JP2010095616A - Polysiloxane-based composition and cured product obtained from it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polysiloxane-based composition being excellent in molding processability, transparency, heat-resistance and light-resistance, being further excellent in crack-resistance at high temperature heating, and especially using a liquid-like polyhedron structure polysiloxane, and a cured product. <P>SOLUTION: The polysiloxane-based composition contains a polyhedron structure polysiloxane-modified substance (A) obtained by modifying compound (b) having a hydrosilyl group capable of being subjected to a hydrosilylation reaction with component (a) and/or an alkenyl group relative to the polyhedron structure polysiloxane based compound (a) containing the alkenyl group and/or the hydrosilyl group, and a curing agent (B) as indispensable components. The polysiloxane-based composition is characterized in that weight reduction at 130°C of the (B) is 2.5% or less. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polysiloxane composition that is excellent in molding processability, transparency, heat resistance, and light resistance, and further excellent in crack resistance during high-temperature heating, and in particular, uses a liquid polyhedral polysiloxane.

  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 these, polyhedral polysiloxanes are known to exhibit superior heat resistance, light resistance, chemical stability, low dielectric constant, and the like due to their specific chemical structure. However, polyhedral polysiloxane is generally a polyfunctional and solid compound, and it is difficult to control the reaction, and it is difficult to obtain a molded body because of poor handling and molding processability.

  For example, a hydrosilylation curable composition using a functional group-containing polyhedral polysiloxane is disclosed (Non-Patent Document 1). However, in the corresponding technology, a polysiloxane having a polyhedral structure as a starting material is polyfunctional. Since it is a solid material, it is difficult to control the curing reaction, and coating and injection molding are difficult.

  Further, as polysiloxane compounds having a polyhedral structure, those having various functional groups are known, for example, those having an epoxy group (Patent Document 1), those having a (meth) acryloyl group (Patent Document) 2) Various compounds such as those having hydrolyzable silyl groups (Patent Document 3) and those having oxetanyl groups (Patent Document 4) have been reported. These compounds are crosslinked by heat or light in the presence of various curing initiators to give a cured product.

  In addition to this, a curable composition using a polysiloxane having a polyhedral structure containing an epoxy group or a phenyl group (Patent Document 1 or Patent Documents 5 to 6) is disclosed. The characteristics of the polysiloxane composition, such as coloring due to heating, are not fully utilized.

  In addition, in the polysiloxane material as described above, it is assumed that the material is used at a very high temperature, specifically, for example, 250 ° C. or more, but due to thermal expansion at this time, and shrinkage at the time of cooling, There is a possibility that cracks may occur, and there are cases where problems remain in the reliability of the material.

As described above, disclosure of a material using a polysiloxane compound having a polyhedral structure is seen, but it has characteristics of a siloxane-based composition, has excellent handling and molding processability, and is resistant to cracking when heated at high temperatures. No example of excellent properties was found, and the development of new materials was desired.
JP 2004-359933 A JP 2004-143449 A JP 2006-269402 A Japanese Patent Laid-Open No. 2005-23256 JP-T-2004-529984 JP 2006-22207 A J. et al. Am. Chem. Soc. 1998, 120, 8380-8391

  The present invention provides a polysiloxane composition and a cured product, in which the above-mentioned problems are solved, excellent in moldability, transparency, heat resistance, light resistance, adhesiveness, and crack resistance during high temperature heating. The purpose is to provide.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have made the present invention. The present invention has the following configuration.

  1). For the polyhedral polysiloxane compound (a) containing an alkenyl group and / or a hydrosilyl group, the compound (b) having a hydrosilyl group and / or alkenyl group capable of hydrosilylation reaction with the component (a) is modified. A polysiloxane composition comprising the modified polyhedral polysiloxane (A) and the curing agent (B) obtained as essential components, wherein the weight loss of the (B) at 130 ° C. is 2. A polysiloxane composition characterized by being 5% or less.

  2). (A) The polysiloxane composition according to 1), wherein the component is liquid at a temperature of 20 ° C.

  3). The polysiloxane composition according to 1) or 2), wherein the compound (b) is a cyclic siloxane containing a hydrosilyl group and / or an alkenyl group.

  4). The polysiloxane composition according to 1) or 2), wherein the compound (b) is a linear siloxane containing a hydrosilyl group and / or an alkenyl group at the molecular end.

  5). The polysiloxane composition according to any one of 1) to 4), wherein the compound (b) has at least three hydrosilyl groups or alkenyl groups in the molecule.

  6). The number of hydrogen atoms and / or alkenyl groups directly bonded to the Si atom of the compound (b) having a hydrosilyl group and / or alkenyl group is such that the polyhedral polysiloxane compound (a) has an alkenyl group and / or hydrosilyl group. It is modified by adding 2.5 to 20 hydrogen atoms per alkenyl group and / or Si atom directly connected to the Si atom, and is obtained by distilling off the unreacted compound (b). The polysiloxane composition according to any one of 1) to 5).

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

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

8). Formula [AR ¹ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group and / or a hydrogen atom provided that at least one is an alkenyl group;. R ¹ is An alkyl group or an aryl group; R ⁴ is a substituent other than an alkenyl group and a hydrogen atom, for example, an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane or siloxane compound) In the polyhedral polysiloxane compound (a) composed of siloxane units, the compound (b) having a hydrosilyl group is within a range of 2.5 to 20 hydrogen atoms directly bonded to Si atoms per alkenyl group. 1) to 7 obtained by adding an excess amount to modify by hydrosilylation reaction and distilling off compound (b) having an unreacted hydrosilyl group. The polysiloxane composition according to any one of 1).

9). Formula [BR ¹ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; B is alkenyl and / or hydrogen atom, provided that at least one is hydrogen atom;. R ¹ is An alkyl group or an aryl group; R ⁴ is a substituent other than an alkenyl group and a hydrogen atom, for example, an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane or siloxane compound) The range in which the polyhedral polysiloxane compound (a) composed of siloxane units has 2.5 to 20 alkenyl groups per hydrogen atom directly bonded to the Si atom of the compound (b) having an alkenyl group. 1) to 8), which are obtained by adding an excessive amount of the above and modifying by hydrosilylation reaction to distill off the compound (b) having an unreacted alkenyl group. The polysiloxane composition according to claim 1.

  10). The polysiloxane composition according to any one of 1) to 9), wherein the weight average molecular weight (Mw) of the curing agent (B) is less than 5000.

  11). Any one of 1) to 10), wherein the curing agent (B) is a linear polysiloxane containing an alkenyl group and / or a hydrosilyl group at a molecular terminal having a weight average molecular weight (Mw) of less than 5000. 2. The polysiloxane composition according to 1.

  12). Any one of 1) to 11), wherein the curing agent (B) is a linear polysiloxane containing an alkenyl group and / or a hydrosilyl group at a molecular terminal having a weight average molecular weight (Mw) of less than 3000. 2. The polysiloxane composition according to 1.

  13). The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the curing agent (B) is less than 1.7, and any one of 1) to 12) The polysiloxane composition as described.

  14). The polysiloxane composition according to any one of 1) to 13), which contains a hydrosilylation catalyst.

  15). Hardened | cured material formed by hardening | curing the polysiloxane type composition of any one of 1) -14).

  According to the present invention, excellent processability, transparency, heat resistance, light resistance and adhesiveness are obtained, and further, crack resistance at high temperature heating is excellent, in particular, a liquid polyhedral polysiloxane modified body is used. A composition can be provided.

  The present invention is described in detail below.

<Modified polyhedral polysiloxane>
The polyhedral polysiloxane-modified product in the present invention is a polyhedral polysiloxane compound (a) containing an alkenyl group and / or a hydrosilyl group, a hydrosilyl group capable of hydrosilylation reaction with the component (a) and / or It can be obtained by modifying the compound (b) having an alkenyl group. In the present invention, the modified polyhedral polysiloxane is not gelled during synthesis of the modified product, and the resulting polyhedral polysiloxane modified product can be made liquid at a temperature of 20 ° C. from the viewpoint of handling properties and molding processability.

  As the modified polyhedral polysiloxane in the present invention, a modified product obtained by modifying the polyhedral polysiloxane compound (a) containing an alkenyl group with the compound (b) having a hydrosilyl group is produced. From the viewpoints of ease and productivity.

The preferred polyhedral polysiloxane-modified product in the present invention will be specifically described below. A preferred polyhedral polysiloxane modified product in the present invention is characterized in that [XR ¹ ₂ SiO—SiO _3/2 ] is an essential unit as a siloxane unit having a reactive functional group, and if necessary, An arbitrary siloxane unit [R ² ₃ SiO—SiO _3/2 ] as a physical property adjusting unit is contained as a structural unit, and the following formula:
[XR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; group having X reactive functional group; R ¹ is an alkyl group or an aryl group,; R ² is Examples of the modified polyhedral polysiloxane include siloxane units represented by an alkyl group, an aryl group, an alkenyl group, a hydrogen atom, or a group connected to another polyhedral polysiloxane. Here, a is an average of 1 or more, preferably 2 or more, and b is 0 or an integer of 1 or more. a + b is an integer of 6 to 24, preferably an integer of 6 to 12.

Hereinafter, the siloxane unit [XR ¹ ₂ SiO—SiO _3/2 ] having a reactive functional group will be described.

  A siloxane unit having a functional group capable of reacting is crosslinked in the presence of a hydrosilylation catalyst described later by a hydrosilylation reaction, or crosslinked in the presence of a thermal curing initiator or a photocuring initiator. This unit is responsible for curing.

  Here, the group X having a preferable reactive functional group is not particularly limited as long as it is a group represented by any one of the general formula (1) and the general formula (2), but m is 1 to 7. And n is preferably an integer of 2 to 4.

(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain Yes, they may be the same or different.

However, at least one of Y or Z is an alkenyl group or a hydrogen atom; R is an alkyl group or an aryl group; and when there are a plurality of X, the structures of the formula (1) or the formula (2) are different. Or the structure of formula (1) or formula (2) may be mixed)
As R ¹ in the siloxane unit having a reactive functional group, a substituent having substantially no reactivity, specifically, for example, an alkyl group or an aryl group can be used.

  The siloxane unit having a functional group capable of reacting in the present invention preferably contains, on average, two or more siloxane units constituting the polyhedral skeleton. That is, a in the general formula (1) is preferably 2 or more. When there are few siloxane units containing the reactive functional group to contain, sclerosis | hardenability will become inadequate and there exists a possibility that the intensity | strength of the hardened | cured material obtained may fall.

Next, an arbitrary siloxane unit [R ² ₃ SiO—SiO _3/2 ] will be described.

  This siloxane unit is a unit for adjusting the physical properties of the modified polyhedral polysiloxane and the resulting cured product in the present invention. Since the present siloxane unit does not substantially contain a reactive substituent, it is possible to adjust the crosslinking density, improve the film property, leveling property, improve brittleness, and the like.

As R ² in the present siloxane unit, an alkyl group, an aryl group, an alkenyl group, a hydrogen atom, or a group linked to another polyhedral polysiloxane can be preferably used. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like. May be replaced. Specific examples of the alkyl group partially substituted with a substituent having substantially no reactivity include, for example, a polysiloxanylalkyl group. Leveling properties and film properties, and a curing agent described later and Compatibility with a curing initiator can be imparted, and the properties of the compound can be made liquid.

  Examples of the group linked to the other polyhedral polysiloxane include groups linked via polymer components such as polysiloxane, poly (meth) acrylate, and polyisobutylene.

<Method for producing modified polyhedral polysiloxane>
The manufacturing method of the polyhedral polysiloxane modified body in the present invention will be described.

  First, the polyhedral siloxane compound (a) will be described.

Examples of the synthesis method of the polyhedral siloxane compound (a) containing the alkenyl group and / or hydrosilyl group include R ³ SiX ^a ₃ (wherein R ³ represents an alkenyl group or a hydrogen atom, and Xa represents (Representing a hydrolyzable functional group such as a halogen atom or an alkoxy group)).

Alternatively, after synthesizing a trisilanol compound having three silanol groups in the molecule by hydrolysis condensation reaction of R ³ SiX ^a _3, the ring is closed by reacting the same or different trifunctional silane compounds. The method of doing is also known. Furthermore, a partial cleavage polyhedral polysiloxane can be synthesized by reacting the trisilanol compound with a monofunctional silane and / or a bifunctional silane.

  As another method for synthesizing the polyhedral siloxane compound (a), for example, a tetraalkoxysilane such as tetraethoxysilane is replaced with a quaternary ammonium hydroxy such as trimethyl (2-hydroxyethyl) ammonium hydroxide or tetramethylammonium hydroxide. A silicate having a polyhedral structure is obtained by a hydrolysis condensation reaction in the presence of a base such as a hydrogen atom, and the obtained silicate is further reacted with a silylating agent such as a silyl chloride having an alkenyl group and / or a hydrosilyl group. Can be synthesized. In the present invention, the same polyhedral polysiloxane can be obtained from a substance containing silica such as silica or rice husk instead of tetraalkoxylane.

As a preferable example of the polyhedral polysiloxane compound (a) in the present invention, specifically, for example, a polyhedral polysiloxane compound having an alkenyl group represented by the following formula:
[AR ¹ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group and / or a hydrogen atom, provided that at least one is an alkenyl group; Group or aryl group; R ⁴ is a substituent other than an alkenyl group and a hydrogen atom, for example, an alkyl group, an aryl group, or a group linked to other polyhedral polysiloxane or siloxane compound).

  When such a component (a) is used, by using a compound having a hydrosilyl group as the component (b), for example, to obtain a modified polyhedral polysiloxane by a hydrosilylation reaction in the presence of a hydrosilylation catalyst described later. Can do. At this time, all the alkenyl groups of the polyhedral siloxane compound (a) do not need to react and may partially remain. A plurality of polyhedral polysiloxane compounds (a) and a compound (b) having a plurality of hydrosilyl groups may react.

As other preferable examples of the polyhedral polysiloxane compound (a) in the present invention, specifically, for example,
[BR ¹ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; B is alkenyl and / or hydrogen atom, provided that at least one is hydrogen atom;. R ¹ is An alkyl group or an aryl group; R ⁴ is a substituent other than an alkenyl group and a hydrogen atom, for example, an alkyl group, an aryl group, or a group linked to another polyhedral polysiloxane or siloxane compound) .

  When such a component (a) is used, by using a compound having an alkenyl group as the component (b), for example, a modified polyhedral polysiloxane is obtained by a hydrosilylation reaction in the presence of a hydrosilylation catalyst described later. Can do. At this time, all the hydrogen atoms of the polyhedral siloxane compound (a) do not need to react and may partially remain. A plurality of polyhedral polysiloxane compounds (a) and a compound (b) having a plurality of alkenyl groups may react.

  Next, the compound (b) having a hydrosilyl group and / or an alkenyl group will be described.

  The compound having a hydrosilyl group has a hydrosilyl group (a hydrogen atom directly bonded to an Si atom) and reacts with the alkenyl group of the polyhedral siloxane compound (a) to form a new polyhedral polysiloxane molecule. It is a component for introducing a group having a reactive functional group.

  As a compound having a preferred hydrosilyl group in the present invention, specifically, for example, a compound having a hydrosilyl group (a hydrogen atom directly bonded to a Si atom) reacts with an alkenyl group of the polyhedral siloxane compound (a). And those that form a reactive functional group X represented by any one of the following general formula (1) and general formula (2).

(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain Each of which may be the same or different, provided that at least one of Y or Z is a hydrogen atom; R is an alkyl group or an aryl group; The structure of formula (2) may be different, and the structure of formula (1) or formula (2) may be mixed)
Preferred examples of the compound having a hydrosilyl group include a hydrosilyl group-containing siloxane compound, specifically, for example, a linear polysiloxane having a hydrosilyl group at both ends, a cyclic siloxane having a hydrosilyl group, and the like. Furthermore, a cyclic siloxane containing a hydrosilyl group is preferable from the viewpoints of industrial availability and good reactivity when reacted, and excellent cured blue laser resistance of the obtained cured product. These compounds having a hydrosilyl group may be used alone or in combination of two or more.

  Specific examples of the linear polysiloxane having hydrosilyl groups at both ends include poly or oligosiloxanes whose ends are blocked with dimethylhydrogensilyl groups, tetramethyldisiloxane, hexamethyltrisiloxane and the like. The

  As cyclic siloxanes containing hydrosilyl groups, 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen- 1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydro Gen-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexahydrogen Examples include -1,3,5,7,9,11-hexamethylcyclosiloxane.

  The amount of the hydrosilyl group-containing compound (b), in particular, the hydrosilyl group-containing siloxane compound is such that the number of hydrogen atoms directly bonded to Si atoms is one per alkenyl group in the polyhedral polysiloxane compound (a). Although it is preferable to use so that it may become 2.5-20 pieces, it is dependent on a compound. When the addition amount is small, gelation occurs due to a crosslinking reaction, resulting in a modified polysiloxane having poor handling properties. When it is too large, the physical properties of the cured product may be adversely affected. Furthermore, in order to allow an excessive amount of the hydrosilyl group-containing siloxane compound to exist, it is preferable to remove the unreacted hydrosilyl group-containing siloxane compound, for example, under reduced pressure and heating conditions.

  The compound (b) having an alkenyl group has an alkenyl group and reacts with the hydrosilyl group of the polyhedral siloxane compound (a) to introduce a new functional group into the polyhedral polysiloxane molecule. Is a component for.

  As the compound (b) having an alkenyl group, an alkenyl group-containing siloxane compound, specifically, for example, a linear polysiloxane having an alkenyl group at both ends, a cyclic siloxane having an alkenyl group, and the like are preferable. Can be mentioned. These compounds having an alkenyl group may be used alone or in combination of two or more.

  Specific examples of the linear polysiloxane having an alkenyl group at both ends include poly or oligosiloxane blocked with dimethylvinylsilyl groups, tetramethyldivinyldisiloxane, hexamethyldivinyltrisiloxane, etc. Is done.

  Examples of the cyclic siloxane containing 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.

  The addition amount of the alkenyl group-containing compound (b), particularly the alkenyl group-containing siloxane compound, is 2.5 to 20 alkenyl groups per hydrogen atom directly bonded to the Si atom of the polyhedral siloxane intermediate. However, it depends on the compound. When the addition amount is small, gelation occurs due to a crosslinking reaction, resulting in a modified polysiloxane having poor handling properties. When it is too large, the physical properties of the cured product may be adversely affected.

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

  The modified polyhedral polysiloxane of the present invention is preferably a liquid from the viewpoint of handling properties and the like when adjusting the cured product, and is preferably transparent in terms of the light transmittance of the molded body.

<Hydrosilylation catalyst>
Next, the hydrosilylation catalyst used in the present invention will be described.

  In the present invention, a hydrosilylation catalyst can be used in synthesizing a polyhedral polysiloxane modified product and curing the composition using the modified product.

  As a hydrosilylation catalyst used by this invention, what is normally used as a hydrosilylation catalyst can be used, there is no restriction | limiting in particular, Arbitrary things can be used.

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) _m , 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, include 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.

The addition amount of the hydrosilylation catalyst used at the time of synthesis and curing of the modified polyhedral polysiloxane is not particularly limited, but is, for example, 10 ⁻¹ to 1 mol per mol of the alkenyl group of the polyhedral polysiloxane compound (a). It is preferable to use in the range of 10 ⁻¹⁰ mol. Preferably, it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. If there are too many hydrosilylation catalysts, depending on the type of hydrosilylation catalyst, it absorbs light at short wavelengths, so the light resistance of the resulting cured product may be reduced, and the cured product may also foam. . Moreover, when there are too few hydrosilylation catalysts, reaction may not progress and there exists a possibility that a target object may not be obtained.

  Moreover, as reaction temperature of hydrosilylation reaction of polyhedral polysiloxane modified body, 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.

<Composition>
Next, the polysiloxane composition obtained by the present invention will be described. In the present invention, a polyhedral polysiloxane modified product can be obtained by adding a curing agent, a hydrosilylation catalyst, a curing retarder, an adhesiveness imparting agent, and the like. Further, among the polyhedral polysiloxane modifieds according to the present invention, the cured product is a base material by a composition in which the polyhedral polysiloxane modified according to the present invention is blended with a curing agent, a hydrosilylation catalyst, and an adhesion imparting agent described later. And a composition having good adhesiveness.

  The polysiloxane composition of the present invention can be made into a transparent liquid composition. In particular, by using a liquid polyhedral polysiloxane-modified product, a liquid composition can be formed without using a solvent, and a molded product can be easily obtained by pouring into a molded product and heating to cure. By being transparent, it can be used as an optical composition.

  For example, a molded product obtained by curing a liquid transparent composition can have a transmittance of 75% or more with a 400 nm light beam in a molded product having a thickness of 3 mm. In addition, it is preferable that the polyhedral polysiloxane-modified product is in liquid form, because the polysiloxane composition of the present invention can be easily obtained in liquid form.

  When the temperature is applied when the composition containing the polyhedral polysiloxane modified is cured by a hydrosilylation reaction, the temperature is preferably 30 to 400 ° C, more preferably 50 to 250 ° C. 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 hydrosilylation catalyst to be used and the amount of hydrosilyl group, and other combinations of the composition of the present application. Furthermore, a good cured product can be obtained by performing the treatment for 5 minutes to 10 hours.

<Curing agent>
Next, the curing agent used in the present invention will be described.

  The curing agent can be properly used depending on the type of main reactive group of the modified polyhedral polysiloxane. When the modified polyhedral polysiloxane has a hydrosilyl group as a main reactive group, a compound having an alkenyl group can be used as a curing agent, and when it has an alkenyl group as a main reactive group, a compound having a hydrosilyl group can be used as a curing agent. . Details will be described below.

  The curing agent in the present invention preferably has a weight loss at 130 ° C. of 2.5% or less, more preferably 2.0%, and a molecular weight of less than 5000, more preferably less than 3000. If the weight loss at 130 ° C. exceeds 2.5%, the toughness of the cured product may be insufficient due to the influence of low molecular weight components contained in the curing agent, and further, cracks may occur during high temperature heating. There is a possibility that the possibility becomes high. Moreover, when the molecular weight is 5000 or more, the elastic modulus and rigidity of the obtained cured product may be insufficient.

  In addition, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the curing agent in the present invention is preferably less than 1.7, and more preferably less than 1.6. If it is 1.7 or more, there is a risk that the possibility of cracking during the high-temperature heating of the resulting cured product increases.

  Here, as an evaluation method of weight reduction in the present invention, specifically, for example, 1 g of the curing agent is weighed in a metal container and then cured in a hot air circulation oven set at 130 ± 5 ° C. for 1 hour. Thereafter, the weight of the curing agent after taking out from the oven is measured, and the weight loss can be calculated. When curing a metal container in which a curing agent is put in an oven, it is necessary to put in a hood or the like so that hot air from the oven does not directly hit the sample.

  In addition, the molecular weight in this invention can be obtained by measuring in GPC method (Toluene is used as a developing solvent, polystyrene conversion).

  The curing agent having an alkenyl group is not particularly limited as long as it is a compound having an alkenyl group, but preferably contains at least two alkenyl groups in one molecule, a linear polysiloxane having an alkenyl group, A siloxane compound such as a polysiloxane having an alkenyl group at the molecular end or a cyclic siloxane containing an alkenyl group is more preferred, and a polysiloxane having a linear structure is particularly preferred from the viewpoint of crack resistance during high-temperature heating. . These compounds having an alkenyl group may be used alone or in combination of two or more.

  Specific examples of the alkenyl group-containing polysiloxane having a linear structure include copolymers of dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units. Copolymer, Copolymer of methylphenylsiloxane unit, methylvinylsiloxane unit and terminal trimethylsiloxy unit, Polydimethylsiloxane blocked with dimethylvinylsilyl group, Polydiphenyl blocked with dimethylvinylsilyl group Examples thereof include siloxane and polymethylphenylsiloxane whose end is blocked with a dimethylvinylsilyl group. The alkenyl group-containing polysiloxane having a linear structure in the present invention preferably has an alkenyl group at the molecular end from the viewpoint of toughness and crack resistance of the resulting cured product.

Specific examples of the polysiloxane having an alkenyl group at the molecular end include polysiloxanes whose ends are blocked with the dimethylalkenyl groups exemplified above, dimethylalkenylsiloxane units and SiO ₂ units, SiO _3/2 units, SiO _2/2 Examples thereof include polysiloxane composed of at least one siloxane unit selected from the group consisting of units.

  Examples of the cyclic siloxane compound containing 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, 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.

  The curing agent having a hydrosilyl group is not particularly limited as long as it is a compound having a hydrosilyl group, but preferably contains at least two hydrosilyl groups in one molecule, a linear polysiloxane having a hydrosilyl group, Siloxane compounds such as polysiloxane having a hydrosilyl group at the molecular terminal and cyclic siloxane having a hydrosilyl group are particularly preferred. These compounds having a hydrosilyl group may be used alone or in combination of two or more.

  Specific examples of hydrosilyl group-containing polysiloxanes having a linear structure include copolymers of dimethylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylhydrogensiloxane units and terminal trimethylsiloxy units. A copolymer of methylphenylsiloxane units with methylhydrogensiloxane units and terminal trimethylsiloxy units, polydimethylsiloxane blocked with dimethylhydrogensilyl groups, and terminal with dimethylhydrogensilyl groups. Examples thereof include polydiphenylsiloxane blocked, polymethylphenylsiloxane blocked at the end with a dimethylhydrogensilyl group, and the like.

Specific examples of the polysiloxane having a hydrosilyl group at the molecular end include polysiloxanes whose ends are blocked with dimethylhydrogensilyl groups exemplified above, dimethylhydrogensiloxane units (H (CH ₃ ) ₂ SiO _1/2 units And a polysiloxane composed of at least one siloxane unit selected from the group consisting of SiO ₂ units, SiO _3/2 units, and SiO _2/2 units.

  Examples of the cyclic siloxane compound containing a hydrosilyl group include 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen. -1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-tri Hydrogen-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexahydro Examples include Gen-1,3,5,7,9,11-hexamethylcyclosiloxane.

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

  Although the addition amount of the curing agent can be variously set, it is desirable that the amount of hydrogen atoms directly bonded to Si atoms is 0.3 to 5, preferably 0.5 to 3, per alkenyl group. 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.

<Curing retarder>
Next, the curing retarder used in the present invention will be described.

  The curing retarder is a component for improving the storage stability of the modified polyhedral polysiloxane of the present invention and the polysiloxane composition 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 retardant is not particularly limited, but it is preferably used in the range of 10-1 to 103 mol, more preferably in the range of 1 to 500 mol, with respect to 1 mol of the hydrosilylation catalyst. . 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 composition of the present invention and the base material, and although there is no limitation on what has such an effect, a silane coupling agent or an epoxy compound is preferable. It can be illustrated as a thing.

  Specifically, for example, a polyhedral polysiloxane modified product containing a hydrosilyl group as a modified polyhedral polysiloxane has a composition in which a curing agent, a hydrosilylation catalyst, and an adhesion imparting agent are also blended, so that the cured product adheres to the substrate. It can be made into a composition with good properties.

  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 adhesion 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.

  Preferable silane coupling agents are specifically 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 -Methacrylic groups such as acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, Alkoxysilanes having a drill group can be exemplified.

  The addition amount of the silane coupling agent is preferably 0.05 to 30% by weight, more preferably 0.1 to 15% by weight, based on the total weight of the polyhedral polysiloxane modified product and the curing agent. 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.

  Examples of the epoxy compound include novolak phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and 2,2′-bis (4-glycidyloxycyclohexyl). Propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3 -Dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate and the like.

  The addition amount of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 0.2 to 15% by weight, based on the total weight of the polyhedral polysiloxane modified body and the curing agent. 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.

  Moreover, a silane coupling agent, an epoxy compound, etc. may be used independently and may be used together 2 types.

  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, boronic acid ester compounds, organoaluminum compounds, and organotitanium compounds.

  In addition to the above components, the polysiloxane-based composition used in the present invention may contain an inorganic filler (filler) such as pulverized quartz, calcium carbonate, carbon black, silica, etc., as long as the effects of the present invention are not hindered. It may be added.

  The inorganic filler that can be used in the present invention 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. , Silica-based inorganic fillers such as ultrafine powder amorphous silica, 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, ferrite, graphite, diatomaceous earth, clay, talc, aluminum hydroxide, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, potassium titanate, calcium silicate, inorganic balloon, silver powder, etc. Can be mentioned. 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 adhesion and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.

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

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

  As the shape of the inorganic filler, various types such as a crushed shape, a piece shape, a spherical shape, and a rod shape can be used. The average particle size and particle size distribution of the inorganic filler are not particularly limited, but the average particle size is preferably 0.005 to 100 μm, and more preferably 0.01 to 50 μm. Similarly, the specific surface area is not particularly limited.

  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 polyhedral polysiloxane modified and the curing agent. 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.

  An inorganic filler can be blended with the modified polyhedral polysiloxane of the present invention and the curing agent to form a composition. The modified polyhedral polysiloxane is preferably a modified product obtained by modifying a compound (b) having a hydrosilyl group with respect to a polyhedral polysiloxane compound (a) containing an alkenyl group.

  The order of mixing the inorganic filler is not particularly limited, but from the viewpoint that the storage stability tends to be good, a method of mixing the modified polyhedral polysiloxane after mixing the inorganic filler and the curing agent is desirable. In addition, it is preferable to mix an inorganic filler into a mixture of a polyhedral polysiloxane modified and a curing agent in that the polyhedral polysiloxane modified and the curing agent are well mixed and a stable molded product is easily obtained. .

  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. In addition, the polysiloxane composition of the present invention includes various additives such as pigments, phosphors, colorants, heat resistance improvers, reaction control agents, mold release agents, and dispersants for fillers, as necessary. Can be optionally 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, in order to make the polysiloxane composition of the present invention flame retardant and fire resistant, a known additive such as titanium dioxide, manganese carbonate, Fe2O3, ferrite, mica, glass fiber, glass flake or the like may be added. Good. In addition, it is preferable to stop these arbitrary components to the minimum addition amount so that the effect of this invention may not be impaired.

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

  The polysiloxane composition of the present invention can be used as a molding material. 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. In addition, the polysiloxane composition of the present invention can be applied to various substrates such as silicon and glass with a spin coater or the like, and can be used as a film. At this time, it may be diluted with an arbitrary solvent for viscosity adjustment.

  The cured product obtained from the polysiloxane composition according to the present invention is excellent in heat resistance and light resistance, and exhibits high transparency in a wide wavelength region and temperature region. It is also suitable as a low dielectric property or low refractive index material.

The cured product / molded body / film obtained from the polysiloxane-based composition according to the present invention is excellent in heat resistance and light resistance, and has high transparency even for light having a wavelength in the ultraviolet region of about 400 nm. . This characteristic makes it possible to use as an optical device member (optical material).
The polysiloxane composition of the present invention can be used as a composition for optical materials, and can be used as an optical device member by curing or the like.

  The optical material mentioned here refers to general materials used for the purpose of allowing light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material. Here, when an application is assumed as an optical material, specifically, for example, the light transmittance at a wavelength of 400 nm at a thickness of 3 mm is desirably 70% or more, and more desirably 75% or more. In recent years, optical materials have been required to have high heat resistance and light resistance, and in particular, the decrease in light transmittance after these tests is small (the decrease rate is preferably 5% or less of the transmittance before the test). ) Is desired.

  Further, the cured product obtained by the present invention is excellent in durability to laser light in a short wavelength region (350 nm to 450 nm). For example, even when irradiated with a blue-violet laser of 405 nm ± 10 nm for a long time, the laser beam transmittance is low. It is possible to suppress the change rate to be small. Therefore, when used as an optical device member, it is possible to extend the life of the device. Further, specifically, for example, when it is desired to develop high durability to a laser in a short wavelength region, the gel fraction is preferably 95% or more. When the gel fraction is less than 95%, the refractive index change of the laser transmitting portion may occur, streaks may occur, or the surface may be uneven.

Specifically, the gel fraction is, for example, under a condition of 20 ± 5 ° C., 1 g of a sample is wrapped in a stainless steel wire mesh, immersed in toluene for 72 hours, and then dried at 100 ° C. for 5 hours. It is calculated by measuring the sample weight before and after the test. Specifically, (gel fraction) = [(weight after test) / (weight before test)] × 100
It can be calculated by the following formula.

  Specific uses of the polysiloxane composition and molded product obtained in the present invention include color filters, resist materials, substrate materials, light guide plates, prism sheets, deflecting plates, retardation plates, visual fields in the field of liquid crystal displays. Examples of the peripheral material of the liquid crystal display device such as a corner correction film, an adhesive, a polarizer protective film, a liquid crystal film, an interlayer insulating film, a gate insulating film, and a passivation film are exemplified.

  In addition, color PDP (plasma display) sealants, antireflection films, antireflection films, optical correction films, housing materials, front glass protective films, front glass substitutes, and adhesives that are expected as next-generation flat panel displays Is exemplified.

  Moreover, the board | substrate material in a plasma address liquid crystal (PALC) display, a light-guide plate, a prism sheet, a deflection plate, a phase difference plate, a viewing angle correction film, an adhesive agent, a sealing agent, and a polarizer protective film are illustrated.

  Also, front glass protective film, front glass substitute materials, various sealants, adhesives in organic EL (electroluminescence) displays, and various film substrates, front glass protective films, front glass substitutes in field emission display (FED). Examples are materials and adhesives.

  Moreover, the mold material of the LED element used for a LED display apparatus, the protective film of a front glass, a front glass alternative material, an adhesive agent, etc. are illustrated.

  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 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 resist materials for microlithography for LSI and VLSI materials.

  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.

  The composition containing the modified polyhedral polysiloxane of the present invention can be suitably used as an optical element sealing agent, an optical element composition, and an insulating film. As the modified polyhedral polysiloxane, the polyhedral polysiloxane of the present invention obtained by modifying a compound (b) having a hydrosilyl group with respect to a polyhedral polysiloxane compound (a) containing an alkenyl group. A modified product is preferred.

  Similarly, the polysiloxane composition of the present invention can be suitably used for an optical element sealing agent, an optical element composition, an insulating film, and the like.

  The optical element sealing agent can be obtained by adding a curing agent, and if necessary, a hydrosilylation catalyst, a curing retarder, and an adhesion imparting agent to the polyhedral polysiloxane modified product. The optical element sealant of the present invention can be handled as a transparent liquid resin composition. By using a liquid composition, element sealing can be easily performed by pouring into a mold, a package, a substrate, etc., and heating and curing. The sealing layer obtained by the optical element sealing agent of the present invention has high transparency and can be preferably used from the viewpoint of light extraction efficiency. In addition, it is excellent in heat resistance, light resistance, and blue-violet laser resistance, and it is possible to extend the life of the optical device.

  As the cured product obtained by curing the liquid optical element sealant, for example, it is possible to obtain a cured product having a thickness of 3 mm and having a transmittance of 75% or more with a light beam of 400 nm. In addition, it is preferable that the polyhedral polysiloxane-modified product is in a liquid form because the optical element sealing agent of the present invention can be easily obtained in a liquid form.

  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 optical element sealant in the present invention can be used by being injected or applied to, for example, a package or substrate on which an element is mounted. After injection or application, the element can be sealed well by curing under the above-described curing conditions.

  In addition to the above essential components, the optical element sealant used in the present invention is optionally filled with silica, pulverized quartz, calcium carbonate, carbon black, oxidation as long as it does not interfere with the effects of the present invention. A filler such as titanium, zinc oxide, alumina, or phosphor may be added.

  In addition, the optical element sealing agent of the present invention may optionally include various additives such as a colorant and a heat resistance improver, a reaction control agent, a mold release agent, or a filler dispersant. Can do.

  Examples of the filler dispersant include diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane, and the like.

  Further, in order to make the optical element sealing agent of the present invention flame retardant and fire resistant, a known additive such as titanium dioxide, manganese carbonate, Fe 2 O 3, ferrite, mica, glass fiber, glass flake or the like may be added. Good. 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 optical element sealant used in the present invention is mixed uniformly using a kneader such as a roll, a Banbury mixer, a kneader, or a planetary stirring and defoaming machine, and heat-treated as necessary. Can be obtained.

  The optical element sealing agent of this invention can be used as a molded object. 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.

  The cured product (sealing layer) obtained by the optical element sealant of the present invention is excellent in heat resistance, light resistance and blue-violet laser resistance, and is high even for light having a wavelength in the near ultraviolet region of about 400 nm. Expresses light transmittance.

  The composition for an optical element can be obtained by adding a curing agent, and, if necessary, a hydrosilylation catalyst, a curing retarder, an adhesiveness imparting agent, etc. to the modified polyhedral polysiloxane. The composition for optical elements of the present invention can be handled as a transparent liquid resin composition. By using a liquid composition, for example, an optical element can be easily manufactured by injection and injection into a mold and curing by heating.

  The optical element obtained by the optical element composition of the present invention has high transparency and can be preferably used from the viewpoint of light extraction efficiency. Moreover, since it is excellent in heat resistance, light resistance, and blue-violet laser resistance, it is possible to suppress deterioration in quality due to the thermal history in the production of the opto device, and to extend the life of the opto device.

  As a cured product (optical element) obtained by curing a liquid composition for optical elements, for example, a cured product having a thickness of 3 mm can have a transmittance of 75% or more with a light beam of 400 nm. In addition, it is preferable that the polyhedral polysiloxane-modified product is in a liquid state because the composition for optical elements of the present invention can be easily obtained in a liquid state.

  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.

  The composition for an optical element in the present invention can be specifically obtained by, for example, injecting, injecting the composition into a mold of the optical element and curing it. Also, it can be applied to a substrate for optical elements such as glass and various plastics, and then cured to be used as a composite material, or it can be cured by pressing a mold with fine grooves, holes, and dots after application. By doing so, it is also possible to produce an optical element having a fine structure on the surface.

  Moreover, the composition for optical elements by this invention can also provide antireflection ability to optical elements, such as glass and a plastics, for example.

  In the composition for optical elements used in the present invention, in addition to the above essential components, silica, pulverized quartz, calcium carbonate, carbon black, oxidation as a filler, if necessary, as long as it does not interfere with the effects of the present invention as an optional component A filler such as titanium, zinc oxide, alumina, or phosphor may be added.

  In addition, the optical element composition of the present invention may be optionally added with various additives such as a colorant and a heat resistance improver, a reaction control agent, a mold release agent, or a filler dispersant. Can do.

  Examples of the filler dispersant include diphenylsilane diol, various alkoxysilanes, carbon functional silane, silanol group-containing low molecular weight siloxane, and the like.

In order to make the composition for optical elements of the present invention flame-retardant and fire-resistant, known additives such as titanium dioxide, manganese carbonate, Fe ₂ O ₃ , ferrite, mica, glass fiber, glass flakes are added. May be. 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 composition for optical elements used in the present invention is uniformly mixed using a kneader such as a roll, a Banbury mixer, a kneader, or a planetary stirring and defoaming machine, and heat-treated as necessary. Can be obtained.

  The composition for optical elements 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.

  The cured product (optical element) obtained by the composition for optical elements of the present invention is excellent in heat resistance, light resistance and blue-violet laser resistance, and has a high light beam even for light in the near-ultraviolet region of about 400 nm. Expresses transmittance.

  The insulating film is a polyhedral polysiloxane modified body, and a curing agent, and if necessary, a hydrosilylation catalyst, a curing retarder, an adhesion-imparting agent, and a solvent are added to form a uniform composition, for example, coated on a substrate Thereafter, the solvent can be removed by heating and the composition can be cured.

  Although the solvent is not particularly limited, specifically, for example, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, methyl isobutyl ketone, γ-butyrolactone, methyl ethyl ketone, methanol, ethanol, dimethylimidazolidinone, ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), tetraethylene glycol dimethyl ether, triethylene glycol mono Butyl ether, triethylene glycol monomethyl ether , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, isopropanol, ethylene carbonate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N 2, N -Dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, diisopropylbenzene, toluene, xylene, mesitylene and the like. These solvents may be used alone or in combination of two or more.

The substrate material is not particularly limited, and may be various electronic components, optical components, a substrate on which a semiconductor element or metal wiring is mounted, or the like. Specifically, for example, semiconductor integrated circuits composed of liquid crystal display elements, solid elements such as transistors and diodes in addition to substrate materials such as glass, glass epoxy, silicon wafer, SiO ₂ wafer, and SiN wafer.

  Although it does not specifically limit as a coating method to a board | substrate, Well-known methods, such as a spin coat method, a roll coat method, a dipping method, a spray method, can be used. The film thickness can be adjusted according to the application and is not particularly limited. 01-100 micrometers, Preferably, it is 0.05-50 micrometers, More preferably, it is 0.1-20 micrometers.

  The heating method is not particularly limited as long as it can be set to a predetermined temperature. Specifically, for example, an oven, a hot plate, an infrared furnace, or the like can be used. Moreover, you may heat in any atmosphere according to a use, such as air | atmosphere, nitrogen atmosphere, argon atmosphere, a vacuum, the pressure reduction which controlled oxygen concentration. The heating temperature is not particularly limited, but is preferably 30 to 600 ° C, more preferably 50 to 500 ° C. If the temperature is too high, the insulating film may be defective in appearance, and if it is too low, curing may be 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 like 70 ° C., 120 ° C., and 150 ° C., a favorable insulating film can be obtained, which is preferable. The heating 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 the combination of other blends, but for example, it is 1 minute to 12 hours, preferably 10 minutes to 8 hours. By performing the time, a good insulating film can be obtained.

  If necessary, the insulating film of the present invention can have a low dielectric constant by using a pore forming agent (foaming agent) within the range allowed by the mechanical strength of the film. Although it does not specifically limit as a hole formation agent, It is preferable that the solubility with a solvent and the compatibility with a composition are satisfy | filled simultaneously.

  Examples of the polymer that can be used as the pore forming agent include polyvinyl aromatic compounds (polystyrene, polyvinyl pyridine, halogenated polyvinyl aromatic compounds, etc.), polyacrylonitrile, polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.), polyethylene, poly Lactic acid, polysiloxane, polycaprolactone, polycaprolactam, polyurethane, polymethacrylate (such as polymethyl methacrylate) or polymethacrylic acid, polyacrylate (such as polymethyl acrylate) and polyacrylic acid, polydiene (such as polybutadiene and polyisoprene), polyvinyl chloride , Polyacetals, and amine capped alkylene oxides.

  In addition, polyphenylene oxide, poly (dimethylsiloxane), polytetrahydrofuran, polycyclohexylethylene, polyethyloxazoline, polyvinylpyridine, polycaprolactone, and the like may be used.

  In particular, polystyrene can be suitably used as a pore forming agent. Examples of polystyrene include anionic polymerized polystyrene, syndiotactic polystyrene, unsubstituted and substituted polystyrene (for example, poly (α-methylstyrene)), and unsubstituted polystyrene is preferred.

  In addition to exhibiting low dielectric properties, the insulating film of the present invention has high transparency and can be preferably used from the viewpoint of light extraction efficiency. Moreover, it is excellent in heat resistance and light resistance, and the lifetime of the optical device can be extended.

  The insulating film of the present invention can be used for various purposes. Specifically, for example, semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, D-RDRAM, Si-TFT, oxide TFT, and organic TFT, and insulating films and semiconductors in electronic components such as multichip module multilayer wiring boards Interlayer insulation film, etching stopper film, surface protective film, buffer coat film, passivation film, alpha ray blocking film, flexographic printing plate cover lay film, overcoat film, flexible copper clad plate cover coat, solder resist film A liquid crystal alignment film, a planarizing film, etc. can be mentioned, but it is not limited to these.

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

(Weight loss evaluation)
A hot air circulation oven (safety oven) in which a sample was weighed in an ointment can so as to be in the range of 1.0 to 1.1 g and placed on an aluminum bat, and the aluminum bat was covered with aluminum foil over the entire surface and set at 130 ° C. SPHH-101, manufactured by ESPEC). After 1 hour, it was allowed to cool at room temperature, the sample weight was weighed, and the weight loss before and after heating was calculated.

(Molecular weight evaluation)
The molecular weight and molecular weight distribution were calculated by GPC (manufactured by TOSOH: HLC-8220 GPC).

(Heat resistance test 1)
In a hot air circulating oven set at 200 ° C., a 3 mm thick plate-like molded body was cured for 24 hours and evaluated according to the following criteria.
○: When the appearance is not changed.
X: When coloring is seen.

(Light resistance test)
A metering weather meter (model M6T) manufactured by Suga Test Instruments Co., Ltd. was used. Black panel temperature 120 ° C., irradiance 0.53 kW / m ^2, after irradiation until the integrated irradiance 50 MJ / m ^2, was evaluated according to the following criteria.
○: When the appearance is not changed.
X: When coloring is seen.

(Heat resistance test 2)
A plate-like cured product (30 mm × 10 mm, thickness 2 mm) was cured for 1 hour in a hot-air circulating oven set at 270 ° C., and the form was visually observed. Evaluation was performed at n = 5, and the ratio of occurrence of cracks after the test was shown.

(Blue resistance laser test)
Using a laser diode (manufactured by Nichia Corporation, product name: NDHV310APC), 400-415 nm, 20 W / mm ² of blue-violet laser light was irradiated in an environment of 60 ° C. for 24 hours. At this time, the laser transmission amount at the start and end of laser irradiation was observed with a power meter (manufactured by Coherent, product name: LM-2VIS) and evaluated according to the following criteria.
○: The laser transmittance change before and after the irradiation test was less than 1%.
Δ: The laser transmittance change before and after the irradiation test was 1% or more and less than 10%.
X: The laser transmittance change before and after the irradiation test is 10% or more.

In addition, the sample after laser irradiation was visually checked for the presence or absence of changes in the appearance of the laser irradiated portion, and evaluated according to the following criteria.
○: No change is observed.
X: Surface irregularities and streaks are generated on the irradiated part.

(Production Example 1)
Low molecular weight components were distilled off by heating 816.48 g of linear polydimethylsiloxane containing vinyl groups at both ends (Clariant, trade name MVD8MV) at 150 ° C. for 10 hours under reduced pressure. The weight of MVD8MV after distilling out the low molecular weight component was 670.88 g. As a result of calculating the molecular weight by GPC, the number average molecular weight (Mn) was 1010 and the weight average molecular weight (Mw) was 1740 before the low molecular weight component was distilled off, and after the distillation, Mn was 1490 and Mw was 2150. there were.

  In addition, about the used linear polydimethylsiloxane, when the weight loss amount at 130 degreeC before the said pressure reduction heat processing was evaluated, 3.3%, Moreover, the weight loss amount at 130 degreeC after the said pressure reduction processing was calculated | required. When evaluated, it was 0.7%.

(Production Example 2)
A mixed solution of 34.5 g of 48% choline aqueous solution and 27.9 g of tetraethoxysilane was stirred at room temperature for 4 hours, and then 30 mL of methanol was added to obtain a uniform solution. Next, the previously prepared solution was slowly added dropwise to a stirring solution of 16.15 g of dimethylchlorovinylsilane, 14.53 g of trimethylchlorosilane, and hexane (50 mL). After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours, hexane was added to extract the organic layer, and the mixture was concentrated under reduced pressure. The crude product is washed with methanol, subjected to suction filtration, and octasilsesquioxane containing vinyldimethylsiloxy group and trimethylsiloxy group whose average composition is represented by the following formula:
[CH ₂ = CH (CH ₃ ) ₂ SiO—SiO _3/2 ] _3.7 10 g of [(CH ₃ ) ₃ SiO—SiO _3/2 ] _4.3 was obtained.

(Production Example 3)
10 g of polyhedral polysiloxane compound obtained in Production Example 2, platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, Pt-VTSC-3X, manufactured by Umicore Precious Metals Japan) 1.2 μL, toluene 40 g The mixed solution was added dropwise to a mixed solution of 18.94 g of 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane and 18.9 g of toluene, and 6.5 at 100 ° C. After warming for hours, it was cooled to room temperature.

After completion of the reaction, 1,31,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane added in excess with toluene was distilled off to obtain 15.31 g of a polysiloxane modified product. Obtained. The obtained modified product is a colorless transparent liquid, and SiH groups derived from 1,3,5,7-tetrahydrogen-1,3,5,7-tetramethylcyclotetrasiloxane are introduced by ¹ H-NMR. Confirmed that it has been.

(Production Example 4)
10 g of polyhedral polysiloxane compound obtained in Production Example 2, 1.5 μL of platinum vinylsiloxane complex (platinum vinylsiloxane complex containing 3 wt% as platinum, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X), 40 g of toluene The mixed solution was dropped into a mixed solution of 21.2 g of tetramethyldisiloxane and 20 g of toluene, heated at 100 ° C. for 6.5 hours, and then cooled to room temperature.

After completion of the reaction, toluene and an excess amount of tetramethyldisiloxane were distilled off to obtain 12.6 g of a modified polysiloxane. The obtained modified product was a colorless transparent liquid, and it was confirmed by ¹ H-NMR that a SiH group derived from tetramethyldisiloxane was introduced.

Example 1
To 3.0 g of the modified product obtained in Production Example 3, 8.4 g of MVD8MV from which the low molecular weight component was distilled off in Production Example 1 was added to obtain a uniform solution.

  The solution thus obtained is poured into a mold and heated at 60 ° C. for 1 hour, 80 ° C. for 1 hour, 100 ° C. for 1 hour, 120 ° C. for 1 hour, 150 ° C. for 1 hour, and 180 ° C. for 1 hour. The mold was removed after curing. Next, the cured product removed from the mold is cut into a predetermined size (30 × 10 × 2 mm) and cured for 2 hours in a hot air circulating oven set at 200 ° C. A plate-like cured product was obtained.

  The obtained cured product was subjected to various evaluations. The results are shown in Table 1.

(Example 2)
To 3.0 g of the modified product obtained in Production Example 4, MVD8MV 3.5 g obtained by distilling off the low molecular weight component in Production Example 1 was added to obtain a uniform solution.

  The solution thus obtained is poured into a mold and heated at 60 ° C. for 1 hour, 80 ° C. for 1 hour, 100 ° C. for 1 hour, 120 ° C. for 1 hour, 150 ° C. for 1 hour, and 180 ° C. for 1 hour. The mold was removed after curing. Next, the cured product removed from the mold is cut into a predetermined size (30 × 10 × 2 mm) and cured for 2 hours in a hot air circulating oven set at 200 ° C. A plate-like cured product was obtained.

  The obtained cured product was subjected to various evaluations. The results are shown in Table 1.

(Comparative Example 1)
A commercial product MVD8MV 8.37 g was added to 3.0 g of the modified product obtained in Production Example 3 to obtain a uniform solution. The solution thus obtained is poured into a mold and heated at 60 ° C. for 1 hour, 80 ° C. for 1 hour, 100 ° C. for 1 hour, 120 ° C. for 1 hour, 150 ° C. for 1 hour, and 180 ° C. for 1 hour. The mold was removed after curing. Next, the cured product removed from the mold is cut into a predetermined size (30 × 10 × 2 mm) and cured for 2 hours in a hot air circulating oven set at 200 ° C. A plate-like cured product was obtained.
The obtained cured product was subjected to various evaluations. The results are shown in Table 1.

(Comparative Example 2)
To 3.0 g of the modified product obtained in Production Example 4, 3.5 g of a commercially available MVD8MV was added to obtain a uniform solution.

  The solution thus obtained is poured into a mold and heated at 60 ° C. for 1 hour, 80 ° C. for 1 hour, 100 ° C. for 1 hour, 120 ° C. for 1 hour, 150 ° C. for 1 hour, and 180 ° C. for 1 hour. The mold was removed after curing. Next, the cured product removed from the mold is cut into a predetermined size (30 × 10 × 2 mm) and cured for 2 hours in a hot air circulating oven set at 200 ° C. A plate-like cured product was obtained.

  The obtained cured product was subjected to various evaluations. The results are shown in Table 1.

Claims (15)

  For the polyhedral polysiloxane compound (a) containing an alkenyl group and / or a hydrosilyl group, the compound (b) having a hydrosilyl group and / or alkenyl group capable of hydrosilylation reaction with the component (a) is modified. A polysiloxane composition comprising the modified polyhedral polysiloxane (A) and the curing agent (B) obtained as essential components, wherein the weight loss of the (B) at 130 ° C. is 2. A polysiloxane composition characterized by being 5% or less.   The polysiloxane composition according to claim 1, wherein the component (A) is liquid at a temperature of 20 ° C.   The polysiloxane composition according to claim 1 or 2, wherein the compound (b) is a cyclic siloxane containing a hydrosilyl group and / or an alkenyl group.   The polysiloxane composition according to claim 1 or 2, wherein the compound (b) is a linear siloxane containing a hydrosilyl group and / or an alkenyl group at the molecular end.   The polysiloxane composition according to any one of claims 1 to 4, wherein the compound (b) has at least three hydrosilyl groups or alkenyl groups in the molecule.   The number of hydrogen atoms and / or alkenyl groups directly bonded to the Si atom of the compound (b) having a hydrosilyl group and / or alkenyl group is such that the polyhedral polysiloxane compound (a) contains an alkenyl group and / or a hydrosilyl group. It is modified by adding 2.5 to 20 hydrogen atoms per alkenyl group and / or Si atom directly connected to the Si atom, and is obtained by distilling off the unreacted compound (b). The polysiloxane composition according to any one of claims 1 to 5. (A) component is
[XR ¹ ₂ SiO—SiO _3/2 ] _a [R ² ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; R ¹ is an alkyl group or an aryl group; R ² is an alkyl group, an aryl group, an alkenyl group, a hydrogen atom Or a group linked to another polyhedral polysiloxane; X has a structure represented by the following general formula (1) or general formula (2), and when there are a plurality of X, the general formula (1 ) Or the structure of the general formula (2) may be different, or the structure of the general formula (1) or the general formula (2) may be mixed.

(L is an integer of 2 or more; m is an integer of 0 or more; n is an integer of 2 or more; Y is bonded to a polyhedral polysiloxane through a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or an alkylene chain. Z may be the same or different; Z is a hydrogen atom, an alkenyl group, an alkyl group, an aryl group, or a site bonded to the polyhedral polysiloxane via an alkylene chain Yes, and may be the same or different, provided that at least one of Y or Z is a hydrogen atom or an alkenyl group; R is an alkyl group or an aryl group; (1) or the structure of formula (2) may be different, or the structure of formula (1) or formula (2) may be mixed). Polysiloxane composition according to any one of to 7. Formula [AR ¹ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; A is an alkenyl group and / or a hydrogen atom provided that at least one is an alkenyl group;. R ¹ is An alkyl group or an aryl group; R ⁴ is a substituent other than an alkenyl group and a hydrogen atom, for example, an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane or siloxane compound) In the polyhedral polysiloxane compound (a) composed of siloxane units, the compound (b) having a hydrosilyl group is within a range of 2.5 to 20 hydrogen atoms directly bonded to Si atoms per alkenyl group. It is obtained by adding an excess amount to modify by a hydrosilylation reaction and distilling off the compound (b) having an unreacted hydrosilyl group. The polysiloxane composition according to any one of? 7. Formula [BR ¹ ₂ SiO—SiO _3/2 ] _a [R ⁴ ₃ SiO—SiO _3/2 ] _b
(A + b is an integer of 6 to 24, a is an integer of 1 or more, b is 0 or an integer of 1 or more; B is alkenyl and / or hydrogen atom, provided that at least one is hydrogen atom;. R ¹ is An alkyl group or an aryl group; R ⁴ is a substituent other than an alkenyl group and a hydrogen atom, for example, an alkyl group, an aryl group, or a group linked to another polyhedral skeleton polysiloxane or siloxane compound) The range in which the polyhedral polysiloxane compound (a) composed of siloxane units has 2.5 to 20 alkenyl groups per hydrogen atom directly bonded to the Si atom of the compound (b) having an alkenyl group. The compound according to claim 1, wherein the compound is obtained by distilling off the compound (b) having an unreacted alkenyl group by adding an excessive amount thereof to modify by hydrosilylation reaction. The polysiloxane composition according to any one of the above.   The polysiloxane composition according to any one of claims 1 to 9, wherein the curing agent (B) has a weight average molecular weight (Mw) of less than 5,000.   11. The curing agent (B) is a linear polysiloxane containing an alkenyl group and / or a hydrosilyl group at a molecular terminal having a weight average molecular weight (Mw) of less than 5000. 2. A polysiloxane composition according to item 1.   The curing agent (B) is a linear polysiloxane containing an alkenyl group and / or a hydrosilyl group at a molecular terminal having a weight average molecular weight (Mw) of less than 3000. 2. A polysiloxane composition according to item 1.   The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the curing agent (B) is less than 1.7. The polysiloxane composition described in 1.   The polysiloxane composition according to claim 1, comprising a hydrosilylation catalyst.   Hardened | cured material formed by hardening | curing the polysiloxane type composition of any one of Claims 1-14.