JPWO2007119627A1 - Curable composition, cured product of silsesquioxane, and production method thereof - Google Patents

Abstract

To provide a cured product of silsesquioxane having both heat resistance and transparency. a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes An oligomer of oxanes, b) a compound having at least two SiH groups in the same molecule, and c) a compound having at least two carbon-carbon double bonds in the same molecule other than those described in a), and D) Silsesquioxane hardened | cured material obtained by carrying out the coupling | bonding formation in the presence of a hydrosilylation catalyst.

Description

  The present invention relates to a cage silsesquioxane having a substituent containing a carbon-carbon double bond and a silsesquioxane mainly composed of a partially cleaved structure of these cage silsesquioxanes. Cured product excellent in heat resistance and transparency obtained by reacting an oligomer, a compound having a SiH group and a compound having a substituent containing a carbon-carbon double bond, and a curable composition capable of obtaining these cured products And a method for producing these cured products.

  In general, glass plates are widely used as display element circuit boards (particularly active matrix type) for liquid crystal display elements and organic EL display elements, color filter substrates, solar cell substrates, and the like. However, in recent years, transparent plastic substrates have been studied as an alternative to glass plates because they are easily broken, cannot be bent, have a large specific gravity, and are not suitable for weight reduction. Here, it is obtained by reacting mainly with transparent thermoplastics such as PMMA (polymethyl methacrylate) and PC (polycarbonate), epoxy resin, curable (meth) acrylate resin, silicone resin, and silsesquioxane. Transparent thermosetting plastics such as cured products have been studied. Especially, the hardened | cured material obtained by reacting silsesquioxane as a main component is excellent in heat resistance.

  Patent Document 1 discloses a method for producing a silicone resin in which an oligomer obtained by cohydrolyzing a trialkoxysilane having an organic group that can be polymerized with phenyltrialkoxysilane is further condensed using a base catalyst. Has been.

  As a copolymer of silsesquioxane and a vinyl monomer, Patent Document 2 discloses a polyorgano having a side chain organic group having a substituent containing at least 1 or 2 polymerizable unsaturated double bonds per molecule. Coating a clear coat layer comprising a silsesquioxane, a copolymer of a polydialkylsiloxane having a substituent containing at least one polymerizable unsaturated bond per molecule and a vinyl monomer or a composition using the same Disclosed is an improved stain resistant coating characterized by being provided on the surface.

  As a cured product having an interpenetrating structure of a reaction product of a vinyl compound and a SiH compound and a silsesquioxane oligomer, Patent Document 3 discloses (A) a silsesquioxane ladder polymer having a number average molecular weight of 500 or more, (B ) A silicon compound having a molecular weight of 1000 or less having at least two SiH groups in the molecule, (C) a silicon compound having a molecular weight of 1000 or less having at least two vinylsilyl groups in the molecule, (D) a neutral platinum catalyst, A curable composition containing is disclosed.

Claim 2 of Patent Document 4 includes vinyltrialkoxysilane represented by (A) CH ₂ ═CHSi (OR ′) ₃ (wherein R ′ is an alkyl group having 1 to 4 carbon atoms), and RSi. (OR ′) ₃ (in the formula, R ′ is an alkyl group having 1 to 4 carbon atoms. R is an alkyl group or aryl group having 1 to 20 carbon atoms which may have a substituent). Or a silsesquioxane oligomer obtained by cohydrolyzing two or more types of trialkoxysilane, (B) a silicon compound having at least two SiH groups in the molecule, and (C) a hydrosilylation catalyst. A curable composition is disclosed.

  Patent Document 5 discloses (A) a ladder-type silsesquioxane polymer, (B) a silanol condensation catalyst, (C) a silicon compound having at least two SiH groups in the molecule, and (D) at least in the molecule. A compound having two carbon-carbon double bonds, (E) a hydrosilylation catalyst, (F) a hydrosilylation inhibitor, and a prepreg composed of these components (A) to (F) and reinforcing fibers are disclosed.

Patent Document 6 discloses a transparent resin composition comprising a cage-type silsesquioxane having a methacryl group or a vinyl group and an unsaturated compound copolymerizable therewith, but the heat resistance of this resin composition is disclosed. Further, it is desirable to further improve the mechanical strength and the total light transmittance.
JP-A-56-151731 JP-A-8-48734 JP-A-8-225647 JP 2001-89662 A JP 2002-194122 A JP 2004-123936 A

  The present invention relates to a cage silsesquioxane having a substituent containing a carbon-carbon double bond and a silsesquioxane mainly composed of a partially cleaved structure of these cage silsesquioxanes. Silsesquioxane cured product having both heat resistance and transparency using oligomer as a raw material, curable composition from which these cured products are obtained, and method for producing silsesquioxane cured product excellent in workability and production efficiency The purpose is to provide.

The first of the present invention is
a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b),
c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the silsesquioxane oligomer as component a (component c), and d) a hydrosilylation catalyst (component d),
Is a curable composition containing.

The second of the present invention is
a) Silsesquioxanes obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Sun oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b),
c) a compound (component c) having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxanes as component a;
d) hydrosilylation catalyst (d component), and e) radical generator (e component),
Is a curable composition containing.

The third aspect of the present invention is
a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b),
c) a compound (component c) having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxanes as component a;
d) hydrosilylation catalyst (d component), and f) reinforcing filler (f component),
Is a curable composition containing.

The fourth aspect of the present invention is
a) Silsesquioxanes obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Sun oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b),
c) a compound (component c) having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxanes as component a;
d) hydrosilylation catalyst (d component),
e) radical generator (e component), and f) reinforcing filler (f component),
Is a curable composition containing.

The fifth aspect of the present invention is
a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers,
b) a compound having at least two SiH groups in the same molecule, and c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxane as a component, A composition comprising
d) in the presence of a hydrosilylation catalyst,
The present invention relates to a cured silsesquioxane obtained by bonding.

The sixth of the present invention is
a) Silsesquioxane obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes San oligomers,
b) a compound having at least two SiH groups in the same molecule, and c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxane as a component, A composition comprising
d) in the presence of a hydrosilylation catalyst, and e) a radical generator,
The present invention relates to a cured silsesquioxane obtained by bonding.

The seventh of the present invention is
a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b), and c) at least two carbon-carbon double bonds in the same molecule, excluding the oligomer of silsesquioxane as the component a. A composition comprising a compound (component c) having
d) in the presence of a hydrosilylation catalyst (d component), and f) a reinforcing filler (f component),
The present invention relates to a cured silsesquioxane obtained by forming a chemical bond.

The eighth of the present invention is
a) Silsesquioxanes obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Sun oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b), and c) at least two carbon-carbon double bonds in the same molecule, excluding the oligomer of silsesquioxane as the component a. A composition comprising a compound (component c) having
d) hydrosilylation catalyst (d component),
e) in the presence of a radical generator (e component), and f) a reinforcing filler (f component),
The present invention relates to a cured silsesquioxane obtained by forming a chemical bond.

The ninth of the present invention is
A process for producing a cured silsesquioxane from the first curable composition of the present invention and / or a process for producing a fifth cured silsesquioxane of the present invention,
a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers,
b) a compound having at least two SiH groups in the same molecule, and c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxane as a component, A composition comprising
d) in the presence of a hydrosilylation catalyst,
The present invention relates to a process for producing a cured silsesquioxane, characterized in that a cured product is obtained by raising the temperature stepwise or continuously in the range of 20 ° C to 400 ° C.

The tenth aspect of the present invention is a process for producing a cured silsesquioxane and / or a sixth process for producing a cured silsesquioxane of the present invention from the second curable composition of the present invention,
a) Silsesquioxane obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes San oligomers,
b) a compound having at least two SiH groups in the same molecule, and c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxane as a component, A composition comprising
d) in the presence of a hydrosilylation catalyst, and e) a radical generator,
It is related with the manufacturing method of the silsesquioxane hardened | cured material characterized by obtaining hardened | cured material by the following reaction A or reaction B.
(Reaction A)
1) Perform hydrosilylation reaction in the range of 20 ° C to 80 ° C,
2) A radical reaction is performed during the hydrosilylation reaction of 1) above.
3) Thereafter, a cured product is obtained by performing a hydrosilylation reaction and a radical reaction in the range of 80 ° C to 400 ° C.
(Reaction B)
1) Perform hydrosilylation reaction in the range of 20 ° C to 80 ° C,
2) Thereafter, a cured product is obtained by performing a hydrosilylation reaction and a radical reaction in the range of 80 ° C to 400 ° C.

Eleventh aspect of the present invention is a process for producing a silsesquioxane cured product and / or a seventh process for producing a silsesquioxane cured product of the present invention from the third curable composition of the present invention,
a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers,
b) a compound having at least two SiH groups in the same molecule, and c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxane as a component, A composition comprising
in the presence of d) hydrosilylation catalyst (d component), and f) reinforcing filler (f component),
The present invention relates to a process for producing a cured silsesquioxane, characterized in that a cured product is obtained by raising the temperature stepwise or continuously in the range of 20 ° C to 400 ° C.

Twelfth aspect of the present invention is a process for producing a silsesquioxane cured product and / or an eighth process for producing a cured silsesquioxane of the present invention from the fourth curable composition of the present invention,
a) Silsesquioxane obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes San oligomers,
b) a compound having at least two SiH groups in the same molecule, and c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxane as a component, A composition comprising
d) hydrosilylation catalyst (d component),
e) in the presence of a radical generator (e component), and f) a reinforcing filler (f component),
The present invention relates to a process for producing a cured product containing silsesquioxane complex, characterized in that a cured product is obtained by the following reaction A or reaction B.
(Reaction A)
1) Perform hydrosilylation reaction in the range of 20 ° C to 80 ° C,
2) A radical reaction is performed during the hydrosilylation reaction of 1) above.
3) Thereafter, a cured product is obtained by performing a hydrosilylation reaction and a radical reaction in the range of 80 ° C to 400 ° C.
(Reaction B)
1) Perform hydrosilylation reaction in the range of 20 ° C to 80 ° C,
2) Thereafter, a cured product is obtained by performing a hydrosilylation reaction and a radical reaction in the range of 80 ° C to 400 ° C.

  In the first, third, fifth, seventh, ninth and eleventh aspects of the present invention, it is preferable not to include a radical generator (component e) as a reaction initiator.

  As the thirteenth aspect of the present invention, the fifth to eighth silsesquioxane cured products of the present invention are used for optical films, optical sheets, substrates for display element circuits, or transparent substrates. Furthermore, the fifth to eighth silsesquioxane cured products of the present invention are used for optical element sealants, light-emitting element sealants, particularly white LED sealants, or semiconductor sealants.

The first to eighth preferred embodiments of the present invention will be described below. A plurality of preferred embodiments can be combined.
(1) The component a, component b and component c are uniformly compatible compositions (first to eighth of the present invention).
(2) The e component is a radical generator that generates radicals by light irradiation (second, fourth, sixth, and eighth of the present invention).
(3) The e-component radical generator has a 10-hour half-life temperature of 100 ° C. or higher and 400 ° C. or lower (second, fourth, sixth and eighth of the present invention).
(4) The refractive index of the f component is 1.48 to 1.60 (third, fourth, seventh and eighth of the present invention).
(5) The f component is a sheet-like material having a thickness of 10 to 2000 μm (third, fourth, seventh and eighth of the present invention).
(6) 1-60 mass parts of a component is included in 100 mass parts of total weight of a component, b component, and c component (the 1st-8th of this invention).
(7) The composition ratio of the a component, the b component, and the c component is the molar ratio of the SiH group of the b component and the sum of the carbon-carbon double bonds of the a component and the c component (SiH group / carbon- The carbon double bond) is 0.4 to 3 (first to eighth of the present invention).
(8) The functional group molar ratio of the carbon-carbon double bond of the c component and the a component (the carbon-carbon double bond of the c component / the carbon-carbon double bond of the a component) is 2 to 200 ( First to eighth of the present invention).
(9) The cage silsesquioxane having a substituent containing a carbon-carbon double bond is represented by the general formula [RSiO _1.5 ] n (wherein R is a hydrogen atom, having 1 to 6 carbon atoms) An alkoxy group or an aryloxy group, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, A group selected from the group consisting of a halogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing group having 1 to 10 silicon atoms, and a plurality of Rs on the same silsesquioxane molecule are the same Or, on average, at least two of them are substituents containing a carbon-carbon double bond, and n is an integer of 6 to 20.) (First to eighth of the present invention).
(10) Sils obtained from at least one compound selected from cage-shaped silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-shaped silsesquioxanes The oligomer of sesquioxanes is a mixture having a number average molecular weight of 500 to 4000 (first to eighth of the present invention).
(11) A silage obtained from at least one compound selected from cage-shaped silsesquioxanes having a substituent containing a carbon-carbon double bond and a partially cleaved structure of these cage-shaped silsesquioxanes. The oligomer of sesquioxane is a mixture having a value of (weight average molecular weight) / (number average molecular weight) of 1 to 1.5 (first to eighth of the present invention).
(12) The cured silsesquioxane is a sheet having a thickness of 10 to 2000 μm (first to eighth of the present invention).
(13) The average coefficient of linear expansion of 20 to 200 ° C. of the cured silsesquioxane is 5 ppm / K or more and 60 ppm or less / K (seventh and eighth of the present invention).
(14) The total light transmittance from a wavelength of 400 nm to 800 nm of the cured silsesquioxane is 85% or more and 100% or less (first to eighth of the present invention).
(14) The 5% weight reduction temperature of the cured silsesquioxane is 400 ° C. or higher and 800 ° C. or lower (first to eighth of the present invention).
(15) The maximum elongation at tensile strength of the cured silsesquioxane is 10% or more and 40% or less (the fifth and sixth aspects of the present invention).

The first, fifth and ninth aspects of the present invention are:
a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers,
b) a compound having at least two SiH groups in the same molecule, and c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxane of a), and A composition comprising
d) By polymerizing in the presence of a hydrosilylation catalyst, a cured product having excellent heat resistance and excellent transparency can be obtained.

The second, sixth and tenth aspects of the present invention are:
a) Silsesquioxane obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes San oligomers,
b) a compound having at least two SiH groups in the same molecule, and c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxane as a component, A composition comprising
d) in the presence of a hydrosilylation catalyst, and e) a radical generator,
By polymerizing, a cured product having excellent heat resistance and excellent transparency can be obtained.

The third, seventh and eleventh aspects of the present invention are:
a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers,
b) a compound having at least two SiH groups in the same molecule, and c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxane as a component, A composition comprising
in the presence of d) a hydrosilylation catalyst, and f) a reinforcing filler,
By generating a chemical bond, a cured product having excellent heat resistance, dimensional stability, mechanical strength, and transparency can be obtained.

The fourth, eighth and twelfth aspects of the present invention are:
a) Silsesquioxane obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes San oligomers,
b) a compound having at least two SiH groups in the same molecule, and c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxane of a), and A composition comprising
d) hydrosilylation catalyst,
e) in the presence of a radical generator, and f) a reinforcing filler,
By generating a chemical bond, a cured product having excellent heat resistance, dimensional stability, mechanical strength, and transparency can be obtained.

In the first to twelfth aspects of the present invention,
(1) By using a composition (mixture) in which the component a, component b and component c are uniformly compatible, a reaction occurs uniformly and a cured product having excellent transparency can be obtained. More preferably, the a component, the b component, the c component, and the d component are compositions that are uniformly compatible. Moreover, in the composition containing e component, it is especially preferable that it is a composition which a component, b component, c component, d component, and e component mixed uniformly.
(2) By using an oligomer of silsesquioxane having a low molecular weight or a low molecular weight dispersity as the component a, preferably an oligomer of silsesquioxane having a low molecular weight and a low molecular weight dispersibility. , B component and c component can be preferably used because of improved compatibility.

  In the second, fourth, sixth, eighth, tenth and twelfth aspects of the present invention, when a bond is formed using a radical reaction, the first-stage cross-linking is allowed to proceed with hydrosilylation and then the second-stage. It is considered important to obtain a transparent molded body by applying cross-linking by the radical reaction of the eye. Therefore, if the radical reaction starts with the carbon-carbon double bond and SiH group still remaining before the crosslinking by hydrosilylation proceeds sufficiently, the carbon- The carbon double bond may be consumed by a radical reaction, may induce phase separation in the curing process, and the molded body may become clouded. In addition, since crosslinking due to hydrosilylation is naturally reduced, it may be considered that the heat resistance and strength of the molded product are adversely affected. In order to avoid this, it is conceivable to add a radical initiator at the stage where hydrosilylation is completed, but it is extremely difficult to uniformly mix the radical initiator into the already cured molded article. Therefore, even radical generators that are known to initiate radical reactions by light rather than thermally, or thermal radical initiators, hardly initiate radical reactions at the temperature and time conditions for bond formation by hydrosilylation. It is considered that it is very effective to select and use an initiator that is said to be used. As a measure of the ease of thermal radical initiation, the 10-hour half-life temperature indicated by the radical initiator can be used as an index.

  The present invention is a long-term storage-stable curable composition capable of obtaining a cured product excellent in heat resistance and transparency using a silsesquioxane composition excellent in moldability. In addition, the present invention is manufactured from a silsesquioxane composition having excellent moldability, excellent in heat resistance and transparency, and includes a liquid crystal element display substrate including an active matrix type, a display element substrate for organic EL, and a color filter. Suitable for substrates, touch panel substrates, electronic paper substrates, solar cell substrates, optical lenses, optical waveguides, optical element encapsulants, light emitting element encapsulants, white LED encapsulants, semiconductor encapsulants, etc. It is a cured body that can be used. Moreover, according to the present invention, a cured product obtained by molding a silsesquioxane cured product having both heat resistance and transparency by a simple method can be produced.

In the present invention,
The component a is a cage silsesquioxane having a substituent containing a carbon-carbon double bond and at least one structure selected from the partially cleaved structures of these cage silsesquioxanes. It means an oligomer of the resulting silsesquioxane.
-The component b means a compound having at least two SiH groups in the same molecule.
-C component means the compound which has at least 2 carbon-carbon double bond in the same molecule | numerator except the oligomer of the silsesquioxane which is a component.
-D component means a hydrosilylation catalyst.
-E component means a radical generating agent.
-F component means a reinforcement filler.
-A curable composition means the composition containing d component from a component to d component, and the composition containing d component, e component, and / or f component from a component.
-Hardened | cured material means the hardened | cured material after hardening a curable composition.

  In the curable composition, it is preferable that the a component, the b component, and the c component are uniformly compatible since a cured product having excellent transparency can be easily obtained. Especially, it is more preferable that a component, b component c component, and d component are mutually compatible. In addition, when the e component is further included, it is particularly preferable that the a component, the b component, the c component, the d component, and the e component are uniformly compatible.

  As the curable composition, a composition (curable composition C, D) containing a radical generator (e component) and a composition not containing (curable composition A, B) are obtained.

The curable composition A is
a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b),
c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the silsesquioxane oligomer as component a (component c), and d) a hydrosilylation catalyst (component d),
It is a composition containing these. A cured product can be obtained by bonding (polymerizing) the c component from the a component with the d component.

The curable composition B is
a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b),
c) a compound (component c) having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxanes as component a;
d) hydrosilylation catalyst (d component),
f) A composition comprising reinforcing filler (component f) and A cured product can be obtained by bonding (polymerizing) the c component from the a component with the d component. Further, when a functional group capable of forming a bond with the c component from the a component exists on the surface of the f component, a cured product is obtained by bonding (polymerizing) the c component and the f component from the a component with the d component. Can do.

The curable composition C is
a) Silsesquioxanes obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Sun oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b),
c) a compound having at least two carbon-carbon double bonds (component c) excluding the oligomer of silsesquioxanes as component a,
d) hydrosilylation catalyst (d component), and e) radical generator (e component),
It is a composition containing these. A cured product can be obtained by forming (polymerizing) the c component from the a component with the d component and the e component.

The curable composition D is
a) Silsesquioxanes obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Sun oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b),
c) a compound having at least two carbon-carbon double bonds (component c) excluding the oligomer of silsesquioxanes as component a,
d) hydrosilylation catalyst (d component),
e) radical generator (e component), and f) reinforcing filler (f component),
It is a composition containing these. A cured product can be obtained by forming (polymerizing) the c component from the a component with the d component and the e component. In addition, when a functional group capable of forming a bond with a to c component exists on the surface of the f component, a cured product is formed by bonding (polymerizing) a to c and f components with the d and e components. Obtainable.

The cured silsesquioxane is
a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b), and c) at least two carbon-carbon double bonds in the same molecule excluding the oligomer of the silsesquioxane of component a. Or a composition containing a compound (c component), or f) a reinforcing filler (f component).
Cured product obtained by bond formation (polymerization) in the presence of d) hydrosilylation catalyst (component d), or d) hydrosilylation catalyst (component d) and e) radical generator (component e) It is.

  When obtaining a cured silsesquioxane, the mixing ratios of the raw material a component, b component and c component can be selected as appropriate.

For example, when a silsesquioxane cured product is obtained from a composition containing a component, b component and c component by using a hydrosilylation catalyst (d component) without containing a radical generator (e component) (No. 1 of the invention). First, third invention, fifth invention, seventh invention)
[1] In the total weight of 100 parts by mass of the component a, the component b and the component c, the component a is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, more preferably 5 to 45 parts by mass,
[2] The composition ratio of the a component, the b component, and the c component is preferably a molar ratio (SiH group) of the SiH group of the b component and the sum of the carbon-carbon double bond groups of the a component and the c component. / Carbon-carbon double bond group) is 0.4 to 3, more preferably 1 to 2, still more preferably 1 to 1.6, and particularly preferably 1.2 to 1.4.

When the composition ratio of the a component, the b component, and the c component is less than the above range, the heat resistance may be lowered. Moreover, when a component is larger than the said range, a crosslinking density becomes low, heat resistance becomes low, and it may become weak. Moreover, when the molar ratio (SiH group / carbon-carbon double bond group) of the Si component of b component and the sum of the carbon-carbon double bond groups of component a and c is smaller than the above range, crosslinking is sufficient. In addition, the heat resistance may be low and may become brittle. In addition, when the molar ratio of the component b, the component a, and the sum of the carbon-carbon double bond groups of the component c is larger than the above range, uncrosslinked SiH groups are increased, the crosslinking density is decreased, and the heat resistance is decreased. And may become brittle.

Silsesquioxane curing from a composition containing a component, b component and c component using a hydrosilylation catalyst (d component) without including a radical generator (e component) and reinforcing filler (f component) When obtaining a product (first invention and fifth invention)
[1] In the total weight of 100 parts by mass of the component a, the component b and the component c, the component a is preferably 1 to 60 parts by mass, more preferably 2 to 50 parts by mass, more preferably 5 to 45 parts by mass,
[2] The composition ratio of the a component, the b component, and the c component is preferably a molar ratio between the SiH group of the b component and the sum of the carbon-carbon double bond groups of the a component and the c component (SiH group). / Carbon-carbon double bond group) 1 to 3, more preferably 1 to 2, still more preferably 1 to 1.6, particularly preferably 1.2 to 1.6,
[3] The functional group molar ratio of the carbon-carbon double bond of component c and component a (carbon component-carbon double bond group of component c / carbon-carbon double bond group of component a) is preferably 8 to 200. , More preferably 8 to 120, still more preferably 8 to 30, particularly preferably 8 to 20,
When a cured product of silsesquioxane is used, it is easy to obtain a cured product having a maximum point elongation of 10% to 40%, preferably 10-30% in tensile property evaluation, and has excellent extensibility. It can be used as a cured product.

  Regarding the composition ratio of the a component, the b component, and the c component, if the content of the a component is smaller than the above range, the heat resistance may be low and the composition may become brittle. Moreover, when content of a component is larger than the said range, a crosslinking density will become low and heat resistance will become low, and it may become weak and transparency may be lost. Moreover, if the molar ratio (SiH group / carbon-carbon double bond group) of the Si component of component b and the sum of the carbon-carbon double bond groups of component a and component c is smaller than the above range, crosslinking is sufficient. In addition, the heat resistance may be low and may become brittle. On the other hand, if the molar ratio is larger than the above range, the number of uncrosslinked SiH groups increases, the crosslinking density is lowered, the heat resistance is lowered, and the material may become brittle. Moreover, when the functional group molar ratio of the carbon-carbon double bond of the c component and the a component (the carbon-carbon double bond group of the c component / the carbon-carbon double bond group of the a component) is smaller than the above range, it becomes brittle. In some cases, transparency may be lost, and tensile elongation may be reduced. On the other hand, when the molar ratio is larger than the above range, the heat resistance is lowered and the material may become brittle.

In addition, when a silsesquioxane cured product is obtained from a composition containing a component, b component and c component using a hydrosilylation catalyst and a radical generator (second invention, fourth invention, sixth invention) In the eighth of the invention,
[1] In a total weight of 100 parts by weight of the component a, the component b, and the component c, the component a is preferably 30 to 60 parts by weight, more preferably 35 to 55 parts by weight, more preferably 40 to 50 parts by weight,
[2] The composition ratio of the a component, the b component, and the c component is preferably a molar ratio of the SiH group of the b component and the sum of the carbon-carbon double bond groups of the a component and the c component (SiH group / Carbon-carbon double bond group) is 0.3 to 1, more preferably 0.5 to 1, and more preferably 0.8 to 1.

  When the composition ratio of the a component, the b component, and the c component is less than the above range, the heat resistance may be lowered. Moreover, when a component is larger than the said range, a crosslinking density may become low, heat resistance may become low, and it may become weak. Further, when the molar ratio (SiH group / carbon-carbon double bond group) of the Si component of b component and the sum of the carbon-carbon double bond groups of component a and c is smaller than the above range, crosslinking is sufficient. In some cases, the heat resistance is low and the material becomes brittle. On the other hand, if the molar ratio is larger than the above range, the number of uncrosslinked SiH groups increases, the crosslinking density is lowered, the heat resistance is lowered, and the material may become brittle.

  The cage silsesquioxanes having a substituent containing a carbon-carbon double bond as the component a are compounds represented by the following general formula (1).

(In the general formula (1), R represents a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms or an aryloxy group, a hydrocarbon group having 1 to 20 carbon atoms, and an oxygen-containing functional group having 1 to 20 carbon atoms. From a basic hydrocarbon group, a nitrogen-containing functional hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functional hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing group having 1 to 10 silicon atoms A plurality of R on the same silsesquioxane molecule may be the same or different, and at least two are substituents containing a carbon-carbon double bond, n is an integer from 6 to 20.)

In general formula (1),
n is an integer from 6 to 20 or a combination of these, and is especially 6, 8, 10, 12, and / or 14, in order to reduce the average molecular weight and increase the compatibility of the cured composition, or A combination of a plurality of these is preferred, and in particular, 8, 10, and / or 12, or a combination of these is preferred.

In the substituent R of the general formula (1),
-As a C1-C6 alkoxy group or an aryloxy group, Preferably it is a C1-C4 alkoxy group or a C6-aryloxy group. Preferable examples include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group and the like.
-As a C1-C20 hydrocarbon group, Preferably it is a C1-C10 hydrocarbon group, More preferably, it is a C1-C6 hydrocarbon group. Preferred examples include saturated hydrocarbon groups such as methyl, ethyl, propyl, butyl, hexyl, cyclopentyl, and cyclohexyl groups, aromatic hydrocarbon groups such as phenyl and methylphenyl groups, vinyl groups, and propenyls. And a hydrocarbon group containing a carbon-carbon double bond such as a group, a butenyl group, and a styryl group.
-The oxygen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms is preferably an oxygen-containing functionalized hydrocarbon group having 1 to 10 carbon atoms, more preferably an oxygen-containing functionalized hydrocarbon group having 1 to 6 carbon atoms. It is an oxygen functionalized hydrocarbon group. Preferred examples include methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, Examples include 3-glycidoxypropyl group, 3-methacryloxypropyl group, 3-acryloxypropyl group and the like.
The nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms is preferably a nitrogen-containing functionalized hydrocarbon group having 1 to 10 carbon atoms, and more preferably containing 1 to 6 carbon atoms. Nitrogen functionalized hydrocarbon group. Preferred examples include aminomethyl group, 2-aminoethyl group, 3-aminopropyl group, N-2-aminomethyl-3-aminopropyl group, N-phenyl-3-aminopropyl group and the like.
The halogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms is preferably a halogen-containing functionalized hydrocarbon group having 1 to 10 carbon atoms, and more preferably containing 1 to 6 carbon atoms. Halogen functionalized hydrocarbon group. Preferred examples include chloromethyl group, 2-chloroethyl group, 3-chloropropyl group, bromomethyl group, 2-bromomethyl group, 3-bromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl. Group, 3-fluoropropyl group, 3,3,3-trifluoropropyl group and the like.
The silicon-containing group having 1 to 10 silicon atoms is preferably a silicon-containing group having 1 to 6 carbon atoms. Preferred examples include a dimethylsiloxy group and a 3- (dimethylsilyl) propyl group.
These contain at least two substituents having a carbon-carbon double bond such as vinyl group, propenyl group, butenyl group, styryl group, 3-methacryloxypropyl group, and 3-acryloxypropyl group in one molecule. It can be appropriately combined with the conditions.

An example of the compound [RSiO _1.5 ] ₈ where n is 8 represented by the general formula (1) is shown in the general formula (2).

The following (a1) to (a3) are examples of the partially-cleavage structure of cage silsesquioxanes having a substituent containing a carbon-carbon double bond as component a.
(A1) One Si—O—Si bond portion constituting the cage silsesquioxane is converted to two Si—OH, and a portion in which the Si—O—Si bond is apparently cleaved by H ₂ O A cage silsesquioxane containing at least one or more locations.
(A2) One RSiO _1.5 unit constituting the cage silsesquioxane is apparently deficient, and the portion remaining in the cage shape of the deficient portion includes at least three Si-OH portions. A cage-shaped silsesquioxane containing one or more locations.
(A3) A cage-shaped silsesquioxane containing a complex cleavage defect portion of the above (a1) and (a2).

  The cleavage structure will be described using the cage silsesquioxane of the general formula (2).

In the cleavage structure of (a1), as shown in the general formula (3), one Si—O—Si bond portion constituting the cage silsesquioxane becomes two Si—OH, and apparently Si This is a cage silsesquioxane containing one portion where the —O—Si bond is cleaved by H ₂ O.

In the cleavage structure of (a2), as shown in the general formula (4), one RSiO _1.5 unit constituting the cage silsesquioxane apparently lacks, and the cage shape of the defect site is The remaining part is cage-shaped silsesquioxane containing one part of three Si—OH.

  As the component a, a mixture having a number average molecular weight (Mn) of preferably 500 to 4000, more preferably a mixture of 500 to 3000, and more preferably a mixture of 500 to 1800 is used. According to this, since compatibility with b component, c component, d component, and e component improves, it is preferable. When the number average molecular weight is less than 500, it is difficult to selectively synthesize a cage structure. Further, when the number average molecular weight exceeds 4000, the compatibility may be lowered.

  The component a is preferably a mixture having a value of (weight average molecular weight Mw) / (number average molecular weight Mn) of 1 to 1.5, more preferably a mixture of 1 to 1.3, further preferably 1 to 1.2. Use a mixture. According to this, since compatibility with b component, c component, d component, and e component improves, it is preferable. On the other hand, if the above value exceeds 1.5, the compatibility with these components may be lowered.

  In the present invention, the a component is preferably a hydrolysis of trialkoxysilane and a subsequent condensation reaction product. Specifically, a co-hydrolysis-condensation reaction product of methyltrialkoxysilane and vinyltrialkoxysilane, a co-hydrolysis-condensation reaction product of phenyltrialkoxysilane and vinyltrialkoxysilane, or the like can be preferably used. .

  As the compound having at least two SiH groups in the molecule of the component b, a known compound having two SiH groups can be used. For example, the following compounds (b1) to (b4) may be used alone or in combination of two or more (for example, a combination of b1 and b1, b1 and b2, etc.).

(B1) (SiR ¹ HO) _h (h is an integer of 2 to 10, preferably 3 to 6).
(B2) R ¹ — (SiR ¹ HO) _m —R ¹ (m is an integer of 2 to 50, preferably an integer of 2 to 12).
(B3) H _x SiR ¹ _(4-x) (x is an integer of 2 to 4, preferably an integer of 2 to 3).
_{^{(B4) H y SiR 1 (}} 3-y) -Q z -SiH y R 1 (3-y) (y is an integer of 1 to 3, preferably 1 to 2 integer, z is 1 to 50 integer, Preferably an integer of 1 to 12.

In the compounds of (b1) to (b4),
Examples of the substituent R ¹ include a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms or an aryloxy group, a hydrocarbon group having 1 to 20 carbon atoms, and an oxygen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms. From a group consisting of a nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 10 silicon atoms, and a polar group There is at least one selected. R ^{1 in} one molecule may be the same or different.

In the substituent R ¹ of the compounds (b1) to (b4),
-As a C1-C6 alkoxy group or an aryloxy group, Preferably it is a C1-C4 alkoxy group or a C6-aryloxy group. Preferable examples include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group and the like.
-As a C1-C20 hydrocarbon group, Preferably it is a C1-C10 hydrocarbon group, More preferably, it is a C1-C6 hydrocarbon group. Preferred examples include saturated hydrocarbon groups such as methyl, ethyl, propyl, butyl, hexyl, cyclopentyl, and cyclohexyl groups, aromatic hydrocarbon groups such as phenyl and methylphenyl groups, vinyl groups, and propenyls. And a hydrocarbon group containing a carbon-carbon double bond such as a group, a butenyl group, and a styryl group.
-The oxygen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms is preferably an oxygen-containing functionalized hydrocarbon group having 1 to 10 carbon atoms, more preferably an oxygen-containing functionalized hydrocarbon group having 1 to 6 carbon atoms. It is an oxygen functionalized hydrocarbon group. Preferred examples include methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, Examples include 3-glycidoxypropyl group, 3-methacryloxypropyl group, 3-acryloxypropyl group and the like.
The nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms is preferably a nitrogen-containing functionalized hydrocarbon group having 1 to 10 carbon atoms, and more preferably containing 1 to 6 carbon atoms. Nitrogen functionalized hydrocarbon group. Preferred examples include aminomethyl group, 2-aminoethyl group, 3-aminopropyl group, N-2-aminomethyl-3-aminopropyl group, N-phenyl-3-aminopropyl group and the like.
The halogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms is preferably a halogen-containing functionalized hydrocarbon group having 1 to 10 carbon atoms, and more preferably containing 1 to 6 carbon atoms. Halogen functionalized hydrocarbon group. Preferred examples include chloromethyl group, 2-chloroethyl group, 3-chloropropyl group, bromomethyl group, 2-bromomethyl group, 3-bromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoroethyl. Group, 3-fluoropropyl group, 3,3,3-trifluoropropyl group and the like.
The silicon-containing group having 1 to 10 silicon atoms is preferably a silicon-containing group having 1 to 6 carbon atoms. Preferred examples include a dimethylsiloxy group and a 3- (dimethylsilyl) propyl group.
-Preferable examples of the polar group include a cyano group, a carbonyl group, and a carboxyl group. These may constitute a substituent by themselves, or may be one substituent in a saturated hydrocarbon group, an alkenyl group, an aryl group, or a silicon skeleton substituent.

In the compounds (b1) to (b4), examples of the divalent substituent represented by Q include at least one selected from the group consisting of a saturated hydrocarbon group, an aryl group, and an oxygen-containing group.
-As for a saturated hydrocarbon group, C1-C10 is preferable and C1-C6 is more preferable. Preferable examples include methylene, ethylene, propylene, butylene and the like, and the carbon may have a substituent such as a saturated hydrocarbon group, an alkenyl group, an aryl group or a polar group.
-As for an aryl group, C6-C18 is preferable and C6-C12 is more preferable. Preferable examples include a phenyl group, a tolyl group, a naphthyl group, and the like, and the carbon may have a substituent such as a saturated hydrocarbon group, an alkenyl group, an aryl group, or a polar group.
-Preferred examples of the oxygen-containing group include a carbonyl group in addition to the oxygen atom itself.

As specific examples of the compounds (b1) to (b4),
Examples of (b1) include cyclosiloxane compounds such as trimethylcyclotrisiloxane, tetramethylcyclotetrasiloxane, and pentamethylcyclopentasiloxane.
Examples of (b2) include linear siloxane compounds such as polymethylhydrosiloxane, polyphenylhydrosiloxane, methylhydrosiloxane-dimethylsiloxane copolymer, and methylhydrosiloxane-phenylmethylsiloxane copolymer.
Examples of (b3) include silane compounds such as dimethylsilane, diphenylsilane, and methylphenylsilane.
Examples of (b4) include terminal hydrosilyl compounds such as bis (dimethylsilyl) benzene, bis (dimethylsiloxy) benzene, bis (dimethylsilyl) methane, bis (dimethylsiloxy) methane, and tetramethyldisiloxane.

The component c is a compound having at least two carbon-carbon double bonds in the molecule, and the following compounds (c1) to (c7) can be used.
(C1) Benzene or diphenyl substituted with two or more of —CH═CH ₂ . Preferable examples include divinylbenzene and divinyldiphenyl.
(C2) An alkane having 2 to 500 main chain carbon atoms, preferably 2 to 200 main chain carbon atoms, substituted by 2 or more of —CH═CH ₂ . Preferable examples include 1,5-hexadiene and 1,2-polybutadiene oligomer.
(C3) A cycloalkane having 5 to 12 main chain carbon atoms, preferably 5 to 8 main chain carbon atoms, substituted by 2 or more of —CH═CH ₂ . Preferable examples include trivinylcyclohexane.
(C4) Alkapolyene having 2 to 500 main chain carbon atoms, preferably 2 to 200 main chain carbon atoms, substituted by 2 or more of —CH═CH ₂ . Preferable examples include a 1,2-vinyl structure-containing compound of a polybutadiene oligomer.
(C5) Alkapolyene having 6 to 500 main chain carbon atoms, preferably 6 to 200 main chain carbon atoms, containing two or more —CH═CH— in the molecular chain. Preferable examples include 2,4-hexadiene and polybutadiene oligomer.
(C6) A cycloalkapolyene having 5 to 18 main chain carbon atoms, preferably 5 to 10 main chain carbon atoms, containing two or more —CH═CH— in the molecular chain. Preferred examples include norbornadiene and cyclooctatriene.
(C7) Ester of vinyl alcohol or allyl alcohol and polycarboxylic acid. Preferable examples include divinyl phthalate and diallyl phthalate.

  As the d component hydrosilylation catalyst, a commonly known catalyst can be used without any particular limitation, and a platinum catalyst is particularly preferred in order to allow the hydrosilylation reaction to proceed with good yield.

Although there is no particular limitation on the use amount of a hydrosilylation catalyst, preferably used in an amount of ¹⁰ -1 ^{to 10} -8 mol relative to SiH groups 1mol in the cured composition, more preferably from ¹⁰ -3 to 10 ^- Used at a ratio of ⁶ mol.

  Examples of the hydrosilylation catalyst for component d include chloroplatinic acid, platinum (0) 1,2-divinyl-1,1,3,3-tetramethylsiloxane complex, platinum (0) -acetylacetonate complex, platinum ( Examples thereof include platinum catalysts such as 0) -decadiene complex.

  As the e-component radical generator, generally known ones can be used without any particular limitation. When manufacturing a silsesquioxane hardened | cured material, the carbon-carbon double bond contained in c component which did not react with SiH group can be combined by using a hydrosilylation catalyst and a radical generator together. And has the effect of increasing the crosslinking density.

  As the component e, either a compound in which radical generation is initiated by light (photodegradable radical generator) or a compound initiating by heat (thermally decomposable radical generator) can be used. Among these, a photodegradable radical generator and a 10-hour half-life temperature can be obtained because the bond formation by radical reaction can be controlled stepwise and the heat resistance and strength are easily improved without impairing the transparency of the cured product. A radical generator having a temperature of 100 ° C. or more and 400 ° C. or less, preferably 100 to 180 ° C. can be used particularly preferably.

Although there is no restriction | limiting in particular as the usage-amount of e component, It is preferable to use in the ratio of 10 ^{< -1} > ^-10 <^-8> mol with respect to ¹ mol of carbon-carbon double bonds in a hardening composition, More preferably, 10 ^<-3>. It is used at a ratio of -10 ⁻⁶ mol.

  As an example of the component e, for example, as a photodegradable radical generator, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name Irgacure 651: Ciba Specialty Chemicals), 1-hydroxy -Cyclohexyl-phenyl-ketone (trade name Irgacure 184: Ciba Specialty Chemicals), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name Darocur 1173: Ciba Specialty Chemicals), 1 -[4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name Irgacure 2959: Ciba Specialty Chemicals) and the like can be mentioned.

  Thermally decomposable radical generators include azobisisobutyronitrile, dibenzoyl peroxide (trade name Nyper BW: Nippon Oil & Fats), t-butylperoxybenzoate (trade name perbutyl Z: Nippon Oil & Fats), dicumyl peroxide (product) No. Park Milta D: Japanese fats and oils).

  Examples of radical generators having a 10-hour half-life temperature of 100 ° C. or higher include di-t-butyl peroxide (trade name Perocta D: Nippon Oil & Fats), p-menthane hydroperoxide (trade name Permenta H: Nippon Oil & Fats), diisopropylbenzene hydro Peroxide (trade name Park Mill P: Nippon Oil & Fats), 1,1,3,3-tetramethylbutyl hydroperoxide (trade name Perocta H: Nippon Oil & Fats), cumene hydroperoxide (trade name Park Mill H: Nippon Oil & Fats), t-butyl Hydroperoxide (trade name perbutyl H: Japanese fats and oils) and the like can be mentioned.

As the reinforcing filler of the f component,
1) Sheet-like materials composed of glass fibers such as glass cloth and glass nonwoven fabric, and fibrous materials made from glass materials such as glass fibers, glass beads, glass flakes, glass powder, milled glass, glass wool, Particulate matter or sheet-like material (nonwoven fabric, woven fabric, fiber sheet and multiple layers of these), etc.
2) A powdery material, a fibrous material, or a sheet-like material, excluding a fibrous material or a particulate material obtained from the glass material of 1) above, can be mentioned.
For example, cellulose fiber sheet, bacterial cellulose fiber sheet, polyimide porous membrane, cellulose fiber, polyimide fiber, aramid fiber, polyimide fiber, polyketone fiber, silica material such as silica wool, fumed silica, porous inorganic material such as zeolite and mesoporous silica Examples include materials, clay materials such as mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite, and nontronite.

  The reinforcing filler is preferably used as a sheet-like material because the deaeration treatment is relatively simple when mixed with the component a to component d or component a to component e. More preferably, it is used as a sheet-like material having a thickness of ˜2000 μm, preferably 50 to 1000 μm.

  By including the reinforcing filler in the curable composition, the linear expansion coefficient of the obtained cured product is reduced, so that the cured product can be easily used as a substrate material.

  The component f is preferably composed of glass fibers such as glass fiber, glass cloth, and glass nonwoven fabric, and is most preferably glass cloth because of its high effect of reducing the linear expansion coefficient.

  When a glass material is used as the f component, the types of glass materials used are E glass, C glass, A glass, S glass, D glass, NE glass, T glass, AR glass, quartz, low dielectric constant glass, and high dielectric constant. Among them, E glass, S glass, T glass, and NE glass, which are easy to obtain with few ionic impurities such as alkali metals, are preferable.

  When a glass material is used as the f component, a silsesquioxane cured product obtained from a curable composition containing the a component, the b component, the c component, and the d component, or the a component, the b component, the c component, and the d of the present invention. The adhesiveness between the silsesquioxane cured product obtained from the curable composition containing the component and the e component and the f component is preferably higher from the viewpoint of the transparency and material strength of the obtained cured product. As a means for improving the adhesion, it is preferable that the surface of the f component is in a state where an appropriate treatment has been performed.

  The glass material used as the component f is preferably in a state where the glass surface treatment state is subjected to heat cleaning and free of unnecessary organic substances on the surface, and in addition to the heat cleaning treatment, a silane commercially available as a so-called silane coupling agent It is more preferable that the surface is modified with a compound for a purpose. For example, a silanol group is treated in the post-heat cleaning treatment, an epoxy group is treated in the 3-glycidoxypropyltrialkoxysilane treatment, an amino group is treated in the 3-aminopropyltrialkoxysilane treatment, and a vinyl group is treated in the vinyltrialkoxysilane treatment. -Acryloxypropyltrialkoxysilane treatment allows acryloyl groups to be present on the glass surface with chemical bonds.

  The functional group present on the glass surface is suitable for the purpose of enhancing the adhesion, as the functional group that forms a bond with the curable composition under curing conditions. Suitable surface functional groups include epoxy groups and acryloyl groups, and more preferably silanol groups and vinyl groups. Moreover, the glass material by which the silane coupling process was carried out is marketed, and you may use a commercial item.

  Even when the f component is not a glass material, when a functional group such as a surface hydroxyl group is introduced by partial oxidation treatment, partial hydrolysis treatment, electron beam irradiation, plasma irradiation, radiation irradiation, etc., the f component surface functional group and the curable composition It is preferable because it can be bonded and formed, and adhesion is enhanced.

  In order to obtain excellent transparency, the refractive index of the f-component reinforcing filler used in the present invention is preferably 1.48 to 1.60. When the material of the reinforcing filler is glass, a refractive index of 1.51 to 1.57 is particularly preferable because a transparent resin close to the Abbe number of glass can be selected. The closer the Abbe number between the transparent resin and the glass, the higher the light transmittance in a wide range because the refractive index matches in a wide wavelength range.

  The precise refractive index of a filler is measured using a solvent that has a higher refractive index than the filler and does not cause a chemical change in the filler, and a solvent that has a lower refractive index than the filler and also does not cause a chemical change in the filler. be able to. Specifically, the filler is immersed in a solvent having a refractive index higher than that of the filler, and a solvent having a refractive index lower than that of the filler is dropped, and the refractive index of the mixed solution is measured when the filler soaked visually cannot be seen, or By immersing the filler in a solvent having a refractive index lower than that of the filler, dropping a solvent having a refractive index higher than that of the filler, and measuring the refractive index of the mixed solution when the filler soaked visually cannot be seen. Refractive index can be known. For example, when an S-based glass cloth (refractive index of about 1.52) is used as a filler, the glass cloth is immersed in a styrene monomer (n = 1.543395), toluene (n = 1.4969) is dropped, and the glass cloth is dropped. The refractive index of the glass cloth can be known by measuring the refractive index of the mixed solution when no longer visible. As a result of this measurement, for example, the refractive index of this S-based glass cloth can be determined to be 1.5203 to 1.5206.

  The silsesquioxane hardened | cured material obtained from the curable composition containing the a component of this invention, b component, c component, and d component, or the a component of this invention, b component, c component, d component, and e component are included. The difference between the refractive index of the silsesquioxane cured product obtained from the curable composition and the refractive index of the reinforcing filler as the f component is preferably 0.01 or less in order to maintain excellent transparency. 0.005 or less is more preferable. When the refractive index difference is larger than 0.01, the transparency of the obtained transparent material tends to be inferior.

  f component is a curable composition containing a component, b component, c component and d component, or curing containing a component, b component, c component, d component and e component, as long as the properties of the present invention are not impaired. It can mix | blend and use for an adhesive composition. Preferably, the blending amount of the component f is 1 to 90% by mass, more preferably 10 to 80% by mass, and further preferably 20 to 70% by mass with respect to the total amount (100% by mass) of the curable composition. And particularly preferably 30 to 60% by mass.

  When a glass material is used as the f component, the blending amount of the glass material is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably, relative to the total amount of the curable composition (100% by mass). 30 to 70% by mass. If the blending amount of the component f is within this range, molding is easy and effective in reducing the linear expansion coefficient.

  In the curable composition and silsesquioxane cured product of the present invention, if necessary, the thermoplasticity or the solvent can be used as long as the properties such as transparency, solvent resistance, heat resistance, dimensional stability, and mechanical strength are not impaired. A thermosetting oligomer or polymer may be used in combination. By using these thermoplastic or thermosetting oligomers and polymers in combination, for example, when a reinforcing filler is further included, the composition ratio is adjusted so that the overall refractive index matches the refractive index of the reinforcing filler (f component). It will be easier to adjust.

  In addition, in the curable composition and silsesquioxane cured product of the present invention, if necessary, as long as the properties such as transparency, solvent resistance, heat resistance, dimensional stability, and mechanical strength are not impaired, Additives that impart functions such as antioxidants, ultraviolet absorbers, dyes and pigments can be included.

  The silsesquioxane cured product of the present invention can be produced by uniformly mixing [a component, b component, c component and d component] or [a component, b component, c component, d component and e component] with stirring and mixing. After dissolution, the curable composition is obtained through a normal deaeration operation, and the curable composition is poured into an appropriate mold, and then the bond formation reaction is allowed to proceed by heating and / or light irradiation. .

  The silsesquioxane cured product containing the f component can be produced by stirring and mixing [a component, b component, c component and d component] or [a component, b component, c component, d component and e component]. After uniform mutual dissolution, after passing through a normal degassing operation, this mixture is infiltrated and impregnated into a reinforcing filler of a sheet-like material such as glass cloth or glass nonwoven fabric, and then cured through a degassing operation if necessary. Composition. Alternatively, a fibrous or particulate reinforcing filler can be uniformly dispersed in this mixture by stirring and mixing and degassing operations to obtain a curable composition. When preparing a curable composition using a fibrous material or a particulate material, the number of steps may be reduced by adding the fibrous material or the particulate material in the stirring and mixing of the mixture.

  And after making this curable composition into the target shape according to a use, a coupling | bonding production | generation reaction can be advanced by heating and / or light irradiation, and can be hardened. When the target shape is a sheet or film, the curable composition obtained by impregnating or impregnating the sheet-like reinforcing filler is fixed on one or both sides with a glass flat plate or stainless steel flat plate, and heated. In addition, a method of curing by curing the bond formation reaction by irradiation with light is preferable. Alternatively, when the target shape is a sheet or film, the curable composition obtained by dispersing the fibrous or particulate reinforcing filler is cast on a glass flat plate, a stainless steel flat plate, etc., and heated and / or Or it is good also as the method of making it harden | cure by making light irradiation advance a bond production | generation reaction.

As an example of a method for producing a cured silsesquioxane,
Silsesquioxanes obtained from at least one compound selected from cage-shaped silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-shaped silsesquioxanes At least two carbon atoms in the same molecule excluding the oligomer (component a), the compound having at least two SiH groups in the same molecule (component b), and the silsesquioxane oligomer that is the component a A compound having a carbon double bond (component c) and, if necessary, a solvent are added and mixed, preferably mixed uniformly, and further a hydrosilylation catalyst (component d) is added and mixed, preferably uniformly. After mixing, a transparent liquid composition (curable composition) is obtained by performing a depressurization treatment under reduced pressure.
The curable composition can be produced by pouring the curable composition into a mold, raising the temperature stepwise or continuously in the range of 20 ° C. to 400 ° C., and reacting for 0.5 to 72 hours. .
The obtained curable composition can be stored for a long period of time without impairing the curability when stored in a hermetically sealed state without contact with air and in a cool and dark place. For example, after filling the obtained transparent liquid curable composition into a commercially available plastic syringe, sealing the tip of the syringe and storing it at a cold temperature of 5 ° C. to 10 ° C., curing is performed in the same procedure. When it is made, the hardened | cured material which has a physical property equivalent to the sample hardened immediately after composition preparation is obtained.

  Further, the cured silsesquioxane containing the reinforcing filler (component f) is cured by impregnating the above composition into the reinforcing filler (component f) of the sheet-like material, and then degassing as necessary. A composition. Alternatively, a fibrous or particulate reinforcing filler (component f) is dispersed in this composition by stirring and mixing, and then degassed as necessary to obtain a curable composition. And a hardened | cured material can be manufactured by heating this curable composition in steps or continuously in the range of 20 to 400 degreeC, and making it react for 0.5 to 72 hours.

As another example of a method for producing a cured silsesquioxane,
a) Silsesquioxanes obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Sun oligomers (component a),
b) a compound (component b) having at least two SiH groups in the same molecule;
c) a compound (component c) having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxane as component a;
Further, if necessary, a solvent is added and mixed, preferably mixed uniformly. Further, the hydrosilylation catalyst (d component) and the radical generator (e component) are added and mixed, preferably mixed uniformly, A transparent liquid composition (curable composition) can be obtained by performing de-treatment under reduced pressure.

  Further, the cured silsesquioxane containing the reinforcing filler (component f) is necessary by adding the reinforcing filler (component f) to the above composition or adding the composition to the reinforcing filler (component f). Accordingly, deaeration is performed to obtain a curable composition.

Then, this curable composition is subjected to a hydrosilylation reaction in the range of 20 ° C. to 120 ° C., preferably in the range of 20 ° C. to 80 ° C. for 0.5 to 24 hours, during the hydrosilylation reaction or after the hydrosilylation reaction. After finishing
(1) Radiation is generated from the radical generator by performing UV irradiation (for example, the UV irradiation amount is sufficient if the radical amount necessary for starting the radical reaction is generated from the radical generator. For example, the UV irradiation time is 0 .1 to 10 minutes.),
Or (2) A cured product can be produced by generating radicals by heat and starting radical reaction, followed by hydrosilylation reaction and radical reaction in the range of 80 to 400 ° C. for 0.5 to 48 hours. .

  In the case where a reinforcing filler (f component) is included and the reinforcing filler (f component) is a fibrous or particulate material, the reinforcing filler (f component) is mixed with stirring in the curable composition. It can be used in a distributed manner. When the reinforcing filler (component f) is a sheet-like material, the reinforcing filler (component f) of one or a plurality of stacked sheets can be used by impregnating the curable composition.

  Further, when a reinforcing filler (f component) is included and a fibrous material or particulate material is used in combination with a sheet material as the reinforcing filler (f component), the fibrous material or the particulate material is used. After the product is dispersed in the curable composition, it can be used after impregnating the curable composition into a sheet-like reinforcing filler (component f).

  In the molding of the cured silseroxane, the curable composition (curable mixture) is poured or cast into a mold that matches the target cured product shape, and then the curing reaction is allowed to proceed. A cured product can be produced.

  For example, a curable composition with a component, b component, c component and d component and a curable composition with a component, b component, c component, d component and e component can be handled as a solution. Moreover, since the viscosity is relatively low, a thin tube can be flowed, and a fine molding process can be performed.

  In addition, when the curable composition contains a solvent component, it is injected or cast into a mold, and after the solvent component is removed by general heating and / or decompression treatment, the curing reaction proceeds, or the solvent component Removal and curing reaction can proceed in parallel.

  In the case where the curable composition contains a reinforcing filler (f component), the composition containing the reinforcing filler (f component) is cast into a mold having a desired shape and then cured and molded, Examples include a method of impregnating a composition containing components other than the reinforcing filler into a glass cloth or a glass nonwoven fabric to obtain a curable composition, and then curing the composition to form a sheet.

  The material of the mold can be appropriately selected from those generally used on the condition that the material does not change in the heating process at the time of curing, and examples thereof include glass, stainless steel, aluminum, and Teflon (registered trademark). be able to. In order to facilitate release of the cured product from the mold, a generally used release agent may be used.

  For example, as an example of a method for producing a film-like molded body, the curable composition (curable mixture) is injected into a mold having a spacer for controlling the thickness between two glass plates, and is heated at 120 ° C. for 2 hours. Furthermore, it can manufacture favorably by heating at 200 degreeC for 30 minutes.

  By the silsesquioxane cured product of the present invention and the production method thereof, cured products of various shapes such as a film, a sheet, a plate shape, a columnar shape, and a cylindrical shape can be obtained. Further, by using a corresponding mold, a cured product having an arbitrary shape such as a lens shape or a prism shape can be obtained. Furthermore, it can also be set as a hardened | cured material in the state which coat | covered or sealed the material by making it harden | cure on another material. In the case of use for coating or sealing, since the viscosity of the curable composition is relatively low, it is possible to easily coat or seal even a material having a complicated shape.

  The cured silsesquioxane of the present invention is excellent in heat resistance, transparency, and molding processability. For example, it is used as a lightweight and flexible material in place of glass, for applications such as transparent coating materials and transparent substrates for electronic circuits. be able to. In particular, it is suitable for use as an electronic circuit transparent substrate for display that requires heat resistance and transparency. Further, it is suitable for use as a sealing material that requires heat resistance, transparency, and moldability, particularly as a sealing material for a high-power light-emitting element, for example, a sealing material for a high-power white LED.

  In addition, the cured silsesquioxane further containing a reinforcing filler (component f) is excellent in heat resistance, dimensional stability, mechanical strength, transparency, and molding processability. Can be used particularly suitably for applications such as a liquid crystal element display substrate, an organic EL display element substrate, a color filter substrate, a touch panel substrate, an electronic paper substrate, and a solar cell substrate. Further, it can be formed into an arbitrary shape, and can be suitably used for an optical lens, an optical waveguide, an optical element sealing material, and the like.

  In addition, when this cured silsesquioxane is used as a liquid crystal display plastic substrate, a color filter substrate, an organic EL display element plastic substrate, an electronic paper substrate, a solar cell substrate, a transparent circuit substrate application such as a touch panel, The thickness of the substrate is preferably 50 to 2000 μm, more preferably 50 to 1000 μm. When the thickness of the substrate is within this range, the flatness is excellent, and the substrate can be reduced in weight as compared with the glass substrate.

  Moreover, when this cured silsesquioxane is used as the transparent circuit board, the average linear expansion coefficient at 20 to 200 ° C. is preferably 5 ppm / K or more and 60 ppm / K or less, more preferably 40 ppm / K or less. Most preferably, it is 20 ppm / K or less. Setting it to 5 ppm / K or less is difficult to select the composition and curing conditions of the curable composition, and is smaller than the glass used as the current transparent substrate. Is not required as a particularly desirable property. On the other hand, if it is 60 ppm / K or more, the difference in thermal expansion from peripheral members such as electronic circuits formed on the circuit board becomes large, and the dimensional stability during circuit manufacturing requiring a high-temperature process becomes insufficient.

For example, when this cured silsesquioxane is used for an active matrix display element substrate, if this upper limit value is exceeded, problems such as warpage and disconnection of wiring may occur in the manufacturing process.
When the cured silsesquioxane is used for the transparent circuit board, the total light transmittance at a wavelength of 400 nm to 800 nm is required to be 85% or more, more preferably 87% or more, and most preferably 90% or more. It is. When the total light transmittance at a wavelength of 400 nm to 800 nm is lower than 85%, the display performance is not sufficient.

  Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited by the following examples.

〔measuring equipment〕
1) Measurement of cage-shaped silsesquioxanes by ²⁹ Si-NMR and ¹ H-NMR: A Varian Unity / 400 spectrum meter or a JEOL JNM / AL400 spectrum meter was used, and the solvent was CDCl ₃ , tetra Measurement was performed using methylsilane as a reference substance. ^{In 29} Si-NMR, integration was performed 1750 times at a pulse width of 5.3 μs and a sampling interval of 30 s.
A peak appearing at δ-80 ppm was attributed to a trisiloxysilyl (hereinafter referred to as T3) -derived peak, and a peak appearing near δ-70 ppm was attributed to a disiloxysilyl (hereinafter referred to as T2) -derived peak.

  2) Measurement of molecular weight (number average molecular weight (Mn), weight average molecular weight (Mw)) and molecular weight distribution (Mw / Mn) of oligomer of silsesquioxane: The sample was made into 1 wt% solution of tetrahydrofuran, manufactured by JASCO Corporation Showa Denko Co., Ltd. GPC (gel filtration chromatography) system with Showa Denko Co., Ltd. SEC column (KF-804L, 2 pieces) attached to Shimadzu high performance liquid chromatography system Using a system equipped with SEC columns (KF-805L, 2), analysis was performed at a column temperature of 40 ° C., tetrahydrofuran as a developing solvent, a flow rate of 1 ml / min, and an injection amount of 250 μl. The number average molecular weight Mn and the degree of dispersion Mw / Mn were determined using polystyrene as a standard substance. The number average molecular weight Mn and the degree of dispersion Mw / Mn were calculated using software attached to the apparatus.

3) Thermal analysis of the cured product: RDC220 and TG / DTA320 manufactured by Seiko Instruments Inc. were used.
i) Measurement of 5% weight reduction temperature (hereinafter referred to as Td5): 5% weight reduction temperature (hereinafter referred to as Td5) was measured by using about 10 mg of a sample from room temperature to 550 ° C. while passing through 200 ml / min of air. The temperature was reduced by 5% from the initial weight when the temperature was raised in min.
ii) Measurement of glass transition temperature (hereinafter referred to as Tg): The temperature was raised from room temperature to 400 ° C. at 20 ° C./min through 40 ml / min of nitrogen, maintained at the same temperature for 5 minutes, and then lowered to 30 ° C. at 40 ° C./min. Then, the temperature was raised again from 30 ° C. to 400 ° C. at 20 ° C./min, and the temperature was obtained from the differential heat curve observed at the second temperature rise.

  4) Measurement of the mechanical strength of the cured product: EZ-TEST manufactured by Shimadzu Corporation was used. A tensile test was performed on a sample molded into a dumbbell shape (IEC-540), and the maximum point stress, elastic modulus, and elongation at break were determined. The measurement conditions were a sample thickness of about 0.1 to 0.5 mm, a tensile rate of 2 mm / min, a temperature of 23 ° C., and a humidity of 50%. At least three samples were measured. The measurement result was an average value of three measurement points.

  5) Measurement of total light transmittance of cured product: Measured in accordance with JIS K7361-1 using a JASCO V-570 spectrum meter.

  6) Measurement of linear expansion coefficient: TMA-50 manufactured by Shimadzu Corporation was used. After raising the temperature from 25 ° C. to 200 ° C. at 5 ° C./min in a load mode of 5 g, the temperature was lowered to 20 ° C. at 10 ° C./min and held for 3 minutes, and again raised to 200 ° C. at 5 ° C./min, The expansion of the sample from 25 ° C. to 200 ° C. at this time was measured, and the linear expansion coefficient was calculated.

[Acetone immersion test]
As a method for evaluating the degree of curing of the cured product, an acetone immersion test was performed according to the following procedure. After the cured product was dried at 110 ° C. for 30 minutes, the weight was measured, and then the cured product was immersed in acetone (20 to 25 ° C.) for 20 to 24 hours in a stationary state. The cured product was taken out from acetone, dried at 110 ° C. for 30 minutes, and then weighed, and the weights before and after the test were compared. Moreover, the presence or absence of cracks or devitrification of the cured product before and after the test was visually observed.

(Synthesis Example 1 of cage silsesquioxane oligomer)
[Phenyl / vinyl ratio = 7/3]
The cage silsesquioxane oligomer was synthesized according to the following procedure. In a 2000 ml volume three-necked flask equipped with a reflux condenser, 45 ml of 1N aqueous sodium hydroxide solution, 1200 ml of tetrahydrofuran, 66.5 g (336 mmol) of phenyltrimethoxysilane, 21.3 g (144 mmol) of vinyltrimethoxysilane, The mixture was heated to 60 ° C. with mechanical stirring and reacted for 20 hours. After the reaction, the temperature was returned to room temperature, 45 ml of 1N hydrochloric acid was added, and 10 ml of a saturated sodium hydrogen carbonate solution was added to make it weakly alkaline. The low boiling point portion was distilled off by a rotary evaporator. Next, 200 ml of diethyl ether was added for extraction, and the organic phase was washed with distilled water and then with saturated saline and dehydrated over anhydrous magnesium sulfate for 3 hours or more. Insoluble matters such as salts were removed by filtration, concentrated by drying under reduced pressure, added to 200 ml of hexane with stirring, and purified by reprecipitation. The product was a white powder, yield 49.2 g, yield 90%.
The molecular weight of the product was Mn = 1.8 × 10 ³ and Mw / Mn = 1.1.
As a result of nuclear magnetic resonance spectrum (NMR) measurement of the product, ¹ H-NMR δ (ppm): 5.3-6.2 (m, 9H), 6.8-8.0 (m, 35H); ²⁹ Si-NMR δ (ppm): −83 −−75 (T3), 88 mol%, −72 − −66 (T2), 12 mol%.
1 g of the product contains 2.61 mmol equivalent as a vinyl group.

From the above analysis results, the synthesized cage silsesquioxane oligomer is composed of 8 to 20 silicon units per molecule from the GPC measurement results, and a part of the cage structure from the ²⁹ Si-NMR results. It can be presumed that the ring is open.
Here, the partial ring-opening cage structure will be described. From the GPC measurement result of the synthesized silsesquioxane oligomer, it can be estimated that the structure is composed of 8 to 20 silicon units. Assuming that the number of silicon units per molecule of the synthesized polysilsesquioxane is 10 and the T2 / T3 ratio is 1/9 from the measurement of silicon NMR, the number of T2 and T3 units is 1 and 9 respectively. It becomes a piece.
Consider a structure that can be formed at this ratio. If these silicon units are all T3 components, their molecular structure is none other than a polyhedron having a completely closed structure (ie, a cage structure). Next, when one side of this polyhedral structure is cut, two units of the T2 component are generated. Further, when the silicon unit forming one vertex of this polyhedral structure is removed, three units of T2 component are generated.
It can be seen that both structures are structures in which a part of the cage structure is opened. Further, it is considered impossible to form a structure other than the cage structure in a range where the number of Si units is 20 or less and the T2 ratio is 1/3 or less.

(Synthesis example 2 of cage silsesquioxane oligomer)
[Phenyl / vinyl ratio = 7/3]
Into an 8 L separable flask, 6000 ml of tetrahydrofuran and 225 ml of 1N aqueous sodium hydroxide solution were added. While stirring the solution vigorously with a stirring blade, 333.13 g (1680 mmol) of phenyltrimethoxysilane and 106.73 g of vinyltrimethoxysilane were added. A mixture of (720 mmol) was added. While maintaining this stirring, the mixture was heated and maintained at 63 ° C. using an oil bath. After 18 hours, the reaction solution was allowed to cool to room temperature, and 225 ml of 1N hydrochloric acid was added. After filtration, the filtrate was concentrated until it became cloudy. The concentrated liquid was transferred to a separatory funnel, and 500 ml of ethyl acetate and 300 ml of saturated saline were added to carry out a liquid separation operation. The organic layer was washed with saturated brine three times and then dehydrated with anhydrous magnesium sulfate for one day. This was filtered and concentrated, and the concentrated solution was added dropwise to 8000 ml of n-heptane to form a precipitate. The precipitate was collected by filtration, redissolved in a mixed solution of diethyl ether: cyclohexane = 1: 3, and dried under reduced pressure. The product was a white powder, yield 222 g, yield 78%.
The molecular weight of the product was Mn = 1.1 × 10 ³ and Mw / Mn = 1.2.
As a result of measurement of the nuclear magnetic resonance spectrum (NMR) of the product, ¹ H-NMR δ (ppm): 5.3-6.2 (m, 9H), 6.8-8.0 (m, 35H); ²⁹ Si-NMR δ (ppm): −83 −−75 (T3), 85 mol%, −72 − −66 (T2), 15 mol%.
1 g of the product contains 2.50 mmol equivalent as a vinyl group.

(Synthesis example 3 of cage silsesquioxane oligomer)
[Phenyl / vinyl ratio = 5/5]
In a 2000 ml threaded three-necked flask equipped with a reflux condenser, 1N aqueous sodium hydroxide solution 45 ml, tetrahydrofuran 1200 ml, phenyltrimethoxysilane 47.5 g (240 mmol), vinyltrimethoxysilane 35.5 g (240 mmol) were placed. The mixture was heated to 60 ° C. with mechanical stirring and reacted for 20 hours. After the reaction, the reaction solution was returned to room temperature and neutralized by adding 45 ml of 1N hydrochloric acid, and then made weakly alkaline by adding 10 ml of a saturated sodium hydrogen carbonate solution. The low boiling point portion was distilled off by a rotary evaporator. Next, 200 ml of diethyl ether was added for extraction, and the organic phase was washed with distilled water and then with saturated saline and dehydrated over anhydrous magnesium sulfate for 3 hours or more. Insoluble matters such as salts were removed by filtration, concentrated by drying under reduced pressure, added to 200 ml of hexane with stirring, and purified by reprecipitation. The product was a white powder, and the yield was 47.5 g and the yield was 95.1%.
The molecular weight of the product was Mn = 2.1 × 10 ³ and Mw / Mn = 1.13.
As a result of measurement of nuclear magnetic resonance spectrum (NMR) of the product, ¹ H-NMR δ (ppm) 5.4-6.2 (m, 15H) 6.8-8.0 (m, 25H). ²⁹ Si-NMR δ (ppm) -84 −−76 (T3), 68 mol%, −72 − −67 (T2), 32 mol%.
1 g of the product contains 4.67 mmol equivalent as a vinyl group.

(Synthesis example 4 of cage-shaped silsesquioxane oligomer)
[Phenyl / vinyl ratio = 3/7]
Reactive polysilsesquioxane was synthesized according to the following procedure. In a 2000 ml threaded three-necked flask equipped with a reflux condenser, 1N sodium hydroxide aqueous solution 45 ml, tetrahydrofuran 1200 ml, phenyltrimethoxysilane 28.5 g (144 mmol), vinyltrimethoxysilane 49.7 g (336 mmol) were placed. The mixture was heated to 60 ° C. with mechanical stirring and reacted for 20 hours. After the reaction, the reaction solution was returned to room temperature and neutralized by adding 45 ml of 1N hydrochloric acid, and then made weakly alkaline by adding 10 ml of a saturated sodium hydrogen carbonate solution. The low boiling point portion was distilled off by a rotary evaporator. Next, 200 ml of diethyl ether was added for extraction, and the organic phase was washed with distilled water and then with saturated saline and dehydrated over anhydrous magnesium sulfate for 3 hours or more. Insoluble matters such as salts were removed by filtration, concentrated by drying under reduced pressure, added to 200 ml of hexane with stirring, and purified by reprecipitation. The product was white powder, yield 40.6 g, yield 90%.
The molecular weight of the product was Mn = 3.4 × 10 ³ and Mw / Mn = 1.2.
As a result of measurement of the nuclear magnetic resonance spectrum (NMR) of the product, ¹ H-NMR δ (ppm) 5.4-6.2 (m, 21H) 6.9-7.9 (m, 15H). ²⁹ Si-NMR δ (ppm) −84 −−75 (T3), 88 mol%, −72 −−67% (T2), 12 mol%.
1 g of the product contains 7.35 mmol equivalent as a vinyl group.

(Synthesis example 5 of cage silsesquioxane oligomer)
[Methyl / vinyl ratio = 5/5]
To a 2 L separable flask, 32.69 g (240 mmol) of methyltrimethoxysilane, 35.57 g (240 mmol) of vinyltrimethoxysilane and 1200 ml of tetrahydrofuran were added, and the mixture was vigorously stirred using a stirring blade. While maintaining this stirring, 45 ml of 1N aqueous sodium hydroxide solution was added, and the mixture was heated and held at 63 ° C. for 24 hours using an oil bath. Thereafter, the reaction solution was allowed to cool to room temperature, and 45 ml of 1N hydrochloric acid was added. The solution was filtered and then concentrated until the filtrate became cloudy. The concentrated liquid was transferred to a separatory funnel, and 150 ml of diethyl ether and 30 ml of saturated saline were added to carry out a liquid separation operation. The organic layer was washed with saturated brine three times and then dehydrated with anhydrous magnesium sulfate overnight. This was filtered and then concentrated, and the concentrated solution was dropped into 2000 ml of n-hexane to remove the precipitate. The supernatant was collected and dried under reduced pressure to obtain a white solid product (yield 23.20 g, yield 66%).
The molecular weight of the product was Mn = 0.86 × 10 ³ and Mw / Mn = 1.2.
As a result of nuclear magnetic resonance spectrum (NMR) measurement of the product, ¹ H-NMR δ (ppm): 0.2 (m, 15 H), 5.9-6.0 (m, 15 H); ²⁹ Si-NMR δ (Ppm): -82--76 (vinyl group-substituted T3), -70--60 (vinyl group-substituted T2 and methyl group-substituted T3), -56--52 (methyl group-substituted T2).
1 g of the product contains 6.70 mmol equivalent as a vinyl group.

(Synthesis Example 6 of cage-shaped silsesquioxane oligomer)
[Phenyl / vinyl ratio = 3/7]
A 2 L separable flask was charged with 1200 ml of tetrahydrofuran and 45 ml of 1N aqueous sodium hydroxide solution, and while stirring the solution vigorously with a stirring blade, 28.55 g (144 mmol) of phenyltrimethoxysilane and 49.80 g of vinyltrimethoxysilane were added. A mixture of (336 mmol) was added. While maintaining this stirring, the mixture was heated to 60 ° C. using an oil bath. After 24 hours, the reaction solution was allowed to cool to room temperature and 45 ml of 1N hydrochloric acid was added. After filtration, the filtrate was concentrated until it became cloudy. The concentrated solution was transferred to a separatory funnel, and 250 ml of diethyl ether and 50 ml of saturated saline were added to carry out a liquid separation operation. The organic layer was washed with saturated brine three times and then dehydrated with anhydrous magnesium sulfate for one day. This was filtered and then concentrated, and the concentrated solution was dropped into 2000 ml of n-hexane to form a precipitate. The supernatant was collected and dried under reduced pressure. The product was a white powder, yield 33.2 g, yield 72%.
The molecular weight of the product was Mn = 0.83 × 10 ³ and Mw / Mn = 1.08.
As a result of measurement of the nuclear magnetic resonance spectrum (NMR) of the product, ¹ H-NMR δ (ppm): 5.3-6.2 (m, 9H), 6.8-8.0 (m, 35H); ²⁹ Si-NMR δ (ppm): −83 −−75 (T3), 81 mol%, −72 − −66 (T2), 19 mol%.
1 g of the product contains 7.30 mmol equivalent as a vinyl group.

[Example 1]
An example of forming a molded body is shown.
4.99 g (12.5 mmol as a vinyl group), 2.50 g (38.3 mmol as a vinyl group) of divinylbenzene, and 1,3,5,7-tetra cage-shaped silsesquioxane oligomer prepared in Synthesis Example 2 When methylcyclotetrasiloxane (4.13 g, 68.7 mmol as SiH group) was mixed and ultrasonically stirred for 10 minutes, they were uniformly mixed. 20 μl of a 1 wt% chloroplatinic acid ethanol solution was added and defoamed by vacuum stirring to obtain a curable composition which was colorless and transparent and was uniformly compatible. Two glass plates coated with a commercially available release agent in advance are sandwiched with a Teflon spacer (thickness 0.3 mm) (Teflon registered trademark). The curable composition was cured by holding for 2 hours and then at 200 ° C. for 30 minutes.
The obtained cured product was a colorless and transparent film (thickness 0.3 mm). In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. The Tg of the cured product was not observed between room temperature and 400 ° C., Td 5 was 447 ° C., tensile properties were elastic modulus 1.30 GPa, maximum point stress 33.6 MPa, elongation at break 8.3%. The total light transmittance was 92%.

[Example 2]
2.00 g of the cage silsesquioxane oligomer synthesized in Synthesis Example 1 (5.21 mmol as a vinyl group) and 1.00 g of divinylbenzene (15.4 mmol as a vinyl group) were mixed with 1,3,5,7-tetramethyl. It was mixed with 0.53 g of cyclotetrasiloxane (8.81 mmol as SiH group) to obtain a uniform solution. To this was added 20 μl of a 2% xylene solution of platinum (0) 1,2-divinyl-1,1,3,3-tetramethylsiloxane complex. A curable composition which was sucked with a vacuum pump and defoamed to be colorless and transparent and uniformly compatible. The curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump and defoamed, and initially held at 110 ° C. for 12 hours and then further maintained at 200 ° C. for 30 minutes to cure the curable composition.
The obtained cured product was a colorless and transparent sheet. Tg of hardened | cured material was not recognized between room temperature and 400 degreeC, and Td5 was 386 degreeC.

[Example 3]
2.00 g of the cage silsesquioxane oligomer synthesized in Synthesis Example 1 (5.21 mmol as a vinyl group) and 1.00 g of divinylbenzene (15.4 mmol as a vinyl group) were mixed with 1,3,5,7-tetramethyl. It was mixed with 1.05 g of cyclotetrasiloxane (17.5 mmol as SiH group) to obtain a uniform solution. To this, 20 μl of a 2% xylene solution of platinum (0) 1,2-divinyl-1,1,3,3-tetramethylsiloxane complex was added. A curable composition which was sucked with a vacuum pump and defoamed to be colorless and transparent and uniformly compatible. The curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump and defoamed, and initially held at 110 ° C. for 12 hours and then further maintained at 200 ° C. for 30 minutes to cure the curable composition.
The obtained cured product was a colorless and transparent sheet. The Tg of the cured product was not observed between room temperature and 400 ° C, and Td5 was 405 ° C.

[Example 4]
2.00 g of the cage silsesquioxane oligomer synthesized in Synthesis Example 1 (5.21 mmol as a vinyl group) and 1.00 g of divinylbenzene (15.4 mmol as a vinyl group) were mixed with 1,3,5,7-tetramethyl. It was mixed with 1.58 g of cyclotetrasiloxane (26.3 mmol as SiH group) to obtain a uniform solution. To this, 20 μl of a 2% xylene solution of platinum (0) 1,2-divinyl-1,1,3,3-tetramethylsiloxane complex was added. A curable composition which was sucked with a vacuum pump and defoamed to be colorless and transparent and uniformly compatible. The curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump and defoamed, and initially held at 110 ° C. for 12 hours and then further maintained at 200 ° C. for 30 minutes to cure the curable composition.
The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. The Tg of the cured product was not observed between room temperature and 400 ° C, Td5 was 419 ° C, tensile properties were an elastic modulus of 0.96 GPa, a maximum point stress of 27.8 MPa, and an elongation at break of 4.5%.

[Example 5]
3.13 g (7.82 mmol as a vinyl group), 1.58 g (24.3 mmol as a vinyl group) of divinylbenzene, and 1,3,5,7-tetra cage-shaped silsesquioxane oligomer prepared in Synthesis Example 2 Methylcyclotetrasiloxane (3.01 g, 50.1 mmol as SiH group) was mixed and ultrasonically stirred for 10 minutes. 20 μl of a 1 wt% chloroplatinic acid ethanol solution was added and defoamed by vacuum stirring to obtain a curable composition which was colorless and transparent and was uniformly compatible. Two glass plates previously coated with a commercially available mold release agent and a Teflon spacer sandwiched between them are used as molds. The above curable composition is injected into the mold and heated in a constant temperature bath at 120 ° C. for 2 hours, and then at 200 ° C. for 30 minutes. Holding and curing the curable composition.
The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. The Tg of the cured product was not observed between room temperature and 400 ° C., Td 5 was 449 ° C., tensile properties were elastic modulus 1.29 GPa, maximum point stress 30.8 MPa, elongation at break 7.6%. The total light transmittance was 92%.

[Example 6]
2.00 g of the cage silsesquioxane oligomer synthesized in Synthesis Example 1 (5.21 mmol as a vinyl group) and 1.00 g of divinylbenzene (15.4 mmol as a vinyl group) were mixed with 1,3,5,7-tetramethyl. It was mixed with 2.18 g of cyclotetrasiloxane (36.3 mmol as SiH group) to obtain a uniform solution. To this was added 20 μl of a 2% xylene solution of platinum (0) 1,2-divinyl-1,1,3,3-tetramethylsiloxane complex. A curable composition which was sucked with a vacuum pump and defoamed to be colorless and transparent and uniformly compatible. The curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump and defoamed, and initially held at 110 ° C. for 12 hours and then further maintained at 200 ° C. for 30 minutes to cure the curable composition.
The obtained cured product was a colorless and transparent sheet. Tg of hardened | cured material was not recognized between room temperature and 400 degreeC, and Td5 was 418 degreeC.

[Example 7]
1.00 g of the cage silsesquioxane oligomer synthesized in Synthesis Example 1 (2.60 mmol as a vinyl group) and 1.00 g of divinylbenzene (15.4 mmol as a vinyl group) were mixed with 1,3,5,7-tetramethyl. It was mixed with 1.48 g of cyclotetrasiloxane (24.6 mmol as SiH group) to obtain a uniform solution. To this was added 20 μl of a 2% xylene solution of platinum (0) 1,2-divinyl-1,1,3,3-tetramethylsiloxane complex. A curable composition which was sucked with a vacuum pump and defoamed to be colorless and transparent and uniformly compatible. The curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump and defoamed, and initially held at 110 ° C. for 12 hours and then further maintained at 200 ° C. for 30 minutes to cure the curable composition.
The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. The Tg of the cured product was not observed between room temperature and 400 ° C., Td 5 was 393 ° C., the tensile properties were elastic modulus 0.87 GPa, maximum point stress 25.7 MPa, and elongation at break 5.8%.

[Example 8]
2.00 g of the cage silsesquioxane oligomer synthesized in Synthesis Example 1 (5.21 mmol as a vinyl group) and 0.50 g of divinylbenzene (7.68 mmol as a vinyl group) were added to 1,3,5,7-tetramethyl. It was mixed with 0.89 g of cyclotetrasiloxane (14.8 mmol as SiH group) to obtain a uniform solution. To this was added 20 μl of a 2% xylene solution of platinum (0) 1,2-divinyl-1,1,3,3-tetramethylsiloxane complex. A curable composition which was sucked with a vacuum pump and defoamed to be colorless and transparent and uniformly compatible. The curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump and defoamed, and initially held at 110 ° C. for 12 hours and then further maintained at 200 ° C. for 30 minutes to cure the curable composition.
The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. The Tg of the cured product was not observed between room temperature and 400 ° C., Td 5 was 403 ° C., tensile properties were elastic modulus 1.10 GPa, maximum point stress 28.6 MPa, elongation at break 3.4%.

[Comparative Example 1]
1.00 g of divinylbenzene (15.4 mmol as a vinyl group) and 0.92 g of 1,3,5,7-tetramethylcyclotetrasiloxane (15.4 mmol as a SiH group) were mixed with each other to obtain a uniform solution. To this was added 20 μl of a 2% xylene solution of platinum (0) 1,2-divinyl-1,1,3,3-tetramethylsiloxane complex. After sucking and defoaming with a vacuum pump, the mixture was poured into a Teflon sheet mold and further sucked with a vacuum pump for defoaming, heated at 110 ° C. for 12 hours, and then heated at 200 ° C. for 30 minutes to obtain a molded body.
The molded body was fragile and the acetone immersion test could not be carried out. Td5 was 327 ° C.

[Comparative Example 2]
3.03 g of the cage silsesquioxane oligomer synthesized in Synthesis Example 2 (7.57 mmol as a vinyl group) and 2.52 g of 1,3,5,7-tetramethylcyclotetrasiloxane (41.9 mmol as a SiH group) ) And ultrasonically stirred for 10 minutes, but did not dissolve each other. A small amount of 1 wt% chloroplatinic acid ethanol solution was added thereto, and defoaming was performed by vacuum stirring. It put into the type | mold with the powder-liquid mixed state, and it hold | maintained for 30 minutes at 200 degreeC after that for 2 hours in a 120 degreeC thermostat. The obtained cured product was a mixture of non-uniform white lump and powder. In the acetone immersion test, the sample disintegrated and the recovered solid weight was 76.7%.

[Comparative Example 3]
2.99 g of the cage silsesquioxane oligomer synthesized in Synthesis Example 2 (7.47 mmol as a vinyl group) and 0.66 g of 1,3,5,7-tetramethylcyclotetrasiloxane (11.0 mmol as a SiH group) ) And ultrasonically stirred for 10 minutes, but they were not mutually dissolved. A small amount of 1 wt% chloroplatinic acid ethanol solution was added thereto, and defoaming was performed by vacuum stirring. It put into the type | mold with the powder-liquid mixed state, and it hold | maintained for 30 minutes at 200 degreeC after that for 2 hours in a 120 degreeC thermostat. The obtained cured product was a mixture of non-uniform white lump and powder. In the acetone immersion test, the sample was disintegrated and the recovered solid weight was 28.5%.

[Example 9]
2.00 g of the cage silsesquioxane oligomer synthesized in Synthesis Example 3 (9.34 mmol as a vinyl group) and 1.00 g of divinylbenzene (15.4 mmol as a vinyl group) were added to 1,3,5,7-tetramethyl. It was mixed with 1.70 g of cyclotetrasiloxane (28.3 mmol as SiH group) to obtain a uniform solution. To this was added 20 μl of a 2% xylene solution of platinum (0) 1,2-divinyl-1,1,3,3-tetramethylsiloxane complex. A curable composition which was sucked with a vacuum pump and defoamed to be colorless and transparent and uniformly compatible. The curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump and defoamed, and initially held at 110 ° C. for 12 hours and then further maintained at 200 ° C. for 30 minutes to cure the curable composition.
The obtained cured product was a colorless and transparent sheet. No change in weight was observed in the acetone immersion test. The Tg of the cured product was not observed between room temperature and 400 ° C., Td 5 was 407 ° C., the tensile properties were an elastic modulus of 1.03 GPa, the maximum point stress was 10.5 MPa, and the elongation at break was 1.4%.

[Example 10]
2.00 g of the cage silsesquioxane oligomer synthesized in Synthesis Example 4 (14.7 mmol as a vinyl group) and 1.00 g of divinylbenzene (15.4 mmol as a vinyl group) were mixed with 1,3,5,7-tetramethyl. It was mixed with 1.82 g of cyclotetrasiloxane (30.3 mmol as SiH group) to obtain a uniform solution. To this was added 20 μl of a 2% xylene solution of platinum (0) 1,2-divinyl-1,1,3,3-tetramethylsiloxane complex. A curable composition which was sucked with a vacuum pump and defoamed to be colorless and transparent and uniformly compatible. The curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump and defoamed, and initially held at 110 ° C. for 12 hours and then further maintained at 200 ° C. for 30 minutes to cure the curable composition.
The obtained cured product was a colorless and transparent sheet. No change in weight was observed in the acetone immersion test. The Tg of the cured product was not observed between room temperature and 400 ° C, Td5 was 415 ° C, the tensile properties were an elastic modulus of 1.01 GPa, the maximum point stress was 12.3 MPa, and the elongation at break was 1.1%.

[Example 11]
2.00 g of vinyl group-substituted polysilsesquioxane synthesized in Synthesis Example 1 (5.21 mmol as a vinyl group) and 1.00 g of divinylbenzene (15.4 mmol as a vinyl group) were mixed with 1,3,5,7-tetra It was mixed with 0.53 g of methylcyclotetrasiloxane (8.81 mmol as SiH group) to obtain a uniform solution. To this, 20 μl of a 2% xylene solution of platinum (0) 1,2-divinyl-1,1,3,3-tetramethylsiloxane complex and 0.017 g of Irgacure 651 [Ciba Specialty Chemicals Co., Ltd.] were added. . A curable composition which was sucked with a vacuum pump and defoamed to be colorless and transparent and uniformly compatible. This curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump, defoamed, initially held at 80 ° C. for 5 hours, then UV irradiation [metal halide lamp 120 W / cm] for 1 minute, and then held at 200 ° C. for 30 minutes. The curable composition was cured.
The obtained cured product was a colorless and transparent sheet. No change in weight was observed in the acetone immersion test. Tg of hardened | cured material was not recognized between room temperature and 400 degreeC, and Td5 was 410 degreeC.

[Example 12]
2.00 g of vinyl group-substituted polysilsesquioxane synthesized in Synthesis Example 1 (5.21 mmol as vinyl group) and 1.00 g of divinylbenzene (15.4 mmol as vinyl group) were mixed with 1,3,5,7-tetra It was mixed with 1.05 g of methylcyclotetrasiloxane (17.5 mmol as SiH group) to obtain a uniform solution. To this, 20 μl of a 2% xylene solution of platinum (0) 1,2-divinyl-1,1,3,3-tetramethylsiloxane complex and 0.017 g of Irgacure 651 [Ciba Specialty Chemicals Co., Ltd.] were added. . A curable composition which was sucked with a vacuum pump and defoamed to be colorless and transparent and uniformly compatible. This curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump, defoamed, initially held at 80 ° C. for 5 hours, then UV irradiation [metal halide lamp 120 W / cm] for 1 minute, and then held at 200 ° C. for 30 minutes. The curable composition was cured.
The obtained cured product was a colorless and transparent sheet. No change in weight was observed in the acetone immersion test. Tg of hardened | cured material was not recognized between room temperature and 400 degreeC, and Td5 was 415 degreeC.

[Example 13]
2.00 g of vinyl-substituted polysilsesquioxane synthesized in Synthesis Example 4 (14.7 mmol as vinyl group) and 1.00 g of divinylbenzene (15.4 mmol as vinyl group) were mixed with 1,3,5,7-tetra A uniform solution was prepared by mixing with 0.61 g of methylcyclotetrasiloxane (10.2 mmol as SiH group). To this, 20 μl of a 2% xylene solution of platinum (0) 1,2-divinyl-1,1,3,3-tetramethylsiloxane complex and 0.017 g of Irgacure 651 [Ciba Specialty Chemicals Co., Ltd.] were added. . A curable composition which was sucked with a vacuum pump and defoamed to be colorless and transparent and uniformly compatible. This curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump, defoamed, initially held at 80 ° C. for 5 hours, then UV irradiation [metal halide lamp 120 W / cm] for 1 minute, and then held at 200 ° C. for 30 minutes. The curable composition was cured.
The obtained cured product was a colorless and transparent sheet. Tg of hardened | cured material was not recognized between room temperature and 400 degreeC, and Td5 was 407 degreeC.

[Example 14]
2.00 g of vinyl-substituted polysilsesquioxane synthesized in Synthesis Example 4 (14.7 mmol as vinyl group) and 1.00 g of divinylbenzene (15.4 mmol as vinyl group) were mixed with 1,3,5,7-tetra It was mixed with 1.21 g of methylcyclotetrasiloxane (20.1 mmol as SiH group) to obtain a uniform solution. To this, 20 μl of a 2% xylene solution of platinum (0) 1,2-divinyl-1,1,3,3-tetramethylsiloxane complex and 0.017 g of Irgacure 651 [Ciba Specialty Chemicals Co., Ltd.] were added. . A curable composition which was sucked with a vacuum pump and defoamed to be colorless and transparent and uniformly compatible. This curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump, defoamed, initially held at 80 ° C. for 5 hours, then UV irradiation [metal halide lamp 120 W / cm] for 1 minute, and then held at 200 ° C. for 30 minutes. The curable composition was cured.
The obtained cured product was a colorless and transparent sheet. No change in weight was observed in the acetone immersion test. Tg of hardened | cured material was not recognized between room temperature and 400 degreeC, and Td5 was 409 degreeC.

[Example 15]
2.00 g of vinyl-substituted polysilsesquioxane synthesized in Synthesis Example 4 (14.7 mmol as vinyl group) and 1.00 g of divinylbenzene (15.4 mmol as vinyl group) were mixed with 1,3,5,7-tetra It was mixed with 1.81 g of methylcyclotetrasiloxane (30.1 mmol as SiH group) to obtain a uniform solution. To this, 20 μl of a 2% xylene solution of platinum (0) 1,2-divinyl-1,1,3,3-tetramethylsiloxane complex and 62 mg (0.42 mmol) of perbutyl D were added. A curable composition which was sucked with a vacuum pump and defoamed to be colorless and transparent and uniformly compatible. The curable composition was poured into a Teflon sheet mold, further sucked with a vacuum pump, defoamed, initially held at 80 ° C. for 5 hours, and then held at 200 ° C. for 15 hours to cure the curable composition.
The obtained cured product was a colorless and transparent sheet. No change in weight was observed in the acetone immersion test. The Tg of the cured product was not observed between room temperature and 400 ° C., Td 5 was 409 ° C., tensile properties were elastic modulus 0.67 GPa, maximum point stress 15.8 MPa, and elongation at break 2.1%.

[Example 16]
6.29 g (15.60 mmol as a vinyl group) of cage-shaped silsesquioxane oligomer (T2: 25 mol%) prepared by the same method as in Synthesis Example 2, 6.17 g (94.85 mmol as a vinyl group) divinylbenzene, Then, 7.37 g (122.59 mmol as SiH group) of 1,3,5,7-tetramethylcyclotetrasiloxane were mixed and ultrasonically stirred for 10 minutes to be compatible. 25 μl of 1 wt% chloroplatinic acid ethanol solution was added and defoamed by vacuum stirring to obtain a curable composition that was colorless and transparent and was compatible with each other. 9.92 g of the curable composition was collected, 0.0273 g of perbutyl D was added thereto, and the mixture was injected into a mold produced in the same manner as in Example 5. Next, the curable composition was cured by holding in a thermostatic bath at 90 ° C. for 3 hours, then heating at a temperature rising rate of 0.5 ° C./min for 3 hours, and further holding at 200 ° C. for 30 minutes. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. Td5 was 455 ° C. and the total light transmittance was 92%.

[Example 17]
5.68 g (14.17 mmol as vinyl group) of cage silsesquioxane oligomer (T2: 19 mol%) prepared by the same method as in Synthesis Example 2, 5.57 g (85.62 mmol as vinyl group) divinylbenzene, Then, 6.50 g of 1,3,5,7-tetramethylcyclotetrasiloxane (108.14 mmol as SiH group) were mixed and ultrasonically stirred for 10 minutes to be compatible. 25 μl of 1 wt% chloroplatinic acid ethanol solution was added and defoamed by vacuum stirring to obtain a curable composition that was colorless and transparent and was compatible with each other. 8.01 g of this curable composition was sampled, 0.0172 g of perbutyl D was added thereto, and the mixture was poured into a mold produced in the same manner as in Example 5. Next, the same heating as in Example 16 was performed to cure the curable composition. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. Td5 was 461 ° C., and the tensile properties were an elastic modulus of 1.01 GPa, a maximum point stress of 21.0 MPa, and an elongation at break of 1.9%. The total light transmittance was 91%.

[Example 18]
1.53 g (11.07 mmol as a vinyl group) of cage-shaped silsesquioxane oligomer (T2: 8 mol%) prepared by the same method as in Synthesis Example 6, 4.36 g (66.93 mmol as a vinyl group) divinylbenzene, Then, 4.72 g (78.54 mmol as SiH group) of 1,3,5,7-tetramethylcyclotetrasiloxane were mixed and ultrasonically stirred for 10 minutes to be compatible. 25 μl of 1 wt% chloroplatinic acid ethanol solution was added and defoamed by vacuum stirring to obtain a curable composition that was colorless and transparent and was compatible with each other. 5.30 g of this curable composition was sampled, 0.0159 g of perbutyl D was added thereto, and the mixture was poured into a mold produced in the same manner as in Example 5. Next, the same heating as in Example 16 was performed to cure the curable composition. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. Td5 was 459 ° C. and the total light transmittance was 91%.

[Example 19]
1.53 g (10.90 mmol as a vinyl group) of cage-shaped silsesquioxane oligomer (T2: 25 mol%) prepared by the same method as in Synthesis Example 6, 4.31 g (66.14 mmol as a vinyl group) divinylbenzene, Then, 4.83 g of 1,3,5,7-tetramethylcyclotetrasiloxane (80.37 mmol as SiH group) were mixed and ultrasonically stirred for 10 minutes to be compatible. 25 μl of 1 wt% chloroplatinic acid ethanol solution was added and defoamed by vacuum stirring to obtain a curable composition that was colorless and transparent and was compatible with each other. 5.35 g of this curable composition was sampled, and 0.0151 g of perbutyl D was added thereto and poured into a mold produced in the same manner as in Example 5. Next, the same heating as in Example 16 was performed to cure the curable composition. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. Td5 was 455 ° C., tensile properties were an elastic modulus of 1.53 GPa, a maximum point stress of 14.0 MPa, and an elongation at break of 1.01%. The total light transmittance was 92%.

[Example 20]
3.51 g (8.75 mmol as a vinyl group), 3.45 g (52.98 mmol as a vinyl group) of divinylbenzene, and 1,3,5,7-tetra cage-shaped silsesquioxane oligomer used in Example 17 Methylcyclotetrasiloxane (4.02 g) (66.82 mmol as SiH group) was mixed and subjected to ultrasonic stirring for 10 minutes. 25 μl of 1 wt% chloroplatinic acid ethanol solution was added and defoamed by vacuum stirring to obtain a curable composition that was colorless and transparent and was compatible with each other. 5.00 g of this curable composition was sampled, and 0.0163 g of perbutyl Z was added thereto, poured into a mold produced in the same manner as in Example 5, and then kept in a constant temperature bath at 90 ° C. for 3 hours. The curable composition was cured by heating at a temperature rising rate of 0.33 ° C./min for 3 hours and further holding at 200 ° C. for 30 minutes. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. Td5 was 452 ° C., tensile properties were an elastic modulus of 1.12 GPa, a maximum point stress of 3.3 MPa, and an elongation at break of 0.22%. The total light transmittance was 91%.

[Example 21]
3.51 g (8.75 mmol as a vinyl group), 3.45 g (52.97 mmol as a vinyl group) of divinylbenzene, and 1,3,5,7-tetra cage-shaped silsesquioxane oligomer used in Example 17 Methylcyclotetrasiloxane (4.01 g, 66.75 mmol as SiH group) was mixed and ultrasonically stirred for 10 minutes to be compatible. 25 μl of 1 wt% chloroplatinic acid ethanol solution was added and defoamed by vacuum stirring to obtain a curable composition that was colorless and transparent and was compatible with each other. 5.45 g of this curable composition was sampled, and 0.0144 g of Perocta H was added thereto, which was then poured into a mold produced in the same manner as in Example 5, and then held in a thermostatic bath at 150 ° C. for 1.5 hours. Then, the curable composition was cured by heating at a rate of temperature rise of 0.33 ° C./min for 2.5 hours and holding at 200 ° C. for 60 minutes. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. Td5 was 454 ° C., tensile properties were elastic modulus 1.29 GPa, maximum point stress 12.8 MPa, elongation at break 1.7%. The total light transmittance was 91%.

[Example 22]
2.05 g (13.37 mmol as a vinyl group), 2.25 g (41.64 mmol as a vinyl group), and 1,3,5,7- of the cage silsesquioxane oligomer prepared in Synthesis Example 5 Tetramethylcyclotetrasiloxane 4.72 g (78.44 mmol as SiH group) was mixed and ultrasonically stirred for 10 minutes to be compatible. 31 μl of a 1 wt% chloroplatinic acid ethanol solution was added and defoamed by vacuum stirring to obtain a curable composition which was colorless and transparent and was compatible with each other. This was heated in a drier set at 60 ° C. for 30 minutes, cooled at room temperature, and then depressurized to perform a defoaming treatment. Next, 0.5 mm thick Teflon was sandwiched between two glass plates each having a side of 15 cm, fixed with a fixture, and the mixture was poured into the gap. After heating at 80 ° C. for 3 hours, the fixture was removed, and the curable composition was cured by heating at 120 ° C. for 1 hour. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. Td5 was 451 ° C. and the total light transmittance was 93%.

[Example 23]
1.05 g (7.03 mmol as a vinyl group), 1.39 g (20.14 mmol as a vinyl group) of divinylbenzene, and 1,3,5,7-tetra cage-shaped silsesquioxane oligomer prepared in Synthesis Example 5 Methylcyclotetrasiloxane (2.44 g, 40.60 mmol as SiH group) was mixed and subjected to ultrasonic stirring for 10 minutes to be compatible. 17 μl of a 1 wt% chloroplatinic acid ethanol solution was added and defoamed by vacuum stirring to obtain a curable composition which was colorless and transparent and uniformly compatible. This was heated in a drier set at 60 ° C. for 30 minutes, cooled at room temperature, and then depressurized to perform a defoaming treatment. Next, 0.5 mm thick Teflon was sandwiched between two glass plates each having a side of 15 cm, fixed with a fixture, and the mixture was poured into the gap. After heating at 80 ° C. for 3 hours, the fixture was removed, and the curable composition was cured by heating at 120 ° C. for 1 hour. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. Td5 was 464 ° C. and the total light transmittance was 92%.

[Example 24]
4.00 g (9.96 mmol as a vinyl group) of cage-shaped silsesquioxane oligomer (T2: 19 mol%) prepared by the same method as in Synthesis Example 2, 4.00 g (61.5 mmol as a vinyl group) divinylbenzene, Then, 5.80 g (96.5 mmol as SiH group) of 1,3,5,7-tetramethylcyclotetrasiloxane were mixed and ultrasonically stirred for 5 minutes to be compatible. 30 μl of 1 wt% chloroplatinic acid ethanol solution was added and defoamed by vacuum stirring to obtain a curable composition which was colorless and transparent and was compatible with each other. This was heated in a dryer set at 60 ° C. for 30 minutes, cooled to room temperature, and then depressurized to perform defoaming. Next, an E glass-based glass cloth (refractive index: 1.558, manufactured by Nittobo Co., Ltd.) having a thickness of 95 μm and a density of 60 × 58 pieces / inch was impregnated into the curable composition and defoamed. This curable composition was sandwiched between release-treated glass plates, heated in a dryer at 120 ° C. for 90 minutes, and then at 200 ° C. for 30 minutes to obtain a transparent film having a thickness of 0.11 mm. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. The cured product had a Td5 of 459.6 ° C., tensile properties of an elastic modulus of 6.80 GPa, a maximum point stress of 214.5 MPa, and an elongation at break of 4.8%. The linear expansion coefficient of the cured product was 12.2 ppm / K, and the total light transmittance was 87.1%.
The refractive index of only the resin portion of the cured composition was 1.527.

[Example 25]
4.02 g (10.01 mmol as a vinyl group) of cage silsesquioxane oligomer (T2: 19 mol%) prepared by the same method as in Synthesis Example 2, 3.79 g (58.2 mmol as a vinyl group) divinylbenzene, Then, 6.60 g of 1,3,5,7-tetramethylcyclotetrasiloxane (109.8 mmol as SiH group) were mixed and ultrasonically stirred for 5 minutes to be compatible. 11.3 μl of 1 wt% chloroplatinic acid ethanol solution was added and subjected to defoaming treatment by vacuum stirring to obtain a curable composition which was colorless and transparent and was uniformly compatible. This was heated in a dryer set at 60 ° C. for 30 minutes, cooled to room temperature, and then depressurized to perform defoaming. Next, the above curable composition was impregnated with S glass glass cloth (refractive index 1.52, vinylsilane coupling agent-treated product, manufactured by Unitika) having a thickness of 0.050 mm and a density of 60 × 58 pieces / inch, and defoamed. . This curable composition was sandwiched between release-treated glass plates, heated at 120 ° C. for 90 minutes in a dryer, and then heated at 200 ° C. for 30 minutes to obtain a transparent film having a thickness of 0.091 mm. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. The cured product had a Td5 of 425.5 ° C., tensile properties of an elastic modulus of 5.49 GPa, a maximum point stress of 210.1 MPa, and an elongation at break of 5.0%. The linear expansion coefficient of the cured product was 10.9 ppm / K, and the total light transmittance was 90.3%.
The refractive index of only the resin portion of the cured composition was 1.519.

[Example 26]
3.00 g (7.47 mmol as vinyl group), 3.00 g (46.1 mmol as vinyl group) of divinylbenzene, and 1,3,5,7-tetra cage-shaped silsesquioxane oligomer prepared in Synthesis Example 2 Methylcyclotetrasiloxane (4.35 g, 72.4 mmol as SiH group) was mixed and ultrasonically stirred for 10 minutes. One drop of a 1 wt% chloroplatinic acid ethanol solution was added and defoamed by vacuum stirring to obtain a curable composition that was colorless and transparent and was compatible with each other. Two glass plates pre-coated with a commercially available mold release agent and a Teflon spacer (registered trademark: Teflon) sandwiched between them are used as a mold, and the curable composition is injected into the mold for 1.5 hours in a constant temperature bath at 120 ° C. Thereafter, the curable composition was further cured at 200 ° C. for 30 minutes.
The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. The Td5 was 467.9 ° C., the tensile properties were an elastic modulus of 0.95 GPa, the maximum point stress was 30.5 MPa, and the elongation at break was 8.99%. The linear expansion coefficient of the cured product was 200 ppm / K, and the total light transmittance was 91.8%.

[Comparative Example 4]
2.00 g of divinylbenzene (30.7 mmol as vinyl group) and 2.46 g of 1,3,5,7-tetramethylcyclotetrasiloxane (40.9 mmol as SiH group) were mixed with each other to obtain a uniform solution. 30 μl of 1 wt% chloroplatinic acid ethanol solution was added to this, defoamed by vacuum stirring, sucked with a vacuum pump and defoamed, and then an E glass-based glass cloth having a density of 60 × 58 / inch (thickness of 100 μm) The refractive index of 1.558, manufactured by Nittobo Co., Ltd.) was impregnated into the curable composition and defoamed. This curable composition was sandwiched between release-treated glass plates, heated in a dryer at 120 ° C. for 90 minutes, and then at 200 ° C. for 30 minutes to obtain a transparent film having a thickness of 0.11 mm. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. The cured product had a Td5 of 400.2 ° C., tensile properties of an elastic modulus of 4.38 GPa, a maximum point stress of 217.5 MPa, and an elongation at break of 4.84.87%. The linear expansion coefficient of the cured product was 11.8 ppm / K, and the total light transmittance was 84.3%.

[Comparative Example 5]
3.00 g (7.50 mmol as a vinyl group) of the cage silsesquioxane oligomer synthesized in Synthesis Example 2 and 0.62 g (10.3 mmol as a SiH group) of 1,3,5,7-tetramethylcyclotetrasiloxane ) And ultrasonically stirred for 10 minutes, but did not dissolve each other. A small amount of a 1 wt% chloroplatinic acid ethanol solution was added thereto, and defoaming was performed by vacuum stirring, but they still did not dissolve each other. Since the impregnation was impossible, the curable composition was spread on an E glass-based glass cloth (thickness: 100 μm, refractive index: 1.558, manufactured by Nittobo Co., Ltd.) with a density of 60 × 58 / inch, and after defoaming treatment Then, it was sandwiched between the release-treated glass plates, heated at 120 ° C. for 90 minutes in a dryer, and then heated at 200 ° C. for 30 minutes. The appearance of the obtained film was cloudy, and in the acetone immersion test, the cured product was disintegrated immediately after immersion and separated from the glass cloth.

[Example 27]
2.00 g (5.18 mmol as a vinyl group) of cage silsesquioxane oligomer (T2: 19 mol%) prepared by the same method as in Synthesis Example 2, 2.70 g (41.50 mmol as a vinyl group) divinylbenzene, Then, 3.76 g of 1,3,5,7-tetramethylcyclotetrasiloxane (62.54 mmol as SiH group) were mixed and ultrasonically stirred for 10 minutes to be compatible. Two drops of 1 wt% chloroplatinic acid ethanol solution were added and defoamed by vacuum stirring to obtain a curable composition which was colorless and transparent and was compatible with each other. Two glass plates previously coated with a commercially available release agent are sandwiched with a Teflon spacer, and the above curable composition is poured into the mold and held in a constant temperature bath at 120 ° C. for 90 minutes. The curable composition was cured by holding for a minute. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, there was almost no change in weight, and no change in appearance was observed, confirming that the curing reaction by crosslinking was sufficiently advanced. Td5 was 462 ° C., tensile properties were elastic modulus 0.96 GPa, maximum point stress 31.7 MPa, elongation at break 11.1%. The total light transmittance was 92%.

[Example 28]
3.00 g of cage silsesquioxane oligomer (T2: 19 mol%) prepared by the same method as in Synthesis Example 2 (7.77 mmol as vinyl group), 8.00 g of divinylbenzene (122.9 mmol as vinyl group), Further, 10.61 g (176.5 mmol as SiH group) of 1,3,5,7-tetramethylcyclotetrasiloxane were mixed and ultrasonically stirred for 10 minutes to be compatible. Two drops of 1 wt% chloroplatinic acid ethanol solution were added and defoamed by vacuum stirring to obtain a curable composition which was colorless and transparent and was compatible with each other. This curable composition was poured into a mold produced in the same manner as in Example 1. Next, the curable composition was cured by holding in a constant temperature bath at 120 ° C. for 90 minutes and then holding at 200 ° C. for 30 minutes. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, there was almost no change in weight, and no change in appearance was observed, confirming that the curing reaction by crosslinking was sufficiently advanced. Td5 was 462 ° C., tensile properties were elastic modulus 1.03 GPa, maximum point stress 26.2 MPa, elongation at break 21.3%. The total light transmittance was 92%.

[Example 29]
0.60 g (1.55 mmol as a vinyl group) of cage-shaped silsesquioxane oligomer (T2: 19 mol%) prepared by the same method as in Synthesis Example 2, and 10.54 g (161.9 mmol as a vinyl group) divinylbenzene, Then, 13.20 g (219.6 mmol as SiH group) of 1,3,5,7-tetramethylcyclotetrasiloxane were mixed and ultrasonically stirred for 10 minutes to be compatible. Two drops of 1 wt% chloroplatinic acid ethanol solution were added and defoamed by vacuum stirring to obtain a curable composition which was colorless and transparent and was compatible with each other. This curable composition was poured into a mold produced in the same manner as in Example 1. Next, the curable composition was cured by holding in a constant temperature bath at 120 ° C. for 90 minutes and then holding at 200 ° C. for 30 minutes. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, there was almost no change in weight, and no change in appearance was observed, confirming that the curing reaction by crosslinking was sufficiently advanced. Td5 was 461 ° C., tensile properties were elastic modulus 1.14 GPa, maximum point stress 25.7 MPa, elongation at break 11.2%. The total light transmittance was 92%.

[Example 30]
1.00 g (7.24 mmol as vinyl group) of cage silsesquioxane oligomer (T2: 8 mol%) prepared by the same method as in Synthesis Example 6, 3.90 g (59.94 mmol as vinyl group) divinylbenzene, Then, 5.45 g (91.47 mmol as SiH group) of 1,3,5,7-tetramethylcyclotetrasiloxane were mixed and ultrasonically stirred for 10 minutes to be compatible. Two drops of 1 wt% chloroplatinic acid ethanol solution were added and defoamed by vacuum stirring to obtain a curable composition which was colorless and transparent and was compatible with each other. This curable composition was poured into a mold produced in the same manner as in Example 1. Next, the curable composition was cured by holding in a constant temperature bath at 120 ° C. for 90 minutes and then holding at 200 ° C. for 30 minutes. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, there was almost no change in weight, and no change in appearance was observed, confirming that the curing reaction by crosslinking was sufficiently advanced. Td5 was 466 ° C., tensile properties were elastic modulus 1.03 GPa, maximum point stress 25.7 MPa, elongation at break 10.2%. The total light transmittance was 92%.

[Example 31]
0.50 g (3.62 mmol as a vinyl group) of cage silsesquioxane oligomer (T2: 8 mol%) prepared by the same method as in Synthesis Example 6, 3.82 g (58.61 mmol as a vinyl group) divinylbenzene, Then, 5.06 g of 1,3,5,7-tetramethylcyclotetrasiloxane (84.11 mmol as SiH group) was mixed and ultrasonically stirred for 10 minutes to be compatible. Two drops of 1 wt% chloroplatinic acid ethanol solution were added and defoamed by vacuum stirring to obtain a curable composition which was colorless and transparent and was compatible with each other. This curable composition was poured into a mold produced in the same manner as in Example 1. Next, the curable composition was cured by holding in a constant temperature bath at 120 ° C. for 90 minutes and then holding at 200 ° C. for 30 minutes. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, there was almost no change in weight, and no change in appearance was observed, confirming that the curing reaction by crosslinking was sufficiently advanced. Td5 was 457 ° C., tensile properties were elastic modulus 1.26 GPa, maximum point stress 24.0 MPa, elongation at break 12.5%. The total light transmittance was 92%.

[Example 32]
0.70 g (4.74 mmol as a vinyl group), 2.30 g (42.59 mmol as a vinyl group) of trivinylcyclohexane, and 1,3,5,7-- of the cage silsesquioxane oligomer prepared in Synthesis Example 5 Tetramethylcyclotetrasiloxane 5.77 g (95.91 mmol as SiH group) was mixed and ultrasonically stirred for 10 minutes. 15 μl of 1 wt% chloroplatinic acid ethanol solution was added and defoamed by vacuum stirring to obtain a curable composition which was colorless and transparent and was compatible with each other. This was heated in a dryer set at 50 ° C. for 30 minutes, cooled to room temperature, and then depressurized to perform a defoaming treatment. Next, 0.5 mm thick Teflon was sandwiched between two glass plates each having a side of 15 cm, fixed with a fixture, and the mixture was poured into the gap. After curing at 80 ° C. for 1.5 hours, the fixture was removed and cured at 150 ° C. for 2 hours to cure the curable composition. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. The tensile properties were an elastic modulus of 399 MPa, a maximum point stress of 12.5 MPa, and an elongation at break of 25.7%. Td5 was 471 ° C. and the total light transmittance was 93%.

[Example 33]
1.10 g of the cage silsesquioxane oligomer prepared in Synthesis Example 5 (7.42 mmol as a vinyl group), 3.60 g of trivinylcyclohexane (66.60 mmol as a vinyl group), and 1,3,5,7- 6.16 g of tetramethylcyclotetrasiloxane (102.37 mmol as SiH group) was mixed and subjected to ultrasonic stirring for 10 minutes to be compatible. 3.7 μl of 1 wt% chloroplatinic acid ethanol solution was added and defoamed by vacuum stirring to obtain a curable composition which was colorless and transparent and was compatible with each other. This was heated in a dryer set at 50 ° C. for 30 minutes, cooled to room temperature, and then depressurized to perform a defoaming treatment. Next, 0.5 mm thick Teflon was sandwiched between two glass plates each having a side of 15 cm, fixed with a fixture, and the mixture was poured into the gap. After curing at 80 ° C. for 1.5 hours, the fixture was removed and cured at 150 ° C. for 2 hours to cure the curable composition. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, neither weight change nor appearance change was observed, and it was confirmed that the curing reaction due to crosslinking was sufficiently advanced. The tensile properties were an elastic modulus of 624 MPa, a maximum point stress of 16.9 MPa, and an elongation at break of 22.3%. Td5 was 454 ° C. and the total light transmittance was 93%.

[Example 34]
3.00 g (7.78 mmol as a vinyl group) of cage silsesquioxane oligomer (T2: 19 mol%) prepared by the same method as in Synthesis Example 2, 1.50 g (23.07 mmol as a vinyl group) divinylbenzene, Then, 2.50 g (41.57 mmol as SiH group) of 1,3,5,7-tetramethylcyclotetrasiloxane were mixed and ultrasonically stirred for 10 minutes to be compatible. Two drops of 1 wt% chloroplatinic acid ethanol solution were added and defoamed by vacuum stirring to obtain a curable composition which was colorless and transparent and was compatible with each other. This curable composition was poured into a mold produced in the same manner as in Example 1. Next, the curable composition was cured by holding in a constant temperature bath at 120 ° C. for 90 minutes and then holding at 200 ° C. for 30 minutes. The obtained cured product was a colorless and transparent sheet. In the acetone immersion test, there was almost no change in weight, and no change in appearance was observed, confirming that the curing reaction by crosslinking was sufficiently advanced. Td5 was 467 ° C., tensile properties were elastic modulus 1.08 GPa, maximum point stress 24.0 MPa, elongation at break 3.1%. The total light transmittance was 93%.

The ²⁹ Si-NMR measurement spectrum of the cage silsesquioxane oligomer of Synthesis Example 2. ¹ H-NMR measurement spectrum of the cage silsesquioxane oligomer of Synthesis Example 2

Claims (39)

a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b),
c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the silsesquioxane oligomer as component a (component c), and d) a hydrosilylation catalyst (component d),
The curable composition characterized by including these. a) Silsesquioxanes obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Sun oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b),
c) a compound (component c) having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxanes as component a;
d) hydrosilylation catalyst (d component), and e) radical generator (e component),
The curable composition characterized by including these. a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b),
c) a compound (component c) having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxanes as component a;
d) hydrosilylation catalyst (d component), and f) reinforcing filler (f component),
The curable composition characterized by including these. a) Silsesquioxanes obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Sun oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b),
c) a compound (component c) having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxanes as component a;
d) hydrosilylation catalyst (d component),
e) radical generator (e component), and f) reinforcing filler (f component),
The curable composition characterized by including these. The curable composition according to any one of claims 1 to 4, wherein the composition comprising the a component, the b component, and the c component is uniformly compatible. The curable composition according to claim 2 or 4, wherein the component e is a radical generator that generates radicals by light irradiation. The curable composition according to claim 2 or 4, wherein the e-component radical generator has a 10-hour half-life temperature of 100 ° C or higher and 400 ° C or lower. The cage silsesquioxane having a substituent containing a carbon-carbon double bond of component a is represented by the general formula [RSiO _1.5 ] n (wherein R is a hydrogen atom, having 1 to 6 carbon atoms) An alkoxy group or an aryloxy group, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, A group selected from the group consisting of a halogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing group having 1 to 10 silicon atoms, and a plurality of Rs on the same silsesquioxane molecule are the same Or, on average, at least two substituents containing a carbon-carbon double bond, and n is an integer of 6 to 20.) Item 5. The hardness according to any one of Items 1 to 4 Gender composition. The curable composition according to claim 3 or 4, wherein the refractive index of the f component is 1.48 to 1.60. The curable composition according to any one of claims 1 to 4, comprising 1 to 60 parts by mass of the a component in 100 parts by mass of the total weight of the a component, the b component, and the c component. The composition ratio of the a component, the b component, and the c component is the molar ratio between the SiH group of the b component and the sum of the carbon-carbon double bonds of the a component and the c component (SiH group / carbon-carbon double). Bonding) is 0.4-3, The curable composition of any one of Claims 1-4. The functional group molar ratio of the carbon-carbon double bond of component c and component a (carbon component-carbon double bond of component c / carbon-carbon double bond of component a) is 2 to 200. The curable composition of any one of these. The curable composition according to any one of claims 1 to 4, wherein the component a is a mixture having a number average molecular weight (Mn) of 500 to 4000. The curable composition according to any one of claims 1 to 4, wherein the component a is a mixture having a value of (weight average molecular weight Mw) / (number average molecular weight Mn) of 1 to 1.5. a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b), and c) at least two carbon-carbon double bonds in the same molecule, excluding the oligomer of silsesquioxane as the component a. A composition comprising a compound (component c) having
d) in the presence of a hydrosilylation catalyst (component d),
A silsesquioxane cured product obtained by forming a bond. a) Silsesquioxane obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes San oligomers,
b) a compound having at least two SiH groups in the same molecule, and c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxane as a component, A composition comprising
d) in the presence of a hydrosilylation catalyst, and e) a radical generator,
A silsesquioxane cured product obtained by forming a bond. a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b), and c) at least two carbon-carbon double bonds in the same molecule, excluding the oligomer of silsesquioxane as the component a. A composition comprising a compound (component c) having
d) in the presence of a hydrosilylation catalyst (d component), and f) a reinforcing filler (f component),
A silsesquioxane cured product obtained by forming a chemical bond. a) Silsesquioxanes obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Sun oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b), and c) at least two carbon-carbon double bonds in the same molecule, excluding the oligomer of silsesquioxane as the component a. A composition comprising a compound (component c) having
d) hydrosilylation catalyst (d component),
e) in the presence of a radical generator (e component), and f) a reinforcing filler (f component),
A silsesquioxane cured product obtained by forming a chemical bond. The silsesquioxane cured product according to any one of claims 15 to 18, wherein the composition comprising the a component, the b component, and the c component is a uniformly compatible composition. The silsesquioxane cured product according to claim 16 or 18, wherein the e component is a radical generator that generates radicals by light irradiation. 19. The cured silsesquioxane according to claim 16, wherein the e-component radical generator has a 10-hour half-life temperature of 100 ° C. or more and 400 ° C. or less. The cage silsesquioxane having a substituent containing a carbon-carbon double bond of component a is represented by the general formula [RSiO _1.5 ] n (wherein R is a hydrogen atom, having 1 to 6 carbon atoms) An alkoxy group or an aryloxy group, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, A group selected from the group consisting of a halogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing group having 1 to 10 silicon atoms, and a plurality of Rs on the same silsesquioxane molecule are the same Or an average of at least two substituents containing a carbon-carbon double bond, and n is an integer of 6 to 20.) Item 19. Any one of Items 15 to 18 Silsesquioxane cured product. The silsesquioxane cured product according to any one of claims 15 to 18, wherein the component a is a mixture having a number average molecular weight (Mn) of 500 to 4000. The silsesquioxane cured product according to any one of claims 15 to 18, wherein the component a is a mixture having a value of (weight average molecular weight Mw) / (number average molecular weight Mn) of 1 to 1.5. The silsesquioxane cured product according to claim 17 or 18, wherein the refractive index of the reinforcing filler of the f component is 1.48 to 1.60. The cured silsesquioxane according to claim 17 or 18, wherein the f-component reinforcing filler is a sheet-like material having a thickness of 10 to 2000 µm. The silsesquioxane cured product according to claim 17 or 18, wherein an average linear expansion coefficient at 20 ° C to 200 ° C is 5 ppm / K or more and 60 ppm / K or less. The silsesquioxane cured product according to any one of claims 15 to 18, wherein the total light transmittance at a wavelength of 400 nm to 800 nm is 85% or more and 100% or less. The silsesquioxane cured product according to any one of claims 15 to 18, which has a 5% weight loss temperature of 400 ° C to 800 ° C. The silsesquik according to any one of claims 15 to 18, obtained by bonding and forming a composition containing 1 to 60 parts by mass of the a component in 100 parts by mass of the total weight of the a component, the b component and the c component. Oxane cured product. The composition ratio of the a component, the b component, and the c component is the molar ratio between the SiH group of the b component and the sum of the carbon-carbon double bonds of the a component and the c component (SiH group / carbon-carbon double). Bond) is 0.4-3, The silsesquioxane hardened | cured material of any one of Claims 15-18. The functional group molar ratio of the carbon-carbon double bond of component c and component a (carbon component-carbon double bond of component c / carbon-carbon double bond of component a) is 2 to 200. The silsesquioxane hardened | cured material of any one of these. The cured silsesquioxane according to any one of claims 15 to 18, which has a maximum point elongation of 10% to 40% in tensile property evaluation. The cured silsesquioxane according to any one of claims 15 to 18, which is used for an optical film, an optical sheet, a display element circuit substrate, or a transparent substrate. It is used for the sealing agent for optical elements, the sealing agent for light emitting elements, especially the sealing agent for white LED, or a semiconductor sealing agent, The silsesquiski of any one of Claims 15-18 characterized by the above-mentioned. Oxane cured product. a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers (component a),
b) a compound having at least two SiH groups in the same molecule (component b), and c) at least two carbon-carbon double bonds in the same molecule, excluding the oligomer of silsesquioxane as the component a. A composition comprising a compound (component c) having
d) in the presence of a hydrosilylation catalyst (component d),
A process for producing a cured silsesquioxane, characterized in that a cured product is obtained by raising the temperature stepwise or continuously in the range of 20 ° C to 400 ° C. a) Silsesquioxane obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes San oligomers,
b) a compound having at least two SiH groups in the same molecule, and c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxane as a component, A composition comprising
d) in the presence of a hydrosilylation catalyst, and e) a radical generator,
The manufacturing method of the silsesquioxane hardened | cured material characterized by obtaining hardened | cured material by the following reaction A or reaction B.
(Reaction A)
1) Perform hydrosilylation reaction in the range of 20 ° C to 80 ° C,
2) A radical reaction is performed during the hydrosilylation reaction of 1) above.
3) Thereafter, a cured product is obtained by performing a hydrosilylation reaction and a radical reaction in the range of 80 ° C to 400 ° C.
(Reaction B)
1) Perform hydrosilylation reaction in the range of 20 ° C to 80 ° C,
2) Thereafter, a cured product is obtained by performing a hydrosilylation reaction and a radical reaction in the range of 80 ° C to 400 ° C. a) silsesquioxane obtained from at least one structure selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes Oxane oligomers,
b) a compound having at least two SiH groups in the same molecule, and c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxane as a component, A composition comprising
in the presence of d) hydrosilylation catalyst (d component), and f) reinforcing filler (f component),
A process for producing a cured silsesquioxane, characterized in that a cured product is obtained by raising the temperature stepwise or continuously in the range of 20 ° C to 400 ° C. a) Silsesquioxane obtained from at least one compound selected from cage-type silsesquioxanes having a substituent containing a carbon-carbon double bond and partial cleavage structures of these cage-type silsesquioxanes San oligomers,
b) a compound having at least two SiH groups in the same molecule, and c) a compound having at least two carbon-carbon double bonds in the same molecule excluding the oligomer of silsesquioxane as a component, A composition comprising
d) hydrosilylation catalyst (d component),
e) in the presence of a radical generator (e component), and f) a reinforcing filler (f component),
The present invention relates to a process for producing a cured product containing silsesquioxane complex, characterized in that a cured product is obtained by the following reaction A or reaction B.
(Reaction A)
1) Perform hydrosilylation reaction in the range of 20 ° C to 80 ° C,
2) A radical reaction is performed during the hydrosilylation reaction of 1) above.
3) Thereafter, a cured product is obtained by performing a hydrosilylation reaction and a radical reaction in the range of 80 ° C to 400 ° C.
(Reaction B)
1) Perform hydrosilylation reaction in the range of 20 ° C to 80 ° C,
2) Thereafter, a cured product is obtained by performing a hydrosilylation reaction and a radical reaction in the range of 80 ° C to 400 ° C.