JP2009173760A - Liquid polysiloxane-based compound having polyhedron structure, composition using the compound and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid polysiloxane compound having a polyhedron structure which has excellent molding processability and transparency and to provide a composition using the compound. <P>SOLUTION: The polysiloxane-based compound having the polyhedron structure has a structural unit of formula [XR<SB>2</SB>SiO-SiO<SB>3/2</SB>]<SB>a</SB>[XR<SB>2</SB>SiO-(R<SB>2</SB>SiO)<SB>m</SB>-SiO<SB>3/2</SB>]<SB>b</SB>[R'-(R<SB>2</SB>SiO)<SB>n</SB>-SiO<SB>3/2</SB>]<SB>c</SB>(wherein, each of a to c denotes an integer of 0 or 1 or more, a+b+c denotes an integer of 6 to 24, b+c denotes an integer of 1 or more, each of m and n denotes an integer of 1 or more, R denotes an alkyl group or an aryl group which may be equal to or different from each other when a plurality of groups exist, R' denotes an another polysiloxane having a polyhedron structure and X denotes a hydrogen atom or an alkenyl group which may be equal to or different from each other). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a liquid polysiloxane compound excellent in molding processability, transparency, heat resistance and light resistance, and a composition and a cured product using the compound.

  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, compositions composed of polysiloxanes having a polyhedral skeleton are known to exhibit even more excellent heat resistance, light resistance, chemical stability, low dielectric properties, etc. due to their specific chemical structure. .

  However, polysiloxanes having a polyhedral skeleton are generally polyfunctional and solid compounds, are difficult to control, and have poor handling properties and molding processability, making them difficult to materialize. For example, although a hydrosilylation curable composition using a functional group-containing polysiloxane is disclosed (Non-Patent Document 1), the polysiloxane having a polyhedral skeleton, which is a starting material, is a polyfunctional solid material. Therefore, it is difficult to control the curing reaction, and coating and injection molding are difficult.

  In addition to this, curable compositions using polysiloxanes having a polyhedral skeleton containing epoxy groups and phenyl groups (Patent Documents 1 to 3) have been disclosed. The properties of the polysiloxane composition are not fully utilized.

As described above, disclosure of a material using a polysiloxane compound having a polyhedral skeleton is seen, but no example of a liquid compound having characteristics of a polysiloxane composition and excellent in handling and molding processability is found. The development of new materials has been desired.
Special table 2004-529984 JP 2004-359933 A JP 2006-22207 A J. et al. Am. Chem. Soc. 1998, 120, 8380-8391

  The object is to provide a liquid polysiloxane compound excellent in molding processability, transparency, heat resistance and light resistance and a composition using the compound.

  As a result of intensive studies to solve the above problems, the present inventors have the following configurations.

1). formula
[XR ₂ SiO—SiO _3/2 ] _a [XR ₂ SiO— (R ₂ SiO) _m —SiO _3/2 ] _b [R ′ — (R ₂ SiO) _n —SiO _3/2 ] _c
(A to c are integers of 0 or 1 or more, a + b + c is an integer of 6 to 24, b + c is an integer of 1 or more, m and n are integers of 1 or more; R is an alkyl group or an aryl group, each of which is plural In some cases, they may be the same or different from each other; R ′ is another polyhedral polysiloxane; X is a hydrogen atom or an alkenyl group, and may be the same or different. A polyhedral polysiloxane compound comprising a structural unit.

  2). The polyhedral polysiloxane compound according to 1), which is liquid at 20 ° C.

  3). The method for producing a polyhedral polysiloxane compound according to 1) or 2), which is obtained by reacting a silicate having a polyhedral structure with a mixture of monochlorosilane and dichlorosilane.

  4). The method for producing a polyhedral polysiloxane compound according to 3), wherein the molar ratio of the mixture of monochlorosilane and dichlorosilane is 0.1 to 4 mol of dichlorosilane with respect to 8 mol of monochlorosilane. .

  5). A polyhedral polysiloxane compound produced by the production method according to 3) or 4).

  6). 1) A polyhedral polysiloxane composition comprising the polyhedral siloxane compound according to any one of 2) or 5), a curing agent, and a hydrosilylation catalyst.

  7). The polyhedral polysiloxane composition according to 6), comprising a curing retarder.

  8). A cured product obtained by curing the polyhedral polysiloxane composition according to 6) or 7).

  9). The cured product according to 8), wherein the 3 mm-thick molded article has a light transmittance of 70% or more at a wavelength of 400 nm.

  A liquid polysiloxane compound excellent in molding processability, transparency, heat resistance, and light resistance and a composition using the compound can be provided.

  The present invention is described in detail below.

<Polyhedral polysiloxane compound>
This polyhedral polysiloxane compound is composed of an oligomer having a siloxane bond in the side chain or two or more polyhedral polysiloxanes linked by a siloxane bond, and is represented by the following formula (1): It consists of siloxane units. This polyhedral polysiloxane compound can be made into a liquid component by introducing a siloxane bond into a side chain or connecting with a siloxane bond.
[XR ₂ SiO—SiO _3/2 ] _a [XR ₂ SiO— (R ₂ SiO) _m —SiO _3/2 ] _b [R ′ — (R ₂ SiO) _n —SiO _3/2 ] _c (1)
(A to c are integers of 0 or 1 or more, a + b + c is an integer of 6 to 24, b + c is an integer of 1 or more, m and n are integers of 1 or more, R is an alkyl group and an aryl group, In the case where there are a plurality of R, R ′ is another polyhedral polysiloxane, and X is a hydrogen atom or an alkenyl group, which may be the same or different.

First, the [XR ₂ SiO—SiO _3/2 ] [XR ₂ SiO— (R ₂ SiO) _m —SiO _3/2 ] unit will be described.

  The siloxane unit is a component constituting a polyhedral polysiloxane having a siloxane bond introduced in the side chain. X is a substituent that generates a crosslinking reaction with the curing agent by a hydrosilylation reaction in the presence of a hydrosilylation catalyst, and is a hydrogen atom or an alkenyl group.

  R is not particularly limited, and is specifically an alkyl group or an aryl group, and when there are a plurality of each, they may be the same as or different from each other. R in the present invention is preferably a methyl group from the viewpoint of heat resistance and light resistance.

[XR ₂ SiO— (R ₂ SiO) _m —SiO _3/2 ] The siloxane bonding site (R ₂ SiO) _{m in the unit} is a component useful for liquefying the polyhedral polysiloxane compound, Is not particularly limited as long as it is an integer of 1 or more, but is preferably an integer of 1 to 20. The siloxane bonding site is also responsible for adjusting the physical properties of the polyhedral polysiloxane and the resulting cured product in the present invention. By adjusting the m number, the crosslinking density is adjusted, the film properties, leveling properties, and brittleness are improved. It becomes possible.

The [R ′ — (R ₂ SiO) _n —SiO _3/2 ] unit is a component linked to another polyhedral polysiloxane. The siloxane bonding site (R ₂ SiO) _n in the siloxane unit is a component useful for liquefying the polyhedral polysiloxane compound, and n is not particularly limited as long as n is an integer of 1 or more. It is desirable to be an integer of ˜20. The siloxane bonding site is also responsible for adjusting the physical properties of the polyhedral polysiloxane and the resulting cured product in the present invention. By adjusting the n number, the crosslinking density is adjusted, the film property, the leveling property, and the brittleness is improved. It becomes possible. R ′ is another polyhedral polysiloxane.

<Method for producing polyhedral polysiloxane>
In the present invention, in order to obtain a desired polyhedral polysiloxane compound, a silicate having a polyhedral structure may be used as a precursor.

  It does not specifically limit as a synthesis method of the silicate which has a polyhedral structure, It can synthesize | combine using a well-known method. Specifically, a method in which tetraalkoxysilane is hydrolytically condensed in the presence of a base such as quaternary ammonium hydroxide can be used. Examples of tetraalkoxysilane include tetraethoxysilane, tetramethoxysilane, and tetrabutoxysilane. Examples of the quaternary ammonium hydroxide include 2-hydroxyethyltrimethylammonium hydroxide and tetramethylammonium hydroxide. In the present invention, it is possible to obtain a silicate having a similar polyhedral structure from a silica-containing substance such as silica or rice husk instead of tetraalkoxylane.

  The desired polyhedral polysiloxane compound can be obtained by silylating the silicate having the polyhedral structure in combination with monochlorosilane and dichlorosilane.

  Chlorosilane is not particularly limited as long as the product after silylation is obtained as a compound represented by the above formula (1).

  Examples of monochlorosilane include dimethylhydrochlorosilane, methylphenylhydrochlorosilane, diphenylhydrochlorosilane, dimethylvinylchlorosilane, methylphenylvinylchlorosilane, and diphenylvinylchlorosilane.

  Examples of dichlorosilane include dimethyldichlorosilane, methylphenyldichlorosilane, and diphenyldichlorosilane.

  Although the addition amount of chlorosilane is not particularly limited, it is used so that the total number of chlorine atoms in chlorosilane is 0.5 to 10 with respect to one silicon atom of silicate having a polyhedral structure as a precursor. It is preferable that it is 0.8-5.

  As a ratio of the addition amount of monochlorosilane and dichlorosilane, it is preferable to use dichlorosilane in the range of 0.1 to 4 mol with respect to 8 mol of monochlorosilane. If the amount of chlorosilane added is large, a siloxane compound that does not include a polyhedral structure in the chemical structure may be produced as a by-product, and if it is too small, solids may remain in the product or gelate.

  In the method for producing a polyhedral polysiloxane compound in the present invention, the number of moles of chlorosilane to be added is reduced by using dichlorosilane in combination with monochlorosilane at the time of silylation, compared with the case of using monochlorosilane alone. Therefore, the polyhedral polysiloxane compound can be obtained more effectively.

<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 the main reactive group of the polyhedral polysiloxane compound. When the polyhedral polysiloxane compound 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 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, and a polysiloxane compound having at least two alkenyl groups is preferable. preferable. As the polysiloxane compound having at least two alkenyl groups, a polysiloxane having a linear structure having an alkenyl group, a polysiloxane having an alkenyl group at the molecular end, and a cyclic siloxane having an alkenyl group are particularly preferable. These compounds having an alkenyl group may be used alone or in combination of two or more.

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

  Specific examples of the linear siloxane having an alkenyl group include copolymers of dimethylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, diphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units. Examples include copolymers, copolymers of methylphenylsiloxane units, methylvinylsiloxane units and terminal trimethylsiloxy units, and polysiloxanes whose ends are blocked with dimethylvinylsilyl groups.

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

  Examples of the cyclic siloxane compound containing an alkenyl group include 1,3,5,7-vinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trivinyl-1,3. , 5,7-tetramethylcyclotetrasiloxane, 1,5-divinyl-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trivinyl-1,3,5 -Trimethylcyclosiloxane, 1,3,5,7,9-pentavinyl-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexavinyl-1,3 Examples include 5,7,9,11-hexamethylcyclosiloxane.

  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. And a copolymer of a methylphenylsiloxane unit, a methylhydrogensiloxane unit and a terminal trimethylsiloxy unit, a polysiloxane having a terminal blocked 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 units.

  Examples of the cyclic siloxane compound containing a hydrosilyl group include 1,3,5,7-hydrogen-1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen- 1,3,5,7-tetramethylcyclotetrasiloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydro Gen-1,3,5-trimethylcyclosiloxane, 1,3,5,7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9 , 11-hexahydrogen-1,3,5,7,9,11-hexamethylcyclosiloxane and the like.

  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.

<Hydrosilylation catalyst>
In the present invention, a hydrosilylation catalyst is used in preparing a polyhedral polysiloxane compound and a composition using the compound.

  As a hydrosilylation catalyst used by this invention, what is normally used as hydrosilylation catalyst formation 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) _n , Pt [(MeViSiO) ₄ ] _m ; platinum-phosphine complex, such as Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ; platinum-phosphite complex, such as Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer) , Pt (acac) _2, also platinum described in U.S. Patent 3,159,601 and in Pat 3159662 of Ashby et al - hydrocarbon complex, and Lamoreaux et al U.S. Patent Platinum is described in the 3220972 Pat Arcola - DOO catalysts may be mentioned.

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

The addition amount of the hydrosilylation catalyst is not particularly limited, but it is preferably used in the range of 10 ⁻¹ to 10 ⁻¹⁰ mol with respect to ¹ mol of the alkenyl group of the polyhedral siloxane intermediate. More preferably, it is used in the range of 10 ⁻⁴ to 10 ⁻⁸ mol. In addition, the hydrosilylation catalyst is generally expensive and corrosive, and a large amount of hydrogen gas may be generated and the cured product may foam, so it is better not to use 10 ⁻¹ mol or more.

  As reaction temperature of hydrosilylation reaction, it is 30-400 degreeC, More preferably, it is preferable that it is 40-250 degreeC, More preferably, it is 50-160 degreeC.

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

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

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

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

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

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

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

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

<Composition>
The polyhedral polysiloxane composition of the present invention can be obtained by adding a curing agent, a hydrosilylation catalyst, and, if necessary, a curing retarder to the polyhedral polysiloxane compound. The polyhedral polysiloxane composition of the present invention can be made into a transparent liquid composition because the polysiloxane compound as a component is in a liquid state. By forming it into a liquid composition, it can be poured into a molded body, heated and cured to obtain a molded body easily. 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 70% or more with a 400 nm light beam when the molded product has a thickness of 3 mm. In addition, it is preferable that the polyhedral polysiloxane compound is in a liquid form because the polyhedral polysiloxane composition of the present invention can be easily obtained as a liquid.

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

  The curing time can be appropriately selected depending on the curing temperature, the amount of hydrosilylation catalyst used and the amount of hydrosilyl group, and other combinations of the composition of the present application. Is carried out for 10 minutes to 2 hours, a good cured product can be obtained.

  In the polyhedral polysiloxane composition used in the present invention, in addition to the above essential components, fillers such as pulverized quartz, calcium carbonate, carbon and the like as an extender may be added as necessary as long as they do not interfere with the effects of the present invention. May be added.

  In addition, various additives such as a colorant and a heat resistance improver, a reaction control agent, a mold release agent, or a dispersant for a filler are optionally added to the polyhedral polysiloxane composition of the present invention as necessary. 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 polysiloxane composition 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 polyhedral polysiloxane composition used in the present invention is a mixture of the above components uniformly using a kneader such as a roll, a Banbury mixer, a kneader, or a planetary stirring deaerator, and if necessary, heat-treated. It can obtain by giving.

  The polyhedral polysiloxane composition of the present invention may be formed by any method such as extrusion molding, compression molding, blow molding, calender molding, vacuum molding, foam molding, injection molding, liquid injection molding, and cast molding. By using it, it can be used as a molded article.

The molded product obtained from the polysiloxane composition according to the present invention is excellent in heat resistance and light resistance, and exhibits high transparency even for light having a wavelength in the near ultraviolet region of about 400 nm.
The polyhedral polysiloxane composition of the present invention can be used as a composition for optical materials. 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.

  Specific uses of the polyhedral polysiloxane composition and molded body obtained in the present invention are specifically resist materials, substrate materials in the field of liquid crystal displays, light guide plates, prism sheets, deflection plates, retardation plates, viewing angles. Examples of the peripheral materials of the liquid crystal display device such as a correction film, an adhesive, a color filter, a passivation film, a polarizer protective film, and a liquid crystal film.

  Color PDP (plasma display) sealant, antireflection film, optical correction film, housing material, front glass protective film, front glass substitute material, adhesive, color filter, which is expected as a next-generation flat panel display Passivation film.

  Moreover, the molding material of the LED element used for a LED display apparatus, the protective film of a front glass, a front glass alternative material, a color filter, a passivation film, an adhesive agent. In addition, substrate materials, light guide plates, color filters, passivation films, prism sheets, deflection plates, phase difference plates, viewing angle correction films, adhesives, polarizer protective films in plasma addressed liquid crystal (PALC) displays. In addition, protective films for front glass, color filters, passivation films, front glass substitute materials, and adhesives in organic EL (electroluminescence) displays. Further, various film substrates, front glass protective films, front glass substitute materials, color filters, passivation films, and adhesives in field emission displays (FED) are exemplified.

  In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Examples include pickup lenses, protective films, sealants, and adhesives.

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

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

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

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

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

  Next-generation DVDs, organic EL element peripheral materials, organic photorefractive elements, light-amplifying elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, etc. Examples thereof include fiber materials, element sealants, and adhesives.

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

(Heat resistance test)
It was cured for 24 hours in a hot air circulating oven set at 150 ° C., and the light transmittance after curing was measured.

(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 measured for light transmittance.

(Light transmittance)
Using a UV-visible spectrophotometer V-560 (manufactured by JASCO Corporation), light transmittance at wavelengths of 700 nm and 400 nm was measured under the conditions of a temperature of 20 ° C./humidity of 50%.

<Polyhedral polysiloxane compound>
(Production Example 1)
To 34.5 g of a 47 wt% aqueous solution of 2-hydroxyethyltrimethylammonium, 27.9 g of tetraethoxysilane was added and stirred for 10 hours. To the obtained silicate having a polyhedral structure, 30 mL of methanol was added and dissolved to obtain a silicate methanol solution A.

(Example 1)
9 mL of silicate methanol solution A was taken out with a syringe, and slowly dropped at room temperature with stirring to a mixed solution of 1.6 g of dimethylvinylchlorosilane, 0.65 g of dimethyldichlorosilane and 7 mL of dimethoxypropane, and allowed to react for 1 hour. After completion of the reaction, 30 mL of water and 30 mL of toluene were added, and the organic layer was extracted and concentrated to obtain a compound that was a brown viscous liquid. Next, the obtained compound was dissolved in a hexane solvent, filtered using Celite (manufactured by Wako Pure Chemical Industries, Ltd.), and the filtrate was concentrated to obtain a polyhedral polysiloxane compound B as a transparent liquid.

^{From the 29} Si-NMR spectrum, the signals of the silicon atoms of ViMe ₂ SiO, Me ₂ SiO ₂ , and SiO ₄ were confirmed to be 1 ppm, −18 ppm, and −110 ppm. From the GPC results, it was found that the product was a mixture of a polyhedral polysiloxane having a siloxane bond in the side chain and an oligomer in which the polyhedral polysiloxane was linked by a siloxane bond.

<Polyhedral polysiloxane composition>
(Example 2)
0.6 g of polyhedral polysiloxane compound B, 1.0 g of linear polydimethylsiloxane containing a hydrosilyl group at the end (DMS-H03, manufactured by Gerest), xylene solution of platinum vinylsiloxane complex (platinum vinyl containing 3 wt% as platinum) 0.03 μL of a siloxane complex, manufactured by Umicore Precious Metals Japan, Pt-VTSC-3X) was added to obtain a polyhedral polysiloxane composition as a uniform solution. The composition thus obtained was poured into a mold and cured by heating at 70 ° C. for 30 minutes, 120 ° C. for 10 minutes, and 150 ° C. for 10 minutes to obtain a 3 mm-thick molded article for evaluation. The light transmittance of the molded product is shown in Table 1 below.

As described above, the polyhedral polysiloxane compound of the present invention can be made into a transparent liquid and is easy to handle, and the molded body obtained from the composition using the compound has excellent heat resistance and light resistance. It is excellent and the decrease in light transmittance is small.

Claims (9)

formula
[XR ₂ SiO—SiO _3/2 ] _a [XR ₂ SiO— (R ₂ SiO) _m —SiO _3/2 ] _b [R ′ — (R ₂ SiO) _n —SiO _3/2 ] _c
(A to c are integers of 0 or 1 or more, a + b + c is an integer of 6 to 24, b + c is an integer of 1 or more, m and n are integers of 1 or more; R is an alkyl group or an aryl group, each of which is plural In some cases, they may be the same or different from each other; R ′ is another polyhedral polysiloxane; X is a hydrogen atom or an alkenyl group, and may be the same or different. A polyhedral polysiloxane compound comprising a structural unit.   The polyhedral polysiloxane compound according to claim 1, which is liquid at 20 ° C.   3. The method for producing a polyhedral polysiloxane compound according to claim 1, wherein the polysiloxane compound is obtained by reacting a silicate having a polyhedral structure with a mixture of monochlorosilane and dichlorosilane.   4. The polyhedral polysiloxane compound according to claim 3, wherein the molar ratio of the mixture of monochlorosilane and dichlorosilane is 0.1 to 4 mol of dichlorosilane with respect to 8 mol of monochlorosilane. Law.   A polyhedral polysiloxane compound produced by the production method according to claim 3 or 4.   A polyhedral polysiloxane composition comprising the polyhedral polysiloxane compound according to claim 1, a curing agent, and a hydrosilylation catalyst.   The polyhedral polysiloxane composition according to claim 6, further comprising a curing retarder.   A cured product obtained by curing the polyhedral polysiloxane composition according to claim 6 or 7.   The cured product according to claim 8, wherein a 3 mm-thick molded article has a light transmittance of 70% or more at a wavelength of 400 nm.