JP2012012557A - Organopolysiloxane composition and optical device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organosiloxane composition having high heat resistance and light resistance and excellent gas barrier property and cold-thermal shock resistance, and to provide an optical device using the composition.SOLUTION: The organopolysiloxane composition comprises: (A) a polyhedral polysiloxane modified product obtained by subjecting polyhedral polysiloxane compounds (a) containing an alkenyl group and a hydrosilyl group to hydrosilylation to obtain a polysiloxane compound (b) and further subjecting the compound (b) to hydrosilylation with a compound (c) having a hydrosilyl group or alkenyl group; (B) an organopolysiloxane having at least two alkenyl groups or hydrosilyl groups in one molecule; and (C) an organosilicon compound having one alkenyl group or hydrosilyl group in one molecule.

Description

The present invention relates to an organopolysiloxane composition having high heat resistance and light resistance and excellent gas barrier properties and thermal shock resistance, and an optical device using the same.

  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, an acrylic resin is previously used as a metal member. Corresponding to coating. However, since the silicone resin itself does not have a gas barrier property, there is a problem in productivity because the silicone resin itself needs to be sealed with a silicone resin after coating.

  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, use has been limited to applications that require high gas barrier properties.

  As described above, disclosure of materials using polysiloxane is seen, but examples of materials that maintain high heat resistance and light resistance, and have excellent thermal and thermal shock resistance and gas barrier properties have not been found. Development was required.

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

  Provided are an organopolysiloxane composition having high heat resistance and light resistance, excellent in thermal shock resistance and gas barrier properties, and an optical device using the same.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by an organopolysiloxane composition comprising (A) and (B) and (C). Invented.

(A) A polysiloxane compound (b) obtained by hydrosilylating a polyhedral polysiloxane compound (a) containing an alkenyl group and a hydrosilyl group is hydrosilylated with a hydrosilyl group or alkenyl group-containing compound (c). Polyhedral polysiloxane modified product obtained,
(B) an organopolysiloxane having two or more alkenyl groups or hydrosilyl groups in one molecule;
(C) Organosilicon compound having one alkenyl group or hydrosilyl group in one molecule, that is, the present invention has the following constitution.

1) An organopolysiloxane composition comprising (A) and (B) and (C).
(A) A polysiloxane compound (b) obtained by hydrosilylating a polyhedral polysiloxane compound (a) containing an alkenyl group and a hydrosilyl group is hydrosilylated with a hydrosilyl group or alkenyl group-containing compound (c). Polyhedral polysiloxane modified product obtained,
(B) an organopolysiloxane having two or more alkenyl groups or hydrosilyl groups in one molecule;
(C) An organosilicon compound having one alkenyl group or hydrosilyl group in one molecule.

  2) The organopolysiloxane composition according to 1), wherein the component (C) is an organosilicon compound containing at least one aryl group.

  3) In the polysiloxane compound (b) of the modified polyhedral polysiloxane (A), either the alkenyl group or hydrosilyl group derived from the polyhedral polysiloxane compound (a) containing an alkenyl group and a hydrosilyl group is The organopolysiloxane composition according to 1), which remains.

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

  5) The organopolysiloxane system according to any one of 1) to 4), wherein the modified polyhedral polysiloxane (A) has at least three hydrosilyl groups or alkenyl groups in the molecule. Composition.

  6) The polyhedral polysiloxane compound (a) containing an alkenyl group and a hydrosilyl group of the modified polyhedral polysiloxane (A) is a vinyl group, 1) to 5) The organopolysiloxane composition according to any one of the above.

  7) In the modified polyhedral polysiloxane (A), the hydrosilyl group or alkenyl group-containing compound (c) component is a siloxane compound containing a hydrosilyl group or an alkenyl group, 1) to 5) The organopolysiloxane composition according to any one of the above.

  8) The organo described in 7) above, wherein in the modified polyhedral polysiloxane (A), the hydrosilyl group- or alkenyl group-containing compound (c) component is a cyclic siloxane having a hydrosilyl group or an alkenyl group. Polysiloxane composition.

  9) The modified polyhedral polysiloxane (A) is characterized in that the hydrosilyl group or alkenyl group-containing compound (c) component is a linear siloxane having a hydrosilyl group or an alkenyl group. An organopolysiloxane composition.

  10) After obtaining the polysiloxane compound (b) obtained by hydrosilylating the polyhedral polysiloxane compounds (a) containing the alkenyl group and the hydrosilyl group, the modified polyhedral polysiloxane (A), The organopolysiloxane composition according to any one of 1) to 9), which is obtained by further hydrosilylating a hydrosilyl group- or alkenyl group-containing compound (c).

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

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

  13) The organopolysiloxane composition according to any one of 1) to 12), which further comprises an adhesion-imparting agent.

  14) The organopolysiloxane composition according to any one of 1) to 13), which contains an inorganic filler.

  15) A cured product obtained by curing the organopolysiloxane composition according to any one of 1) to 14).

  16) An optical element sealing agent comprising the organopolysiloxane composition according to any one of 1) to 15).

  17) An optical device using the optical element sealant according to 16).

18) The optical device according to 17), wherein the moisture permeability after curing of the optical element sealing agent is not more than ^30g / m 2 / 24h.

An organopolysiloxane composition having high heat resistance and light resistance and excellent in thermal shock resistance and gas barrier properties, and an optical device using the same can be provided.

Hereinafter, the present invention will be described in detail.

<Moisture permeability>
While moisture permeability after curing of the LED sealant with organopolysiloxane-based composition of the present invention is less than ^30g / m 2 / 24h, it is the gas barrier properties still are below ^20g / m 2 / 24h It is preferable from the viewpoint.
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.

Moisture permeability (g / m ² / 24h) = {(total weight of specimen after moisture permeability test (g)) − (total weight of specimen before moisture permeability test (g))} × 10000/9 cm ²

Upon curing the sealing agent using organopolysiloxane compositions 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.

<(A) Modified polyhedral polysiloxane>
The modified polyhedral polysiloxane that is the component (A) of the present invention is obtained by hydrosilylating a polysiloxane compound (b) obtained by hydrosilylating polyhedral polysiloxane compounds (a) containing alkenyl groups and hydrosilyl groups. It can be obtained by hydrosilylating the group or alkenyl group-containing compound (c). In the production of the modified polyhedral polysiloxane which is the component (A) of the present invention, the polyhedral compound is obtained by subjecting the polyhedral polysiloxane compound (a) containing alkenyl groups and hydrosilyl groups to hydrosilylation between molecules. After obtaining (b), a hydrohedral group-containing polysiloxane modified compound (A) can be obtained by further hydrosilylating the hydrosilyl group- or alkenyl group-containing compound (c).

  The polyhedral polysiloxane modified body, which is the component (A) in the present invention, is preferably liquid at a temperature of 20 ° C. from the viewpoint of handling properties and processability.

  In addition, the polyhedral polysiloxane modified body as component (A) has at least three hydrosilyl groups in the molecule from the viewpoint of the strength and hardness of the resulting cured product, and further, heat resistance and light resistance, or The molecule preferably has at least three alkenyl groups, and more preferably has at least three hydrosilyl groups in the molecule from the viewpoint of higher heat resistance and light resistance.

<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. The same or different, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms unsubstituted selected from a halogen atom, a chloromethyl group substituted with a cyano group, a trifluoropropyl group, a cyanoethyl group, or the like This is a substituted monovalent hydrocarbon group. 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 hydrogen atom, 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 resulting cured product is not too rigid, and a good molded product 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 hydrogen atom, 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

  In addition, the average number of alkenyl groups and hydrosilyl groups present on Si atoms forming the polyhedral structure in (a) of the present invention is 2.5 or less, and more preferably 1.5 or less. It is preferable. 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.

  On the other hand, from the viewpoint of gas barrier properties, on average, at least one of alkenyl groups and hydrosilyl groups present on Si atoms forming the polyhedral structure in (a) of the present invention is 0.5 or more, The number is 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 property, and dicing property (cutting property) of the cured product obtained using the polyhedral polysiloxane modified product (A) 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, From the viewpoints of hardness and strength, gas barrier properties and dicing properties (cutting workability) of the cured product obtained using the polyhedral polysiloxane modified product (A). 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, the heat resistance and light resistance of a cured product obtained by curing a polyhedral polysiloxane modified (A) or a polyhedral polysiloxane modified (A) finally obtained, for example. From this viewpoint, it is preferable that only the alkenyl group 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 (O
Bu) ₃ ] ₄ } (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, n and m represent an integer), Pt (acac) ₂ , and Ashby And platinum platinum hydrocarbon catalysts described in US Pat. Nos. 3,159,601 and 3,159,622, and platinum alcoholate catalysts described in US Pat. No. 3,220,972 to Lamoreaux et al.

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).

<Hydrosilyl group or alkenyl group-containing compound (c)>
The hydrosilyl group- or alkenyl group-containing compound (c) in the present invention is not particularly limited as long as it contains at least one hydrosilyl group or alkenyl group on average in the molecule, but the modified polyhedral polysiloxane (A From the viewpoint of transparency, heat resistance and light resistance of the cured product obtained by using the modified polyhedral polysiloxane (A). In addition, from the viewpoint of blue laser resistance, gas barrier properties, etc., the hydrosilyl group or alkenyl group is preferably a siloxane compound, a cyclic siloxane having a hydrosilyl group or alkenyl group, a linear siloxane having a hydrosilyl group or alkenyl group. Examples of preferred cyclic siloxanes It is.

  The hydrosilyl group or alkenyl group-containing compound (c) in the present invention 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, Examples thereof include a copolymer of a methylphenylsiloxane unit, a methylvinylsiloxane unit, and a terminal trimethylsiloxy unit, and a polysiloxane whose terminal is blocked with a dimethylvinylsilyl group.

Examples of the cyclic siloxane having an alkenyl group include 1,3,5,7-vinyl-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-1,3,5,7,9,11 -Hexamethylcyclosiloxane and the like are exemplified.
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.

  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.

  From the viewpoint of heat resistance and light resistance, the hydrosilyl group- or alkenyl group-containing compound (c) in the present invention is preferably composed of a hydrogen atom, a vinyl group, or a methyl group on the Si atom. 3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 1,1,3,3-tetramethyldisiloxane are preferred because of their excellent availability. 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 hydrosilyl group or alkenyl group-containing compound (c) is such that the number of hydrogen atoms or alkenyl groups directly bonded to Si atoms is 2. It is preferable to use 5-20, but it depends on the compound. When the amount added is small, gelation occurs due to the crosslinking reaction, resulting in a modified polyhedral polysiloxane (A) having poor handling properties, and when too large, the physical properties of the cured product obtained using (A) are adversely affected. There is. Furthermore, in order to allow an excess amount of the hydrosilyl group or alkenyl group-containing compound (c) to exist, it is preferable to remove the unreacted hydrosilyl group or alkenyl group-containing compound (c), for example, under reduced pressure and heating conditions.

<(B) Organopolysiloxane having two or more alkenyl groups or hydrosilyl groups in one molecule>
(B) component in this invention should just contain 2 or more of alkenyl groups or hydrosilyl groups in 1 molecule, More preferably, it is 2-10. If the number of alkenyl groups in one molecule is large, a more crosslinked structure is obtained, and the gas barrier property of the cured product using the organopolysiloxane composition is improved. However, if the number is too large, the heat resistance and light resistance may be lowered. is there.

  The number of siloxane units as the component (B) in the present invention is not particularly limited, but two or more units are preferable examples. When the number of siloxane units is small, volatilization tends to occur from within the organopolysiloxane 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 organopolysiloxane having two or more alkenyl groups or hydrosilyl groups in one molecule as the component (B) in the present invention is a straight chain having two or more alkenyl groups or hydrosilyl groups from the viewpoint of heat resistance and light resistance. Preferred examples include polysiloxanes, polysiloxanes having two or more alkenyl groups or hydrosilyl groups at the molecular terminals, and cyclic siloxanes having two or more alkenyl groups or hydrosilyl groups. These compounds having two or more alkenyl groups or hydrosilyl groups 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-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7-vinyl-1-phenyl. -3,5,7-trimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,5 -Diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-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-tri Nyl-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-tetramethylcyclotetrasiloxane, 1,5- Examples include divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane. Among these, from the viewpoint of heat resistance and light resistance, 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-vinyl-1-phenyl-3, 5,7-trimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-1,5-diphenyl- 3,7-dimethylcyclotetrasiloxane, 1,3,5,7-vinyl-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-trivinyl-1,3,5 -Trimmer Lucyclosiloxane, 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.

  Specific examples of the linear polysiloxane having two or more hydrosilyl groups include copolymers of dimethylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylhydrogensiloxane units and terminal trimethyl. Copolymers with siloxy units, copolymers of methylphenylsiloxane units with methylhydrogensiloxane units and terminal trimethylsiloxy units, polysiloxanes end-capped with dimethylhydrogensilyl groups, dimethylsiloxane units and methylhydrogen Copolymer of siloxane unit and terminal triethylsiloxy unit, copolymer of diphenylsiloxane unit and methylhydrogensiloxane unit and terminal triethylsiloxy unit, methylphenyl Copolymers of Rokisan units and methylhydrogensiloxane units and terminal triethylsiloxy units, such as polysiloxanes terminals blocked with diethyl hydrogen silyl groups. Among them, from the viewpoint of heat resistance and light resistance, a copolymer of a dimethylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, a copolymer of a diphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, Preferred examples include a copolymer of a methylphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, and a polysiloxane whose ends are blocked with dimethylhydrogensilyl groups.

Specific examples of the polysiloxane having two or more hydrosilyl groups at the molecular ends include polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups exemplified above, dimethylhydrogensiloxane units (H (CH ₃ ) ₂ SiO _{1 / 2} units), SiO ₂ units, SiO _3/2 units, polysiloxanes comprising at least one siloxane unit selected from the group consisting of SiO units, polysiloxanes end-capped with diethyl hydrogensilyl groups, diethyl hydrogen Examples thereof include polysiloxanes composed of at least one siloxane unit selected from the group consisting of siloxane units (H (CH ₃ ) ₂ SiO _1/2 units), SiO ₂ units, SiO _3/2 units, and SiO units. Among them, from the viewpoint of heat resistance and light resistance, polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups, dimethylhydrogensiloxane units (H (CH ₃ ) ₂ SiO _1/2 units) and SiO ₂ units, SiO _{3 / A} preferred example is polysiloxane comprising at least one siloxane unit selected from the group consisting of ₂ units and SiO units.

  Examples of cyclic siloxane compounds having two or more hydrosilyl groups include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7-tetrahydrogen. -1-phenyl-3,5,7-trimethylcyclotetrasiloxane, 1,3,5,7-tetrahydrogen-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7 -Tetrahydrogen-1,5-diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-tetrahydrogen-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1- Phenyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-diphenyl-5,7 Dihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentahydro Gen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7- Examples include tetramethylcyclotetrasiloxane. Among these, from the viewpoint of heat resistance and light resistance, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetrahydrogen-1- Phenyl-3,5,7-trimethylcyclotetrasiloxane, 1,3,5,7-tetrahydrogen-1,3-diphenyl-5,7-dimethylcyclotetrasiloxane, 1,3,5,7-tetrahydro Gen-1,5-diphenyl-3,7-dimethylcyclotetrasiloxane, 1,3,5,7-tetrahydrogen-1,3,5-triphenyl-7-methylcyclotetrasiloxane, 1-phenyl-3 , 5,7-trihydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3-diphenyl-5,7-dihydrogen-1,3, , 7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7 , 9-pentamethylcyclosiloxane and 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane are preferred examples.

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

  The amount of the organopolysiloxane having two or more alkenyl groups or hydrosilyl groups in one molecule as the component (B) can be variously set. However, when the component (B) has an alkenyl group, one alkenyl group is added. The number of hydrogen atoms directly connected to Si atoms contained in the modified polyhedral polysiloxane that is the component (A) is 0.3-5, preferably 0.5-3. desirable. 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. Further, when the component (B) has a hydrosilyl group, 0.2 to 3 alkenyl groups directly connected to Si atoms contained in the modified polyhedral polysiloxane as the component (A) per hydrosilyl group are 0.2 to 3 It is desirable to add them at a rate of 0.3 to 2 pieces. If the proportion of hydrogen atoms directly connected to Si atoms is too small, the physical properties of the cured product may be adversely affected. If it is too large, poor appearance due to foaming or the like tends to occur.

<(C) Organosilicon compound having one alkenyl group or hydrosilyl group in one molecule>
The component (C) in the present invention is an organosilicon compound having one alkenyl group or hydrosilyl group in one molecule, and by using the component (C), the cured product can have low elasticity, Crack resistance can be improved.

  The component (C) in the present invention preferably contains at least one aryl group in one molecule from the viewpoints of gas barrier properties and refractive index, and further, the aryl group is directly bonded to a silicon atom. This is a more preferable example from the viewpoint of heat resistance and light resistance. In such a component (C), the larger the number of aryl groups in one molecule, the greater the effect of improving the gas barrier property and refractive index of the cured product.

    The component (C) in the present invention is preferably a silane or polysiloxane from the viewpoint of heat resistance and light resistance. When the component (C) is a silane having one alkenyl group in one molecule, specifically, for example, vinyltrimethylsilane, vinyldimethylphenylsilane, vinyldiphenylmethylsilane, vinyltriphenylsilane, vinyltriethyl Examples include silane, vinyldiethylphenylsilane, vinyldiphenylethylsilane, allyldimethylphenylsilane, allyldiphenylmethylsilane, allyltriphenylsilane, allyldiethylphenylsilane, allyldiphenylethylsilane, and the like. Among these, vinyltrimethylsilane, vinyldimethylphenylsilane, vinyldiphenylmethylsilane, and vinyltriphenylsilane are preferable examples from the viewpoint of heat resistance and light resistance. In addition, when the component (C) is a silane having one hydrosilyl group in one molecule, specifically, for example, trimethylsilane, dimethylphenylsilane, diphenylmethylsilane, triphenylsilane, triethylsilane, diethylphenylsilane, diphenyl Examples include ethylsilane. Among these, trimethylsilane, dimethylphenylsilane, diphenylmethylsilane, and triphenylsilane are preferable examples from the viewpoint of heat resistance and light resistance.

  In addition, when the component (C) is a polysiloxane, a polysiloxane having a linear structure having one alkenyl group or hydrosilyl group, a polysiloxane having one alkenyl group or hydrosilyl group at the molecular end, 1 alkenyl group or hydrosilyl group The cyclic siloxane etc. which have one are illustrated.

  In the case where the component (C) is a polysiloxane having a straight chain structure having one alkenyl group in one molecule, specifically, for example, polydimethyl having one end each blocked with a dimethylvinylsilyl group and a trimethylsilyl group. Siloxane, polymethylphenylsiloxane blocked with a dimethylvinylsilyl group and a trimethylsilyl group each at one end, polydiphenylsiloxane blocked with a dimethylvinylsilyl group and a trimethylsilyl group, respectively, and a dimethylvinylsilyl group Copolymers of dimethylsiloxane units and methylphenylsiloxane units each end-capped with trimethylsilyl groups, and dimethylsiloxane units and diphenylsiloxy units each end-capped with dimethylvinylsilyl groups and trimethylsilyl groups. Copolymer, polydimethylsiloxane with one end blocked with diethylvinylsilyl group and triethylsilyl group, polymethyl with one end blocked with diethylvinylsilyl group and triethylsilyl group, respectively. Phenylsiloxane, polydiphenylsiloxane capped with one each by diethylvinylsilyl group and triethylsilyl group, dimethylsiloxane unit and methylphenylsiloxane capped with one each by diethylvinylsilyl group and triethylsilyl group Examples thereof include a copolymer with a unit, and a copolymer of a dimethylsiloxane unit and a diphenylsiloxane unit each having one end blocked with a diethylvinylsilyl group and a triethylsilyl group. Among them, from the viewpoint of heat resistance and light resistance, polydimethylsiloxane having one end each blocked with a dimethylvinylsilyl group and one trimethylsilyl group, and polymethylsiloxane having one end blocked with a dimethylvinylsilyl group and one trimethylsilyl group. Phenylsiloxane, polydiphenylsiloxane blocked with dimethylvinylsilyl group and trimethylsilyl group each at one end, dimethylsiloxane unit and methylphenylsiloxane unit blocked with dimethylvinylsilyl group and trimethylsilyl group at one end respectively A preferred example is a copolymer of a dimethylsiloxane unit and a diphenylsiloxane unit each having one end blocked with a dimethylvinylsilyl group and a trimethylsilyl group.

  In addition, when the component (C) is a polysiloxane having a linear structure having one hydrosilyl group in one molecule, specifically, for example, each end is blocked with a dimethylhydrogensilyl group and a trimethylsilyl group. Polydimethylsiloxane, polymethylphenylsiloxane capped with dimethylhydrogensilyl group and trimethylsilyl group each at one end, polydiphenylsiloxane capped with dimethylhydrogensilyl group and trimethylsilyl group, respectively Copolymers of dimethylsiloxane units and methylphenylsiloxane units each blocked with a hydrogensilyl group and a trimethylsilyl group, and one terminal each with a dimethylhydrogensilyl group and a trimethylsilyl group. Copolymer of dimethylsiloxane units and diphenylsiloxane units, polydimethylsiloxane blocked with one each of diethylhydrogensilyl group and triethylsilyl group, and one end with diethylhydrogensilyl group and triethylsilyl group. Polymethylphenylsiloxane blocked one by one, polydiphenylsiloxane blocked one by one with diethylhydrogensilyl group and triethylsilyl group, one terminal each with diethylhydrogensilyl group and triethylsilyl group Copolymers of dimethylsiloxane units and methylphenylsiloxane units blocked one by one, and dimethylsiloxane units and diphenyls blocked one by one with a diethylhydrogensilyl group and a triethylsilyl group, respectively. A copolymer of siloxane units can be exemplified. Among them, from the viewpoint of heat resistance and light resistance, polydimethylsiloxane having one end blocked with a dimethylhydrogensilyl group and one trimethylsilyl group, and one end each blocked with a dimethylhydrogensilyl group and a trimethylsilyl group. Polymethylphenylsiloxane, polydiphenylsiloxane blocked with dimethylhydrogensilyl group and trimethylsilyl group each at one end, dimethylsiloxane unit and methyl blocked at one end with dimethylhydrogensilyl group and trimethylsilyl group, respectively Preferred are copolymers with phenylsiloxane units, and copolymers of dimethylsiloxane units and diphenylsiloxane units, each of which is capped with a dimethylhydrogensilyl group and a trimethylsilyl group. It is mentioned as examples.

When the component (C) is a polysiloxane having one alkenyl group at the molecular end, specifically, for example, a polysiloxane having one end blocked with a dimethylvinylsilyl group, and the polysiloxane is a SiO ₂ unit, A polysiloxane comprising at least one siloxane unit selected from the group consisting of SiO _3/2 units and SiO units, a polysiloxane having one end blocked with a diethylvinylsilyl group, and the polysiloxane is an SiO ₂ unit, SiO ₃ Examples include polysiloxane composed of at least one siloxane unit selected from the group consisting of _{/ 2} units and SiO units. Among them, from the viewpoint of heat resistance and light resistance, at least 1 selected from the group consisting of a polysiloxane having one end blocked with a dimethylvinylsilyl group, the polysiloxane being composed of SiO ₂ units, SiO _3/2 units, and SiO units. A preferred example is polysiloxane comprising two siloxane units.

When the component (C) is a polysiloxane having one hydrosilyl group at the molecular end, specifically, for example, a polysiloxane having one end blocked with a dimethylhydrogensilyl group, and the polysiloxane is SiO A polysiloxane composed of at least one siloxane unit selected from the group consisting of ₂ units, SiO _3/2 units, and SiO units, and a polysiloxane having one end blocked with a dimethylhydrogensilyl group, wherein the polysiloxane is SiO _2. Examples thereof include polysiloxanes composed of at least one siloxane unit selected from the group consisting of units, SiO _3/2 units, and SiO units. Among them, from the viewpoint of heat resistance and light resistance, at least one selected from the group consisting of SiO ₂ units, SiO _3/2 units, and SiO units is a polysiloxane having one end blocked with a dimethylhydrogensilyl group. A preferred example is polysiloxane composed of one siloxane unit.
When the component (C) is a cyclic siloxane having one alkenyl group, specifically, for example, 1-vinyl-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1-vinyl -3-phenyl-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-vinyl-3,5-diphenyl-1,3,5,7,7-pentamethylcyclotetrasiloxane, 1 -Vinyl-3,5,7-triphenyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-vinyl-1,3,3,5,5,7,7-heptaethylcyclotetrasiloxane, 1-vinyl-3-phenyl-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-vinyl-3,5-diphenyl-1,3,5,7,7-pentaethylcyclo Tetrashiroki Down, 1-vinyl-3,5,7-triphenyl-1,3,5,7-tetraethyl cyclotetrasiloxane and the like. Among them, from the viewpoint of heat resistance and light resistance, 1-vinyl-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1-vinyl-3-phenyl-1,3,5,5, 7,7-hexamethylcyclotetrasiloxane, 1-vinyl-3,5-diphenyl-1,3,5,7,7-pentamethylcyclotetrasiloxane, 1-vinyl-3,5,7-triphenyl-1 3,5,7-tetramethylcyclotetrasiloxane is a preferred example.

  When the component (C) is a cyclic siloxane having one hydrosilyl group, specifically, for example, 1-hydrogen-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1-hydrogen-3-phenyl-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-hydrogen-3,5-diphenyl-1,3,5,7,7-pentamethyl Cyclotetrasiloxane, 1-hydrogen-3,5,7-triphenyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-hydrogen-1,3,3,5,5,7,7 -Heptaethylcyclotetrasiloxane, 1-hydrogen-3-phenyl-1,3,5,5,7,7-hexamethylcyclotetrasiloxane, 1-hydrogen-3,5 Diphenyl -1,3,5,7,7- pentaethyl cyclotetrasiloxane, 1-hydrogen-3,5,7 triphenyl-1,3,5,7 tetraethyl cyclotetrasiloxane and the like. Among these, from the viewpoint of heat resistance and light resistance, 1-hydrogen-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1-hydrogen-3-phenyl-1,3,5, 5,7,7-hexamethylcyclotetrasiloxane, 1-hydrogen-3,5-diphenyl-1,3,5,7,7-pentamethylcyclotetrasiloxane, 1-hydrogen-3,5,7- A preferred example is triphenyl-1,3,5,7-tetramethylcyclotetrasiloxane.

The amount of the component (C) can be variously set, but the component (C) is preferably 1% relative to the sum (100% by weight) of the component (C) and the component (A) and the component (B). It is preferably used in the range of from 60% to 60% by weight, more preferably from 5 to 50% by weight. When there are too many (C) components, hardened | cured material will become soft too much and there exists a possibility that a malfunction may arise. Moreover, when there are too few, the crosslinking density of a composition may be too high, and there exists a possibility that a crack may arise.
These organosilicon compounds having one alkenyl group or one hydrosilyl group in one molecule as the component (C) may be used alone or in combination of two or more.

<Hydrosilylation catalyst>
In the present invention, a hydrosilylation catalyst is used when the organopolysiloxane composition 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.

<Curing retarder>
The curing retarder is a component for improving the storage stability of the organopolysiloxane 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 organopolysiloxane composition and the substrate in the present invention, and is not particularly limited as long as it has such an effect. The 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.

<Inorganic filler>
An inorganic filler can be added to the organopolysiloxane composition of the present invention as necessary.

By using an inorganic filler as a component of the organopolysiloxane composition of the present invention, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical characteristics, light reflection of the molded product obtained Various physical properties such as rate, 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 organopolysiloxane composition, the strength, hardness, elastic modulus, thermal expansion coefficient, thermal conductivity, heat dissipation, electrical characteristics, light reflectance of the molded article obtained, Various physical properties such as flame retardancy 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 equation, the BET equation shows the relationship between the adsorption equilibrium pressure P when in an adsorption equilibrium state at a constant temperature and the adsorption amount V at that pressure, and is expressed as follows.

Formula: P / V (Po−P) = (1 / VmC) + ((C−1) / VmC) (P / Po)
(Po: saturated vapor pressure, Vm: adsorption amount of monomolecular layer, adsorption amount when gas molecules form a monomolecular layer on a solid surface, C: parameters 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.

  The addition amount of the inorganic filler is not particularly limited, but is 1 to 1000 parts by weight, more preferably 5 to 500 parts by weight, and still more preferably, with respect to 100 parts by weight of the mixture of the component (A) and the component (B). 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. However, in terms of easy storage stability, a method of mixing the component (A) after mixing with the component (B) is desirable. Moreover, in the point that the (A) component and (B) component which are reaction components are mixed well and it is easy to obtain a stable molded product, the inorganic filler is added to the mixture of the (A) component and the (B) component. It is preferable to mix.

  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.

<Organopolysiloxane composition>
The organopolysiloxane composition of the present invention is a modified polyhedral polysiloxane (A), an organopolysiloxane (B) having two or more alkenyl groups or hydrosilyl groups in one molecule, or an alkenyl group in one molecule or It can be obtained by adding an organosilicon compound (C) having one hydrosilyl group and, if necessary, a hydrosilylation catalyst, a curing retarder and an adhesion promoter. The organopolysiloxane 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 organopolysiloxane composition of the present invention has high hardness and low coefficient of thermal expansion, 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 to be 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 for 10 minutes to 8 hours.

  Specifically, the organopolysiloxane 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.

  Further, the organopolysiloxane 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.

  The organopolysiloxane composition used in the present invention is a mixture of the above components uniformly using a kneader such as a roll, a Banbury mixer, a kneader, or a planetary stirring deaerator, and heat-treated as necessary. You may give it.

The organopolysiloxane 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.
<Moisture permeability>
Moisture permeability of LED sealant with organopolysiloxane-based composition of the present invention is ^30g / m 2 / 24h or less, preferably further is less ^20g / m 2 / 24h.
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 moisture measurement) manufactured by Wako Pure Chemical Industries, Ltd. is filled into a square shape and used as a test specimen. Further, a 5 ± 0.1 cm square cured product for evaluation (2 mm thickness) is fixed to the upper part, and cured at a temperature of 40 ° C., a humidity of 90% RH for 24 hours in a thermo-hygrostat (PR-2KP manufactured by ESPEC).
The moisture permeability is calculated according to the following formula.

Moisture permeability (g / m ² / 24h) = {(total weight of specimen after moisture permeability test (g)) − (total weight of specimen before moisture permeability test (g))} × 10000/9 cm ²

  The moisture permeability in the present invention is a value that serves as a standard for suppressing the corrosiveness of, for example, a silver lead frame or a reflector in an LED. When the moisture permeability of the sealant is high, specifically, when it is higher than 30 g / m 2/24 h, moisture, gas, such as oxygen, hydrogen sulfide, etc. can easily pass through. May be corroded, leading to deterioration of the light emitting characteristics of the LED.

<Optical device>
The optical device of the present invention is an optical device using the organopolysiloxane composition of the present invention.
By using the organopolysiloxane 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.

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

(Light transmittance)
Two pieces of 10 cm × 10 cm plate glass were washed pure and dried. Then, after spraying with a fluorine-type mold release agent (Daikin Kogyo's die-free, GA6010) and uniformly applying with Kimwipe, the excess was removed. A glass cell is created by sandwiching a 2 mm thick silicone rubber cut into a U-shape with a Teflon (registered trademark) seal wound between two glass plates and fixing it with a clip. did.
An organopolysiloxane-based composition was poured into this glass cell, and a cured product having a thickness of 2 mm was prepared by thermosetting in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 6 hours.

  The value after curing was a value obtained by measuring a light transmittance of 400 nm in air using a trial ultraviolet visible spectrophotometer (JASCO JSV 560 manufactured by JASCO Corporation) for a cured product having a thickness of 2 mm.

  The value after the heat resistance test is that a cured product having a thickness of 2 mm is further cured in air at 150 ° C. for 100 hours. The light transmittance at 400 nm was measured.

The value after the light resistance test is UV irradiation of a cured product having a thickness of 2 mm (manufactured by Suga Test Instruments Co., Ltd., metering weather meter, black panel temperature 120 ° C., irradiance 0.53 kW / m ² , integrated irradiance 50 MJ / m ² was irradiated), and the light transmittance of the cured product at 400 nm in air was measured with an ultraviolet-visible spectrophotometer (JASCO JSV 560 manufactured by JASCO Corporation).

(Moisture permeability test)
The organopolysiloxane-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. × 6 hours to prepare a sample having a thickness of 2 mm. 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 water vapor transmission rate was calculated according to equation (3).

Moisture permeability (g / m ² / 24h) = {(total weight of specimen after moisture permeability test (g)) − (total weight of specimen before moisture permeability test (g))} × 10000 / 9.0 cm ² ( 3)

(Hydrogen sulfide test, H ₂ S test)
An organopolysiloxane composition is injected into an LED package manufactured by Enomoto Co., Ltd. (product name: TOP LED 1-IN-1) and heated in a convection oven at 80 ° C. × 2 hours, 100 ° C. × 1 hour, 150 ° C. × 6 hours. A sample was prepared by curing. 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 ×.

(Crack test)
Enomoto Co., Ltd. LED package (product name: TOP LED 1-IN-1), 0.4mm x 0.4mm x 0.2mm single crystal silicon chip, Henkel Japan Co., Ltd. epoxy adhesive (product name) : LOCTITE 348) and placed in an oven at 150 ° C. for 30 minutes. An organopolysiloxane 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.

(Heat cycle test, thermal shock test)
An organopolysiloxane-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.

(Production Example 1)
As a method for synthesizing a polysiloxane having a polyhedral structure, 1042 g of tetraalkoxysilane was added to 1288 g of a 48% trimethyl-2hydroxyethylammonium hydroxide aqueous solution (choline aqueous solution), and the mixture was vigorously stirred at room temperature for 3 hours. The reaction system generates heat,
When the solution became homogeneous, 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.

(Production Example 2)
A mixed solution of 40 g of the polyhedral polysiloxane compound containing alkenyl groups and hydrosilyl groups obtained in Production Example 1 and 200 g of toluene is mixed with 10.1 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 had disappeared.
Next, it was added dropwise to a mixed solution of 64 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane (manufactured by Clariant) and 64 g of toluene, and heated at 105 ° C. for 2 hours. And cooled to room temperature. ^{From 1} H-NMR, it was confirmed that the vinyl group derived from polysiloxane had disappeared. The polyhedral polysiloxane modified product is obtained by distilling unreacted 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane with toluene from the obtained reaction solution. 48 g was obtained.

Example 1
To 5.00 g of the modified polyhedral polysiloxane obtained in Production Example 2, 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane (manufactured by Gelest, SID4609.0) After 2.48 g and 1.32 g of vinyldiphenylmethylsilane (LS5600, manufactured by Shin-Etsu Chemical Co., Ltd.) were added and stirred, the mixture was stirred and defoamed with a planetary stirring deaerator to obtain an organopolysiloxane composition. Using the thus obtained organopolysiloxane composition, it was evaluated according to each test method described above. The results are shown in Table 1.

(Example 2)
To 5.00 g of the modified polyhedral polysiloxane obtained in Production Example 2, 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane (manufactured by Gelest, SID4609.0) 2.48 g, vinyl diphenylmethylsilane (LS5600, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.32 g and 0.26 parts by weight of SH6040 manufactured by Toray Dow Corning, which is 3-glycidoxypropyltrimethoxysilane, were added and stirred. Furthermore, 1.06 μl of ethynylcyclohexanol and 0.62 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) 0.15 μl was added and stirred, followed by stirring and defoaming with a planetary stirring deaerator to obtain an organopolysiloxane composition. Using the thus obtained organopolysiloxane composition, it was evaluated according to each test method described above. The results are shown in Table 1.

(Example 3)
To 5.00 g of the modified polyhedral polysiloxane obtained in Production Example 2, 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane (manufactured by Gelest, SID4609.0, (Weight average molecular weight 385, Vi valence 5.20 mol / kg) 2.48 g, vinyldiphenylmethylsilane (LS5600, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.32 g, 3-glycidoxypropyltrimethoxysilane manufactured by Toray Dow Corning SH6040 Was added and stirred. Further, 0.44 g of fumed silica (manufactured by Nippon Aerosil Co., Ltd., R812, primary average particle size 7 nm and BET specific surface area 260 (m ^{2 /} g)) was added and stirred. Furthermore, 1.06 μl of ethynylcyclohexanol and 0.62 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) 0.13 μl was added and stirred, followed by stirring and defoaming with a planetary stirring deaerator to obtain an organopolysiloxane composition. Using the thus obtained organopolysiloxane composition, it was evaluated according to each test method described above. The results are shown in Table 1.

Example 4
To 5.00 g of the modified polyhedral polysiloxane obtained in Production Example 2, 4.33 g of phenylsiloxane containing a vinyl group at both ends (FX-T180A, manufactured by Adeka), diphenylmethylsilane (SID4555.0, Gelest) 1.25 g, 0.32 parts by weight of SH6040 manufactured by Toray Dow Corning, which is 3-glycidoxypropyltrimethoxysilane, was added and stirred. Further, 0.53 μl of ethynylcyclohexanol and 0.31 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) 0.10 μl was added and stirred, followed by stirring and defoaming with a planetary stirring deaerator to obtain an organopolysiloxane composition. Using the thus obtained organopolysiloxane composition, it was evaluated according to each test method described above. The results are shown in Table 1.

(Example 5)
To 5.00 g of the modified polyhedral polysiloxane obtained in Production Example 2, 2.39 g of phenylsiloxane (FX-T180A, manufactured by Adeka) containing vinyl groups at both ends, vinylpentamethyldisiloxane (SIV9090.0, 0.26 parts by weight of SH6040 manufactured by Toray Dow Corning, which is 3-glycidoxypropyltrimethoxysilane, was added and stirred. Furthermore, 1.06 μl of ethynylcyclohexanol and 0.62 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 an organopolysiloxane composition. Using the thus obtained organopolysiloxane composition, it was evaluated according to each test method described above. The results are shown in Table 1.

(Example 6)
To 5.00 g of the modified polyhedral polysiloxane obtained in Production Example 2, 2.14 g of linear polydimethylsiloxane having a vinyl group at the terminal (DMS-V03, manufactured by Gelest), vinyl diphenylmethylsilane (LS5600, 2.38 g (manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred. Further, 1.06 μl of ethynylcyclohexanol and 0.62 μl of dimethyl maleate were added and stirred, followed by stirring and defoaming with a planetary stirring deaerator to obtain an organopolysiloxane composition. Using the thus obtained organopolysiloxane composition, it was evaluated according to each test method described above. The results are shown in Table 1.

(Comparative Example 1)
To 5.00 g of the modified polyhedral polysiloxane obtained in Production Example 2, 1,5-divinyl-3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane (manufactured by Gelest, SID4609.0) 0.24 parts by weight of SH6040 manufactured by Toray Dow Corning, which is 3.12 g, 3-glycidoxypropyltrimethoxysilane, was added and stirred. Furthermore, 1.06 μl of ethynylcyclohexanol and 0.62 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) 0.12 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)
To 5.00 g of the modified polyhedral polysiloxane obtained in Production Example 2, 6.49 g of linear polydimethylsiloxane containing a vinyl group at the terminal (MVD8MV, manufactured by Clariant) was added, and 3-glycidoxypropyltri 0.34 parts by weight of SH6040 manufactured by Toray Dow Corning, which is methoxysilane, was added and stirred. Furthermore, 1.06 μl of ethynylcyclohexanol and 0.62 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) 0.12 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 3)
To 5.00 g of the modified polyhedral polysiloxane obtained in Production Example 2, 3.25 g of linear polydimethylsiloxane containing a vinyl group at the terminal (DMS-V03, manufactured by Gelest) was added, and 3-glycidoxy was added. 0.25 parts by weight of SH6040 manufactured by Toray Dow Corning, which is propyltrimethoxysilane, was added and stirred. Furthermore, 1.06 μl of ethynylcyclohexanol and 0.62 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) 0.12 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 has been found that the molded product obtained from the organopolysiloxane composition of the present invention has high heat resistance and light resistance, and is excellent in thermal shock resistance and gas barrier properties. By using the organopolysiloxane 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.

Claims (18)

An organopolysiloxane composition comprising (A), (B) and (C).
(A) A polysiloxane compound (b) obtained by hydrosilylating a polyhedral polysiloxane compound (a) containing an alkenyl group and a hydrosilyl group is hydrosilylated with a hydrosilyl group or alkenyl group-containing compound (c). Polyhedral polysiloxane modified product obtained,
(B) an organopolysiloxane having two or more alkenyl groups or hydrosilyl groups in one molecule;
(C) An organosilicon compound having one alkenyl group or hydrosilyl group in one molecule. The organopolysiloxane composition according to claim 1, wherein the component (C) is an organosilicon compound containing at least one aryl group.
In the polysiloxane compound (b) of the modified polyhedral polysiloxane (A), either an alkenyl group or a hydrosilyl group derived from the polyhedral polysiloxane compound (a) containing an alkenyl group and a hydrosilyl group remains. The organopolysiloxane composition according to claim 1, wherein the composition is an organopolysiloxane composition. The organopolysiloxane composition according to any one of claims 1 to 3, wherein the modified polyhedral polysiloxane (A) is liquid at a temperature of 20 ° C. The organopolysiloxane composition according to any one of claims 1 to 4, wherein the polyhedral polysiloxane modified product (A) has at least three hydrosilyl groups or alkenyl groups in the molecule. . The alkenyl group of the polyhedral polysiloxane compound (a) containing an alkenyl group and a hydrosilyl group of the modified polyhedral polysiloxane (A) is a vinyl group. 2. The organopolysiloxane composition according to item 1. 6. The modified polyhedral polysiloxane (A), wherein the component (c) containing a hydrosilyl group or alkenyl group is a siloxane compound containing a hydrosilyl group or alkenyl group. 2. The organopolysiloxane composition according to item 1. The organopolysiloxane according to claim 7, wherein in the modified polyhedral polysiloxane (A), the hydrosilyl group or alkenyl group-containing compound (c) component is a cyclic siloxane having a hydrosilyl group or an alkenyl group. Siloxane-based composition. 8. The modified polyhedral polysiloxane (A), wherein the hydrosilyl group or alkenyl group-containing compound (c) component is a linear siloxane having a hydrosilyl group or an alkenyl group. Organopolysiloxane composition. After obtaining the polysiloxane compound (b) obtained by hydrosilylating the polyhedral polysiloxane compound (a) containing the alkenyl group and the hydrosilyl group, the modified polyhedral polysiloxane (A) is further hydrosilylated. The organopolysiloxane composition according to any one of claims 1 to 9, which is obtained by hydrosilylation reaction of a group or alkenyl group-containing compound (c). 11. The organopolysiloxane composition according to any one of claims 1 to 10, comprising a hydrosilylation catalyst. The organopolysiloxane composition according to any one of claims 1 to 11, which contains a curing retarder. The organopolysiloxane composition according to any one of claims 1 to 12, wherein the composition contains an adhesion-imparting agent. The organopolysiloxane composition according to any one of claims 1 to 13, wherein the composition contains an inorganic filler. Hardened | cured material obtained by hardening | curing the organopolysiloxane type composition of any one of Claims 1-14. The optical element sealing agent formed using the organopolysiloxane type composition of any one of Claims 1-15. An optical device comprising the optical element sealant according to claim 16. The optical device of claim 17, moisture permeability after curing of the optical element sealing agent is equal to or less than 30g / m 2 / ^24h.