of claims 9 to 14, comprising an adhesiveness imparting agent. Hardened | cured material formed by hardening | curing the polysiloxane type composition of any one of Claims 9-15.