JP2009079163A - Curable composition, cured silsesquioxane, and method for producing cured silsesquioxane - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cured silsesquioxane having heat-resistance and transparency in combination. <P>SOLUTION: The cured silsesquioxane is produced by combining a composition containing (a) an oligomer mixture of silsesquioxanes containing ≥50 mol% cage-type silsesquioxane structure expressed by [RSiO<SB>1.5</SB>]<SB>a</SB>[RSiO<SB>2</SB>H]<SB>b</SB>and/or its partially cleaved structure, (b) a compound containing 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 and excluding oligomers of silsesquioxanes cited as the component (a), in the presence of (d) a hydrosilylation catalyst. <P>COPYRIGHT: (C)2009,JPO&INPIT

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 with excellent heat resistance and transparency obtained by reacting an oligomer with a compound having a SiH group and a compound having a substituent containing a carbon-carbon double bond, and curing capable of obtaining these cured products The present invention relates to an adhesive composition 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 polyorganosyl having a side chain organic group as a substituent containing at least 1 to 2 polymerizable unsaturated double bonds per molecule. A clear coat layer comprising a copolymer of sesquioxane, a polydialkylsiloxane having a substituent containing at least one polymerizable unsaturated bond per molecule, and a vinyl monomer or a composition using the same is applied to the coating surface. Disclosed are coatings having improved contamination resistance that are characterized by being provided.

  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. 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. Production of silsesquioxane cured product having both heat resistance and transparency using oligomer as raw material, curable composition from which these cured products are obtained, and cured silsesquioxane cured product excellent in workability and production efficiency It aims to provide a method.

The first of the present invention is
a) an oligomer mixture of silsesquioxane (component a) containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partially cleaved structure thereof;
[RSiO _1.5 ] _a [RSiO ₂ H] _b (1)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , A nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 4 to 12, b is an integer of 1 to 3, and a + b is an integer of 7 to 14.)
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 silsesquioxane as component a, and d) a hydrosilylation catalyst (component d),
It is a curable composition characterized by including these.

The second of the present invention is
a) an oligomer mixture of silsesquioxane (component a) containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partially cleaved structure thereof;
[RSiO _1.5 ] _a [RSiO ₂ H] _b (1)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , A nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 4 to 12, b is an integer of 1 to 3, and a + b is an integer of 7 to 14.)
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),
It is a curable composition characterized by including these.

The third aspect of the present invention is
a) an oligomer mixture of silsesquioxane (component a) containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partially cleaved structure thereof;
[RSiO _1.5 ] _a [RSiO ₂ H] _b (1)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , A nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 4 to 12, b is an integer of 1 to 3, and a + b is an integer of 7 to 14.)
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 which is a component. A compound having a compound (component c),
d) in the presence of a hydrosilylation catalyst (component d),
A silsesquioxane cured product obtained by forming a bond.

The fourth aspect of the present invention is
a) an oligomer mixture of silsesquioxane (component a) containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partially cleaved structure thereof;
[RSiO _1.5 ] _a [RSiO ₂ H] _b (1)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , A nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 4 to 12, b is an integer of 1 to 3, and a + b is an integer of 7 to 14.)
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 which is a component. A compound having a compound (component c),
d) in the presence of a hydrosilylation catalyst (component d), and e) a radical generator (component e),
A silsesquioxane cured product obtained by forming a bond.

5th of this invention is the manufacturing method of the silsesquioxane hardened | cured material from the 1st curable composition of this invention, and / or the manufacturing method of the 3rd silsesquioxane hardened | cured material of this invention,
a) an oligomer mixture of silsesquioxane (component a) containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partially cleaved structure thereof;
[RSiO _1.5 ] _a [RSiO ₂ H] _b (1)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , A nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 4 to 12, b is an integer of 1 to 3, and a + b is an integer of 7 to 14.)
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 which is a component. A compound having a compound (component c),
d) in the presence of a hydrosilylation catalyst (component d),
It is a process for producing a cured silsesquioxane, wherein a cured product is obtained by raising the temperature stepwise or continuously in the range of 20 ° C to 400 ° C.

6th of this invention is the manufacturing method of the silsesquioxane hardened | cured material from the 2nd curable composition of this invention, and / or the manufacturing method of the 4th silsesquioxane hardened | cured material of this invention,
a) an oligomer mixture of silsesquioxane (component a) containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partially cleaved structure thereof;
[RSiO _1.5 ] _a [RSiO ₂ H] _b (1)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , A nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 4 to 12, b is an integer of 1 to 3, and a + b is an integer of 7 to 14.)
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 which is a component. A compound having a compound (component c),
d) in the presence of a hydrosilylation catalyst (component d), and e) a radical generator (component e),
It is a 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) Performing a radical reaction 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 and fifth aspects of the present invention, it is preferable not to include a radical generator (e component) as a reaction initiator.

  As the seventh aspect of the present invention, the third and fourth silsesquioxane cured products of the present invention are an optical film, an optical sheet, a display element circuit board, a transparent substrate, an optical element sealant, and a light emitting element seal. Used as a stopper.

  The first to fourth preferred embodiments of the present invention will be described below. A plurality of preferred embodiments can be combined.

  <1> The content of the cage-type silsesquioxane structure represented by the following formula (2) is less than 30 mol% in the a component (first to fourth of the present invention).

[RSiO _1.5 ] _c (2)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 6 to 20.)

  <2> The composition in which the component a, component b and component c are uniformly compatible (first to fourth aspects of the present invention).

  <3> The e component is a radical generator that generates radicals by light irradiation (second and fourth aspects of the present invention).

  <4> The e-component radical generator has a 10-hour half-life temperature of 100 ° C. or higher and 400 ° C. or lower (second and fourth aspects of the present invention).

  <5> 1 to 60 parts by mass of the a component is included in 100 parts by mass of the total weight of the a component, the b component, and the c component (first to fourth of the present invention).

  <6> 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 fourth of the present invention).

  <7> 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 ( First to fourth of the present invention).

  <8> The component a is a mixture having a number average molecular weight (Mn) of 500 to 4000 (first to fourth of the present invention).

  <9> 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 (first to fourth of the present invention).

  <10> The total light transmittance of the silsesquioxane cured product having a wavelength of 400 nm to 800 nm is 85% or more and 100% or less (third and fourth aspects of the present invention).

  <11> The 5% weight reduction temperature of the cured silsesquioxane is 400 ° C. or higher and 800 ° C. or lower (third and fourth aspects of the present invention).

  <12> The maximum elongation at tensile strength of the cured silsesquioxane is 10% or more and 40% or less (third and fourth aspects of the present invention).

The first, third and fifth aspects of the present invention are as follows:
a) an oligomer mixture of silsesquioxane (component a) containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partially cleaved structure thereof;
[RSiO _1.5 ] _a [RSiO ₂ H] _b (1)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , A nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 4 to 12, b is an integer of 1 to 3, and a + b is an integer of 7 to 14.)
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 which is a component. A compound having a compound (component c),
d) By polymerizing in the presence of a hydrosilylation catalyst (component d), a cured product having excellent heat resistance and transparency can be obtained.

The second, fourth and sixth aspects of the present invention are:
a) an oligomer mixture of silsesquioxane (component a) containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partially cleaved structure thereof;
[RSiO _1.5 ] _a [RSiO ₂ H] _b (1)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , A nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 4 to 12, b is an integer of 1 to 3, and a + b is an integer of 7 to 14.)
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 which is a component. A compound having a compound (component c),
d) in the presence of a hydrosilylation catalyst (component d), and e) a radical generator (component e),
By polymerizing, a cured product having excellent heat resistance and excellent transparency can be obtained.

In the first to sixth 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 mixture of silsesquioxanes whose content of the cage silsesquioxane structure represented by the following formula (2) is less than 30 mol% as the a component, the b component and the c component Can be preferably used because of improved compatibility.
[RSiO _1.5 ] _c (2)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 6 to 20.)

  In the second, fourth, and sixth aspects of the present invention, when a bond is formed using a radical reaction, the first-stage crosslinking is allowed to proceed with hydrosilylation, and then the second-stage radical reaction is applied. Therefore, it is important to obtain a transparent molded body. Therefore, if the radical reaction starts with the carbon-carbon double bond and the 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 silsesquioxane cured product 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 a component means an oligomer mixture of silsesquioxanes containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partial cleavage structure thereof.
[RSiO _1.5 ] _a [RSiO ₂ H] _b (1)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , A nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 4 to 12, b is an integer of 1 to 3, and a + b is an integer of 7 to 14.)
-The component b means a compound having at least two SiH groups in the same molecule.
The component c means a compound having at least two carbon-carbon double bonds in the same molecule excluding the silsesquioxane oligomer which is the component a.
-D component means a hydrosilylation catalyst.
-E component means a radical generating agent.
-A curable composition means the composition containing d component from a component, or the composition containing e 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 containing a radical generator (e component) (curable composition B) and a composition not containing it (curable composition A) are obtained.

  The curable composition A is a composition including an a component, a b component, a c component, and a d component, and the cured component is formed (polymerized) by combining the c component from the a component with the d component. Obtainable.

  The curable composition B is a composition including an a component, a b component, a c component, a d component, and an e component, and the c component is generated from the a component by the d component and the e component ( Polymerized) to obtain a cured product.

  The cured silsesquioxane is formed by bonding (polymerizing) a composition containing a component, b component, and c component in the presence of d component or in the presence of d component and e component. It is a cured product obtained.

  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) (in the present invention) The first and third)
[1] In a 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, particularly 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.

  As for the composition ratio of the a component, the b component, and the c component, if the a component is smaller than the above range, the heat resistance may decrease. Moreover, when a component is larger than the said range, a crosslinking density becomes low, heat resistance becomes low, and it may become weak. Further, when the molar ratio (SiH group / carbon-carbon double bond group) 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 is smaller than the above range, crosslinking is caused. It is not sufficient, heat resistance is low, and it may become brittle. On the other hand, when 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, without including the radical generator (e component) and the reinforcing filler described later, the silsesquioxane cured product is obtained from the composition containing the a component, the b component, and the c component using a hydrosilylation catalyst (d component). When obtained (first and third aspects of the invention)
[1] In a 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, particularly 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, 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.

  As for 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 lowered 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. Further, when the molar ratio (SiH group / carbon-carbon double bond group) 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 is smaller than the above range, crosslinking is caused. It is not sufficient, heat resistance is low, and it may become brittle. On the other hand, when 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.

Further, when a silsesquioxane cured product is obtained from a composition containing a component, b component and c component using a hydrosilylation catalyst (d component) and a radical generator (e component) (second and second aspects of the invention). In the fourth aspect of the invention,
[1] In a total weight of 100 parts by mass of the component a, the component b, and the component c, the component a is preferably 30 to 60 parts by mass, more preferably 35 to 55 parts by mass, particularly preferably 40 to 50 parts by mass,
[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 particularly preferably 0.8 to 1.

  As for the composition ratio of the a component, the b component, and the c component, if the a component is smaller than the above range, the heat resistance may decrease. 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) 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 is smaller than the above range, crosslinking is caused. It is not sufficient, heat resistance is low, and it may become brittle. On the other hand, when 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 component a is an oligomer mixture of silsesquioxanes containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partially cleaved structure thereof. It is preferable to contain 50-90 mol% of the cage silsesquioxane structure represented by the above and / or its partial cleavage structure. By containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partially cleaved structure thereof, compatibility with the b component and the c component is improved. An excellent cured silsesquioxane can be obtained.

[RSiO _1.5 ] _a [RSiO ₂ H] _b (1)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , A nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 4 to 12, b is an integer of 1 to 3, and a + b is an integer of 7 to 14.)

Among these, the compound [RSiO _1.5 ] ₈ [RSiO ₂ H] ₁ represented by a = 8, b = 1 and the compound [RSiO _1.5 ] ₁₀ [RSiO ₂ represented by a = 10, b = 1. H] ₁ and a compound [RSiO _1.5 ] ₁₂ [RSiO ₂ H] ₁ represented by a = 12, b = 1 in total of 25 mol% or more are in a phase with the b component and the c component. From the viewpoint of solubility.

Of the compounds represented by the formula (1), an example of the compound [RSiO _1.5 ] ₄ [RSiO ₂ H] ₃ represented by a = 4 and b = 3 is shown in the following formula (1-1).

Among the compounds represented by the formula (1), examples of the compound [RSiO _1.5 ] ₆ [RSiO ₂ H] ₂ represented by a = 6, b = 2 are represented by the following formulas (1-2), (1 -3).

Of the compounds represented by the formula (1), an example of the compound [RSiO _1.5 ] ₈ [RSiO ₂ H] ₁ represented by a = 8 and b = 1 is shown in the following formula (1-4).

Among the compounds represented by the formula (1), examples of the compound [RSiO _1.5 ] ₆ [RSiO ₂ H] ₃ represented by a = 6 and b = 3 are represented by the following formulas (1-5) to (1 -9).

Among the compounds represented by the formula (1), examples of the compound [RSiO _1.5 ] ₈ [RSiO ₂ H] ₂ represented by a = 8, b = 2 are represented by the following formulas (1-10) to (1 -16).

Of the compounds represented by the formula (1), examples of the compound [RSiO _1.5 ] ₁₀ [RSiO ₂ H] ₁ represented by a = 10, b = 1 are represented by the following formulas (1-17), (1 -18).

Among the compounds represented by the formula (1), examples of the compound [RSiO _1.5 ] ₁₀ [RSiO ₂ H] ₂ represented by a = 10, b = 2 are represented by the following formulas (1-19) to (1 -26).

Among the compounds represented by the formula (1), examples of the compound [RSiO _1.5 ] ₁₂ [RSiO ₂ H] ₁ represented by a = 12, b = 1 are represented by the following formulas (1-27), (1 -28).

Among the compounds represented by the formula (1), examples of the compound [RSiO _1.5 ] ₁₂ [RSiO ₂ H] ₂ represented by a = 12, b = 2 are represented by the following formulas (1-29) to (1 -43).

  Moreover, it is preferable that content of the cage silsesquioxane structure represented by the following Formula (2) is less than 30 mol% from a compatible viewpoint with b component and c component.

[RSiO _1.5 ] _c (2)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 6 to 20.)

Of the compounds represented by the formula (2), an example of the compound [RSiO _1.5 ] ₈ represented by c = 8 is shown in the following formula (2-1).

Of the compounds represented by the formula (2), an example of the compound [RSiO _1.5 ] ₁₀ represented by c = 10 is shown in the following formula (2-2).

Of the compounds represented by the formula (2), examples of the compound [RSiO _1.5 ] ₁₂ represented by c = 12 are shown in the following formulas (2-3) and (2-4).

Of the compounds represented by the formula (2), examples of the compound [RSiO _1.5 ] ₁₄ represented by c = 14 are shown in the following formulas (2-5) to (2-7).

In the substituent R of the formulas (1) and (2),
-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-methacryloyloxypropyl group, 3-acryloyloxypropyl 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-bromoethyl group, 3-bromopropyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoro Examples thereof include an ethyl group, a 3-fluoropropyl group, and a 3,3,3-trifluoropropyl group.
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 include at least two substituents having a carbon-carbon double bond such as vinyl group, propenyl group, butenyl group, styryl group, 3-methacryloyloxypropyl group, and 3-acryloyloxypropyl group in one molecule. It can be appropriately combined with the conditions.

  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 particularly 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, particularly 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) can be used alone or in combination of two or more (for example, b1 and b1, b1 and b2, etc. are combined).

(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-methacryloyloxypropyl group, 3-acryloyloxypropyl 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-bromoethyl group, 3-bromopropyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2-fluoro Examples thereof include an ethyl group, a 3-fluoropropyl group, and a 3,3,3-trifluoropropyl group.
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 1,2-vinyl structure-containing compounds of polybutadiene oligomers.
(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 of 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 producing a silsesquioxane cured product, by using a hydrosilylation catalyst (d component) and a radical generator (e component) in combination, the carbon-carbon bismuth contained in the c component that did not react with the SiH group. Double bonds can be bonded to each other, and there is an 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 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) Name park mill 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 Parkmill P: Nippon Oil & Fats), 1,1,3,3-tetramethylbutyl hydroperoxide (trade name Perocta H: Nippon Oil & Fats), cumene hydroperoxide (trade name Parkmill H: Nippon Oil & Fats), t-butyl Hydroperoxide (trade name perbutyl H: Japanese fats and oils) and the like can be mentioned.

  The curable composition and silsesquioxane cured product of the present invention may further contain a reinforcing filler.

As a reinforcing filler,
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 a plurality of these layers), etc.
2) A powdery material, a fibrous material, or a sheet-like material, excluding a fibrous material or a particulate material made from the glass material of 1) above, can be mentioned.

  For example, cellulose fiber sheet, bacterial cellulose fiber sheet, polyimide porous film, cellulose fiber, polyamide 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 can be reduced, so that the cured product can be easily used as a substrate material.

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

  When a glass material is used as the reinforcing filler, 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 have few ionic impurities such as alkali metals and are easily available, are preferable.

  When a glass material is used as the reinforcing filler, a silsesquioxane cured product obtained from a curable composition containing a component, b component, c component, and d component, or a component, b component, c component, 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 reinforcing filler 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 reinforcing filler is in a state where an appropriate treatment has been performed.

  The glass material used as the reinforcing filler is preferably in a state in which 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 marketed 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. -In acryloyloxypropyltrialkoxysilane treatment, acryloyl groups can 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 reinforcing filler is not a glass material, surface functional groups and hardening of the reinforcing filler are introduced by introducing functional groups such as surface hydroxyl groups by partial oxidation treatment, partial hydrolysis treatment, electron beam irradiation, plasma irradiation, radiation irradiation, etc. It is preferable because it can be bonded and formed with an adhesive composition, and adhesion is enhanced.

  The refractive index of the reinforcing filler is preferably 1.48 to 1.60 so that the cured silsesquioxane has excellent transparency. 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 higher refractive index 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 cured product obtained from the curable composition containing the a component, b component, c component and d component of the present invention, or the a component, b component, c component, d component and e component of the present invention The difference between the refractive index of the cured silsesquioxane obtained from the curable composition and the refractive index of the reinforcing filler is preferably 0.01 or less and 0.005 or less in order to maintain excellent transparency. Is more preferable. When the refractive index difference is larger than 0.01, the transparency of the obtained transparent material tends to be inferior.

  The reinforcing filler is a curable composition containing a component, b component, c component and d component, or a cure 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 compounding amount of the reinforcing filler 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 reinforcing filler, 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 based on the total amount of the curable composition (100% by mass). Is 30-70 mass%. If the blending amount of the reinforcing filler 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, thermoplasticity or a range of 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 overall refractive index is adjusted to match the refractive index of the reinforcing filler. It becomes easy.

  In addition, in the curable composition and silsesquioxane cured product of the present invention, if necessary, in a range that does not impair characteristics such as transparency, solvent resistance, heat resistance, dimensional stability, mechanical strength, 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, it can be carried out by subjecting it to a curable composition through a normal degassing operation, pouring the curable composition into an appropriate mold, and then proceeding with a bond formation reaction by heating and / or light irradiation. .

  In addition, the silsesquioxane cured product containing the reinforcing filler is 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 the 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 a fibrous material or a particulate material in the stirring and mixing of the above mixture. And after making this curable composition into the target shape according to a use, it can carry out by making it harden | cure by making a coupling | bonding production reaction advance by heating and / or light irradiation. 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 plate or stainless steel plate, and heated. And / or the method of making it harden | cure by making a bond formation reaction advance by irradiating 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. Or it is good also as the method of making it harden | cure by light-irradiating a bond production reaction.

  As an example of a method for producing a silsesquioxane cured product, component a, component b, component c, and a solvent as necessary are added and mixed, preferably uniformly mixed, and further component d is added, After mixing, preferably uniformly mixing, a defoaming treatment is performed under reduced pressure to obtain a transparent liquid composition (curable composition).

  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 where contact with air is cut off in a cool and dark place. For example, the obtained transparent liquid curable composition is filled in a commercially available plastic syringe, the tip of the syringe is sealed and stored in a cold state of 5 ° C. to 10 ° C., and then cured 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 is impregnated with the above-mentioned composition in the reinforcing filler of the sheet-like material, and then deaerated as necessary to obtain a curable composition. Alternatively, a fibrous or particulate reinforcing filler is dispersed in the 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, component a, component b, component c, and, if necessary, a solvent are added and mixed, preferably mixed uniformly, and further component d The e component is added and mixed, preferably mixed uniformly, and then subjected to defoaming treatment under reduced pressure to obtain a transparent liquid composition (curable composition).

  Further, the silsesquioxane cured product further containing a reinforcing filler is obtained by adding a reinforcing filler to the above composition or adding a composition to the reinforcing filler, and deaeration as necessary to obtain a curable composition. obtain.

  The 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. (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, UV irradiation time is in the range of 0.1 to 10 minutes.) Or (2) Radiation is generated by heat to initiate radical reaction, and then in the range of 80 to 400 ° C. for 0.5 to 48 hours. A cured product can be produced by performing a chemical reaction and a radical reaction.

  In the case where the reinforcing filler is included and the reinforcing filler is a fibrous or particulate material, the reinforcing filler can be dispersed in the curable composition by a method such as stirring and mixing. Further, when the reinforcing filler is a sheet-like material, it can be used by impregnating the curable composition into one or a plurality of sheet-like reinforcing fillers.

  In addition, when a reinforcing filler is included, and the reinforcing filler is used in combination with a fibrous or particulate material and a sheet-like material, the fibrous or particulate material is used as a curable composition. It can be used after being dispersed and then impregnated with the curable composition into a sheet-like reinforcing filler.

  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 reduced pressure treatment, the curing reaction is allowed to proceed, or the solvent component Removal and curing reaction can proceed in parallel.

  In the case where the curable composition contains a reinforcing filler, the composition containing the reinforcing filler is cast into a mold having a desired shape and then cured, or a composition containing components other than the reinforcing filler. Examples thereof include a method of impregnating a product with a glass cloth or a glass nonwoven fabric to obtain a curable composition, and then curing and molding into 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 method for producing a cured silsesquioxane of the present invention, various forms of cured silsesquioxane such as a film, a sheet, a plate, a column, and a cylinder 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. When used for coating or sealing purposes, the curable composition of the present invention has a relatively low viscosity, so that it can be easily coated or sealed even on materials having complicated shapes.

  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 has excellent heat resistance, dimensional stability, mechanical strength, transparency, and molding processability. Therefore, the liquid crystal element is formed into a sheet shape and includes an active matrix type. It can be particularly suitably used for applications such as a 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 weight of the substrate can be reduced as compared with the glass substrate.

  When this silsesquioxane cured product is used as a 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 Preferably it is 20 ppm / K or less. Setting it to 5 ppm / K or less is difficult to select the composition of the curable composition and the curing conditions, 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 as a 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. . 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 method〕
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.
The peak appearing at δ-80 ppm was attributed to a trisiloxysilyl (hereinafter referred to as T3) peak, and the peak appearing near δ-70 ppm was attributed to a peak derived from disiloxysilyl (hereinafter referred to as T2).

2) TOF-MS measurement of cage-shaped silsesquioxanes: Measurements were made by the direct infusion method using Varian's microOTOF focus manufactured by Bruker Daltonics. ESI + was used for the ionization method. The solvent used was methanol / acetonitrile = 1/1, the sample measurement concentration was about 50 ppm, and the sample injection rate was 180 μL / h. The m / z observed under these conditions was attributed to the sodium adduct of the compound to be measured.
Then, considering the abundance ratio of Si, C, O, and H isotopes with respect to the numerical value obtained by subtracting the sodium content from m / z, the following formula (3 ), R, d, and e are assigned, and the sum of signal intensities of m / z expressed by the general formula using the same d and e is obtained, and the value is derived from the structure represented by the general formula Signal strength. Separately, the sum of signal intensities over the entire measurement range was obtained. The signal intensity derived from each structure was divided by the sum of the signal intensity over the entire measurement range to obtain a signal intensity ratio relative to the whole, and this was defined as the presence ratio of the structure in the measured composition.
[RSiO _1.5 ] _d [RSiO ₂ H] _e (3)

  3) Measurement of molecular weight (number average molecular weight (Mn), weight average molecular weight (Mw)) and molecular weight distribution (Mw / Mn) of oligomers of silsesquioxanes: 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.

4) 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): The 5% weight reduction temperature (hereinafter referred to as Td5) was measured at 20 ° C. from room temperature to 550 ° C. using about 10 mg of sample and 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 while passing through nitrogen 40 ml / min, the same temperature was maintained for 5 minutes, and the temperature was 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 a differential heat curve observed at the second temperature rise.

  5) Measurement of 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 obtained. 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.

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

  7) 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 load, 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 and 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]
In an 8 L separable flask, 6000 ml of tetrahydrofuran and 225 ml of 1N aqueous sodium hydroxide solution were placed, and 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 then concentrated, and the concentrated solution was dropped into 8000 ml of n-heptane to form a precipitate. The precipitate was collected by filtration, redissolved in a mixture 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.
The measurement result of the nuclear magnetic resonance spectrum (NMR) of the product was as follows: 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%. The ²⁹ Si-NMR measurement spectrum of the product is shown in FIG. 1, and the ¹ H-NMR measurement spectrum is shown in FIG. 2.
1 g of the product contains 2.50 mmol equivalent as a vinyl group.
The TOF-MS measurement spectrum of the product is shown in FIG. 3, and the structural composition of the product analyzed by the TOF-MS measurement of the product is shown in Table 1.

(Synthesis example 2 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 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 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 3 times with saturated brine, 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.
Nuclear magnetic resonance spectrum (NMR) measurement results of the product were as follows: ¹ H-NMR δ (ppm): 0.2 (m, 15H), 5.9-6.0 (m, 15H); 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). It was.
1 g of the product contains 6.70 mmol equivalent as a vinyl group.
The structural composition of the product analyzed by TOF-MS measurement of the product is shown in Table 1.

(Synthesis example 3 of cage 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. 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 liquid 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.
The measurement result of the nuclear magnetic resonance spectrum (NMR) of the product was as follows: 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.
The structural composition of the product analyzed by TOF-MS measurement of the product is shown in Table 1.

[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 each of the cage silsesquioxane oligomer prepared in Synthesis Example 1 Methylcyclotetrasiloxane (4.13 g, 68.7 mmol as SiH group) was mixed and ultrasonically stirred for 10 minutes. 20 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. 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), and the curable composition is injected into the mold in a constant temperature bath at 120 ° C. 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]
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 1 Methylcyclotetrasiloxane (3.01 g, 50.1 mmol as SiH group) was mixed and ultrasonically stirred for 10 minutes. 20 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. 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%.

[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 1 (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 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 disintegrated and the recovered solid weight was 76.7%.

[Comparative Example 3]
2.99 g of the cage silsesquioxane oligomer synthesized in Synthesis Example 1 (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 disintegrated and the recovered solid weight was 28.5%.

[Example 3]
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 1, 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 4]
5.68 g (14.17 mmol as a vinyl group) of cage-shaped silsesquioxane oligomer (T2: 19 mol%) prepared by the same method as in Synthesis Example 1, 5.57 g (85.62 mmol as a vinyl group) divinylbenzene, Then, 6.50 g of 1,3,5,7-tetramethylcyclotetrasiloxane (108.14 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. 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 2. Next, the same heating as in Example 3 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., 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 5]
1.53 g (11.07 mmol as vinyl group) of cage silsesquioxane oligomer (T2: 8 mol%) prepared by the same method as in Synthesis Example 3, 4.36 g (66.93 mmol as vinyl group) divinylbenzene, Then, 4.72 g (78.54 mmol as SiH group) of 1,3,5,7-tetramethylcyclotetrasiloxane was mixed and subjected to ultrasonic stirring 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 2. 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 6]
1.53 g (10.90 mmol as vinyl group) of cage silsesquioxane oligomer (T2: 25 mol%) prepared by the same method as in Synthesis Example 3, 4.31 g (66.14 mmol as 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 injected into a mold produced in the same manner as in Example 2. Next, the same heating as in Example 3 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 7]
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 4 Methylcyclotetrasiloxane (4.02 g) (66.82 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. 5.00 g of this curable composition was sampled, 0.0163 g of perbutyl Z was added thereto, poured into a mold produced in the same manner as in Example 2, and then kept in a thermostatic bath at 90 ° C. for 3 hours. The curable composition was cured by heating at a rate of temperature increase 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 8]
3.51 g (8.75 mmol as vinyl group), 3.45 g (52.97 mmol as vinyl group) of divinylbenzene, and 1,3,5,7-tetra cage-shaped silsesquioxane oligomer used in Example 4 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 2, 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 an elastic modulus of 1.29 GPa, a maximum point stress of 12.8 MPa, and an elongation at break of 1.7%. The total light transmittance was 91%.

[Example 9]
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 2 Tetramethylcyclotetrasiloxane 4.72g (78.44mmol 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 dryer 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 10]
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 2 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 dryer 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%.

[Comparative Example 4]
0.60 g (7.60 mmol as a vinyl group) of a commercially available vinyl group-substituted silsesquioxane oligomer (Aldrich Octavinyl-POSS ^™ , ²⁹ Si-NMR δ (ppm): -80 (T3) 100 mol%), divinylbenzene 3 .05 g (46.82 mmol as a vinyl group) and 4.43 g (73.73 mmol as a SiH group) of 1,3,5,7-tetramethylcyclotetrasiloxane were mixed and ultrasonically stirred for 10 minutes. Without becoming a cloudy mixture. A small amount of 1 wt% chloroplatinic acid ethanol solution was added thereto, and defoaming was performed by vacuum stirring. The mixture was kept in a cloudy mixed state and kept in a constant temperature bath at 120 ° C. for 1.5 hours, and then kept at 200 ° C. for 30 minutes. The obtained cured product was in a non-uniform white turbid state.

[Example 11]
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 1, 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 subjected to ultrasonic stirring 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 that was colorless, transparent and 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, 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 12]
4.02 g (10.01 mmol as a vinyl group) of cage-shaped silsesquioxane oligomer (T2: 19 mol%) prepared in the same manner as in Synthesis Example 1, 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 13]
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 1 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 5]
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 Td5 of the cured product was 400.2 ° C., the tensile properties were an elastic modulus of 4.38 GPa, a maximum point stress of 217.5 MPa, and an elongation at break of 4.87%. The linear expansion coefficient of the cured product was 11.8 ppm / K, and the total light transmittance was 84.3%.

[Comparative Example 6]
3.00 g (7.50 mmol as a vinyl group) of the cage silsesquioxane oligomer synthesized in Synthesis Example 1 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 14]
2.00 g (5.18 mmol as vinyl group) of cage silsesquioxane oligomer (T2: 19 mol%) prepared by the same method as in Synthesis Example 1, 2.70 g (41.50 mmol as 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 15]
3.00 g of cage silsesquioxane oligomer (T2: 19 mol%) prepared by the same method as in Synthesis Example 1 (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 16]
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 1, 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 17]
1.00 g (7.24 mmol as a vinyl group) of cage silsesquioxane oligomer (T2: 8 mol%) prepared by the same method as in Synthesis Example 3, 3.90 g (59.94 mmol as a 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 18]
0.50 g (3.62 mmol as vinyl group) of cage silsesquioxane oligomer (T2: 8 mol%) prepared by the same method as in Synthesis Example 3, 3.82 g (58.61 mmol as 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 19]
0.70 g (4.74 mmol as vinyl group), 2.30 g of trivinylcyclohexane (42.59 mmol as vinyl group), and 1,3,5,7- Tetramethylcyclotetrasiloxane 5.77 g (95.91 mmol as SiH group) was mixed and ultrasonically stirred for 10 minutes to be compatible. 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 effect defoaming. 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 20]
1.10 g of the cage silsesquioxane oligomer prepared in Synthesis Example 2 (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 effect defoaming. 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 21]
3.00 g of cage silsesquioxane oligomer (T2: 19 mol%) prepared by the same method as in Synthesis Example 1 (7.78 mmol as vinyl group), 1.50 g of divinylbenzene (23.07 mmol as vinyl group), Then, 2.50 g of 1,3,5,7-tetramethylcyclotetrasiloxane (41.57 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 467 ° C., tensile properties were an elastic modulus of 1.08 GPa, a maximum point stress of 24.0 MPa, and an elongation at break of 3.1%. The total light transmittance was 93%.

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

Claims (29)

a) an oligomer mixture of silsesquioxane (component a) containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partially cleaved structure thereof;
[RSiO _1.5 ] _a [RSiO ₂ H] _b (1)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , A nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 4 to 12, b is an integer of 1 to 3, and a + b is an integer of 7 to 14.)
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 silsesquioxane as component a, and d) a hydrosilylation catalyst (component d),
The curable composition characterized by including these. a) an oligomer mixture of silsesquioxane (component a) containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partially cleaved structure thereof;
[RSiO _1.5 ] _a [RSiO ₂ H] _b (1)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , A nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 4 to 12, b is an integer of 1 to 3, and a + b is an integer of 7 to 14.)
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. The curable composition according to claim 1 or 2, wherein the component a has a content of the cage silsesquioxane structure represented by the following formula (2) of less than 30 mol%.
[RSiO _1.5 ] _c (2)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 6 to 20.)   The curable composition according to any one of claims 1 to 3, wherein the composition comprising the a component, the b component, and the c component is uniformly compatible.   The curable composition according to claim 2, wherein the component e is a radical generator that generates radicals by light irradiation.   The curable composition according to claim 2, wherein the e-component radical generator has a 10-hour half-life temperature of 100 ° C. or more and 400 ° C. or less.   The curable composition according to any one of claims 1 to 6, comprising 1 to 60 parts by mass of a component in 100 parts by mass of the total weight of component a, component b and component c.   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 1-7.   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 9, 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 10, 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) an oligomer mixture of silsesquioxane (component a) containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partially cleaved structure thereof;
[RSiO _1.5 ] _a [RSiO ₂ H] _b (1)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , A nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 4 to 12, b is an integer of 1 to 3, and a + b is an integer of 7 to 14.)
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 which is a component. A compound having a compound (component c),
d) in the presence of a hydrosilylation catalyst (component d),
A silsesquioxane cured product obtained by forming a bond. a) an oligomer mixture of silsesquioxane (component a) containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partially cleaved structure thereof;
[RSiO _1.5 ] _a [RSiO ₂ H] _b (1)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , A nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 4 to 12, b is an integer of 1 to 3, and a + b is an integer of 7 to 14.)
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 which is a component. A compound having a compound (component c),
d) in the presence of a hydrosilylation catalyst (component d), and e) a radical generator (component e),
A silsesquioxane cured product obtained by forming a bond. The silsesquioxane cured product according to claim 12 or 13, wherein the component a has a cage silsesquioxane structure content of less than 30 mol% represented by the following formula (2).
[RSiO _1.5 ] _c (2)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 6 to 20.)   The silsesquioxane cured product according to any one of claims 12 to 14, 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 13, wherein the e component is a radical generator that generates radicals by light irradiation.   14. The cured silsesquioxane according to claim 13, wherein the e-component radical generator has a 10-hour half-life temperature of 100 ° C. or more and 400 ° C. or less.   The silsesquioxane cured product according to any one of claims 12 to 17, 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 12 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 any one of claims 12 to 19, wherein the total light transmittance at a wavelength of 400 nm to 800 nm is 85% or more and 100% or less.   21. The cured silsesquioxane according to any one of claims 12 to 20, having a 5% weight loss temperature of 400 ° C or higher and 800 ° C or lower.   The silsesquih according to any one of claims 12 to 21, 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 12-22.   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.   25. The cured silsesquioxane according to any one of claims 12 to 24, wherein the maximum point elongation is 10% or more and 40% or less in tensile property evaluation.   The cured silsesquioxane according to any one of claims 12 to 25, which is used for an optical film, an optical sheet, a display element circuit substrate, or a transparent substrate.   The cured silsesquioxane according to any one of claims 12 to 25, which is used for an optical element sealant, a light-emitting element sealant, particularly a white LED sealant, or a semiconductor sealant. a) an oligomer mixture of silsesquioxane (component a) containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partially cleaved structure thereof;
[RSiO _1.5 ] _a [RSiO ₂ H] _b (1)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , A nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 4 to 12, b is an integer of 1 to 3, and a + b is an integer of 7 to 14.)
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 which is a component. A compound having a compound (component c),
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) an oligomer mixture of silsesquioxane (component a) containing 50 mol% or more of the cage silsesquioxane structure represented by the following formula (1) and / or a partially cleaved structure thereof;
[RSiO _1.5 ] _a [RSiO ₂ H] _b (1)
(In the formula, 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 functionalized hydrocarbon group having 1 to 20 carbon atoms. , A nitrogen-containing functionalized hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing functionalized 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 on average, at least two are substituents containing a carbon-carbon double bond. (It is an integer of 4 to 12, b is an integer of 1 to 3, and a + b is an integer of 7 to 14.)
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 which is a component. A compound having a compound (component c),
d) in the presence of a hydrosilylation catalyst (component d), and e) a radical generator (component e),
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) Performing a radical reaction 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.