JP2006283012A - Silicon-containing curable composition and thermally cured material therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicon-containing curable composition, which is excellent in stability, transparency and curability, and can be used for forming a cured product excellent in various properties such as crack resistance, heat resistance, solvent resistance and alkali resistance. <P>SOLUTION: The silicon-containing curable composition includes at least one silicon-containing polymer among component (A), component (B) and component (C). The component (A) is a silicon-containing polymer having one or more reactive groups selected from the group consisting of Si-CH=CH<SB>2</SB>, Si-R<SP>1</SP>-CH=CH<SB>2</SB>and Si-R<SP>1</SP>-OCOC(R<SP>2</SP>)=CH<SB>2</SB>and having at least one bridging structure by an Si-O-Si bond. The component (B) is a silicon-containing polymer having Si-H group and having at least one bridging structure by an Si-O-Si bond. The component (C) is a silicon-containing polymer having one or more above reactive groups and further an Si-H group and having at least one bridging structure by an Si-O-Si bond. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a silicon-containing curable composition and a cured product obtained by thermally curing the composition. Specifically, silicon is excellent in stability, transparency, and curability, and the cured product has excellent physical properties such as crack resistance, heat resistance, solvent resistance, alkali resistance, weather resistance, optical characteristics, and electrical characteristics. The present invention relates to a curable composition.

  Various studies have been conducted on organic / inorganic composite materials combining organic and inorganic materials, and industrially, inorganic fillers are combined with organic polymers, and metal surfaces are modified with organic polymers. A coating method is used. In these organic / inorganic composite materials, the material that composes them is larger than the micrometer order, so some physical properties can be improved more than expected, but many other performances. The physical properties simply indicate values expected from the addition rules of the performance and physical properties of the organic material and the inorganic material, respectively.

  On the other hand, in recent years, organic / inorganic composite materials in which the sizes of domains of organic materials and inorganic materials are in the order of nanometers and are combined at the molecular level have been actively studied. Such materials not only have the characteristics of each material, but also have the advantages of each material, and also have a new functionality that is completely different from each material itself, which cannot be predicted by the additive law. There is expected.

Such organic / inorganic composite materials include a chemical bond type in which one material and the other material are bonded at a molecular level via a covalent bond, and one material as a matrix, and the other material is contained therein. There is a mixed type that is finely dispersed and combined.
A mixed composite material that is simply dispersed / combined is separated because there is no strong bond between the two materials. For example, when used as a curing material, various physical properties such as heat resistance and solvent resistance are improved. There were cases where there was insufficient. In particular, the sol-gel method is often used as a method for synthesizing inorganic materials used in mixed types. This sol-gel method is the hydrolysis of precursor molecules and the subsequent polycondensation reaction. Thus, a crosslinked inorganic oxide can be obtained at a low temperature. The inorganic material obtained by this sol-gel method has a problem of poor storage stability, such as gelation in a short period of time. In Non-Patent Document 1, paying attention to the difference in condensation rate due to the chain length of the alkyl group of alkyltrialkoxysilane, a long-chain alkyltrialkoxysilane having a slow polycondensation rate is added after polycondensation of methyltrimethoxysilane. Sealing the silanol group in the polysiloxane, and further performing a polycondensation reaction of methyltrimethoxysilane using an aluminum catalyst, and adding acetylacetone when the molecular weight is reached, in the reaction system Attempts to improve storage stability by ligand exchange have been described. However, these methods have been insufficient in improving storage stability.

  On the other hand, a curable composition containing a specific silicon-containing polymer has been proposed as a chemically bonded organic / inorganic composite material (see, for example, Patent Document 1). However, the performance of the curable composition containing the silicon-containing polymer is not sufficient, and in particular, the heat resistance and electrical characteristics of the cured product are not satisfactory.

JP 2002-356617 A The Chemical Society of Japan, No. 9, 571 (1998)

  Therefore, the object of the present invention is excellent in stability, transparency and curability, and the cured product has various properties such as crack resistance, heat resistance, solvent resistance, alkali resistance, weather resistance, optical characteristics, electrical characteristics, etc. An object of the present invention is to provide a silicon-containing curable composition having excellent physical properties.

  As a result of diligent investigation focusing on the heat resistance, electrical characteristics, etc. of the cured product of the silicon-containing curable composition, the present inventors have determined that a silicon-containing curable composition having a specific reactive group is a platinum-based catalyst and It was found that a cured product having excellent performance and physical properties can be obtained by thermosetting together with the iron group-containing complex.

The present invention (the invention described in claim 1) is based on the above knowledge, and contains at least one silicon-containing polymer among the following components (A), (B) and (C) (however, , (C) component is not contained, both (A) component and (B) component are contained), and a silicon-containing curable composition containing the following components (D) and (E) is provided: Is.
Component (A): Si—CH═CH ₂ , Si—R ¹ —CH═CH ₂ and Si—R ¹ —OCOC (R ² ) ═CH ₂ [wherein R ¹ is an alkylene group having 1 to 9 carbon atoms. Or a phenylene group, and R ² is hydrogen or a methyl group]. One or two or more reactive groups (A ′) selected from the group consisting of a group consisting of Si—O—Si bonds are provided at one place. A silicon-containing polymer having a molecular weight of 1,000,000 to 1,000,000 (excluding those having a Si-H group);
Component (B): A silicon-containing polymer having Si—H groups, having one or more cross-linked structures by Si—O—Si bonds, and having a molecular weight of 1,000,000 to 1,000,000 (however, the above reactive groups ( Except those having A ′);
Component (C): One or more of the above reactive groups (A ′), a Si—H group, one or more cross-linked structures with Si—O—Si bonds, and a molecular weight of 100 A silicon-containing polymer of ~ 1 million;
(D) component: a curing reaction catalyst which is a platinum-based catalyst;
(E) Component: Iron group-containing complex

Further, in the present invention (the invention according to claim 2), the component (A) is Si—OH, Si—R ³ —OH, Si—O—R ⁴ and Si—X [wherein R ³ is carbon. An alkylene group or a phenylene group having 1 to 9 carbon atoms, R ⁴ is an alkyl group having 1 to 5 carbon atoms, and X is a halogen atom]. Silicon-containing polymer precursor (1) having ') and silicon that is a linear polysiloxane having a reactive group (2') that can react with the reactive group (1 ') to form a covalent bond at the terminal The silicon-containing polymer precursor (3) obtained by reacting the containing polymer precursor (2) is further obtained by introducing the reactive group (A '). A silicon-containing curable composition is provided.

In the present invention (the invention according to claim 3), the component (B) is obtained by further introducing Si-H groups into the silicon-containing polymer precursor (3). The silicon-containing curable composition according to 1 or 2 is provided.
In the present invention (invention according to claim 4), the component (C) further introduces the reactive group (A ′) and / or Si—H group into the silicon-containing polymer precursor (3). It provides the silicon-containing curable composition according to any one of claims 1 to 3.

In the present invention (invention according to claim 5), at least one other atom bonded to the silicon atom in the reactive group (A ′) of the component (A) is an oxygen atom. The silicon-containing curable composition according to any one of -4 is provided.
Further, according to the present invention (invention 6), at least one other atom bonded to the silicon atom in the Si—H group of the component (B) is an oxygen atom. The silicon-containing curable composition according to any one of the above is provided.
Further, the present invention (invention according to claim 7) is characterized in that at least one other bonded to a silicon atom in the reactive group (A ′) of the component (C) or a silicon atom in the Si—H group. One atom is an oxygen atom, The silicon-containing curable composition of any one of Claims 1-6 is provided.

  Moreover, this invention (invention of Claim 8) provides the hardened | cured material formed by thermosetting the silicon-containing curable composition of any one of Claims 1-7.

  According to the present invention, it is excellent in stability, transparency and curability, and further, the cured product has various physical properties such as crack resistance, heat resistance, solvent resistance, alkali resistance, weather resistance, optical characteristics, electrical characteristics and the like. An excellent silicon-containing curable composition can be provided.

First, the silicon-containing polymer (A) component (hereinafter also referred to as silicon-containing polymer (A)) will be described.
The silicon-containing polymer as component (A) is composed of Si—CH═CH ₂ , Si—R ¹ —CH═CH ₂ and Si—R ¹ —OCOC (R ² ) ═CH ₂ [wherein R ¹ is carbon. An alkylene group or a phenylene group of formulas 1 to 9, and R ² is hydrogen or a methyl group], having one or more reactive groups (A ′) selected from the group consisting of Si—O—Si bond It has one or more cross-linked structures and has a molecular weight of 100 to 1,000,000. The molecular weight is a weight average molecular weight.

R ¹ is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of heat resistance and electrical properties of the cured product.
The reactive group (A ′) is particularly preferably Si—CH═CH ₂ from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability, and handling properties.
In addition, at least one other atom bonded to the silicon atom in the reactive group (A ′) of the component (A) from the viewpoint of heat resistance, electrical properties, curability, mechanical properties, storage stability and handling properties Is preferably an oxygen atom.

  The component (A) can be obtained by forming a Si—O—Si siloxane bond by hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane having a reactive group (A ′). In addition, the component (A) is obtained after hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane having no reactive group (A ′) to obtain a polymer having a Si—O—Si siloxane bond. It can also be obtained by introducing a reactive group (A ′) using a reactive functional group such as Si—OH or Si—Cl in the polymer. Moreover, you may obtain (A) component by using both together.

  In particular, the silicon-containing polymer of component (A) is the silicon-containing polymer precursor (3) obtained by reacting the silicon-containing polymer precursor (1) and the silicon-containing polymer precursor (2). ) Is preferably obtained by further introducing a reactive group (A ′).

Hereinafter, the silicon-containing polymer precursor (1) will be described.
The silicon-containing polymer precursor (1) includes one or more reactive groups (1 ′) that can react with the reactive groups (2 ′) of the silicon-containing polymer precursor (2) to form a covalent bond. Have. Examples of the reactive group (1 ′) include Si—OH, Si—R ³ —OH, Si—O—R ⁴ , Si—X [wherein R ³ is an alkylene group having 1 to 9 carbon atoms or phenylene. R ⁴ is an alkyl group having 1 to 5 carbon atoms, and X is a halogen atom]. This reactive group (1 ′) is preferably a Si—OH group, a Si—Cl group, a Si—O—CH ₃ group, or a Si—O—C ₂ H ₅ group, particularly a Si—OH group, from the viewpoint of reactivity. Si-Cl groups are preferred.

  The molecular weight (weight average molecular weight) of the silicon-containing polymer precursor (1) is preferably from 100 to 500,000, more preferably from 500 to 10,000, from the viewpoint of handling.

  Moreover, the silicon-containing polymer precursor (1) has one or more cross-linked structures with Si—O—Si bonds. The bridge structure in the silicon-containing polymer precursor (1) may be a ladder structure (ladder shape), a cage shape, a ring shape, or the like as long as it is formed by Si—O—Si bonds. All of these ladder-like, cage-like, and annular structures may be formed of Si—O—Si bonds, or a part thereof may be formed of Si—O—Si bonds. Of course, a plurality of Si—O—Si bonds may be repeated continuously.

In addition, the silicon-containing polymer precursor (1) includes Si—CH═CH ₂ , Si—R ¹ —CH═CH ₂ and Si—R ¹ —OCOC (R ² ) = CH ₂ [wherein R ¹ is One or two or more reactive groups (A ′) selected from the group consisting of an alkylene group having 1 to 9 carbon atoms or a phenylene group, and R ² is hydrogen or a methyl group, Or it may not have.

The silicon-containing polymer precursor (1) can be obtained by hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane.
As the alkoxysilane or chlorosilane that can obtain the silicon-containing polymer precursor (1) by hydrolysis / condensation reaction, the reactive group (A ′) when the silicon-containing polymer of the component (A) is finally obtained is used. Alkoxysilane or chlorosilane that already has, alkoxysilane or chlorosilane that does not have this reactive group (A ′).

  Examples of alkoxysilanes and chlorosilanes having no reactive group (A ′) that can be used to synthesize the silicon-containing polymer precursor (1) include acetoxymethyltrimethoxysilane, benzyltriethoxysilane, Bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, bis (triethoxysilyl) hexane, 3-bromopropyltrimethoxysilane, butyltrimethoxysilane, chloromethyltriethoxysilane, chlorophenyltriethoxysilane, 3- Chloropropyltrimethoxysilane, diethyldiethoxysilane, dimethyldiethoxysilane, dimethyldimethoxylane, dodecyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, methoxypropyl Pyrtrimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, octyltrimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, tetramethoxysilane, tolyl Alkoxy silanes such as trimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylethoxysilane, etc., and some or all of the alkoxy groups of these alkoxysilanes are chloro groups In addition, the alkoxy group of these alkoxysilanes or the chloro group of these chlorosilanes is added. Are decomposed include those which is a silanol group. Furthermore, deuterated compounds in which all or part of the hydrogen atoms of these alkoxysilanes and chlorosilanes are substituted with deuterium, or fluorinated compounds in which fluorine atoms are substituted are also included. These alkoxysilanes and chlorosilanes can be used alone or in combination of two or more. In particular, from the viewpoint of heat resistance, electrical properties, curability, mechanical properties, storage stability and handling properties, one or more selected from phenyltrimethoxysilane, methyltriethoxysilane and methyltrimethoxysilane should be used. preferable. Moreover, when using the silicon-containing curable composition of this invention for an optical material etc., such a deuteride or a fluorinated material is preferable.

  Examples of alkoxysilanes and chlorosilanes already having the reactive group (A ′) that can be used to synthesize the silicon-containing polymer precursor (1) include (3-acryloxypropyl) methyldimethoxysilane, ( 3-acryloxypropyl) trimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, butenyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyl Alkoxy silanes such as trimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, etc. All chlorosilanes given by substituting chloro groups are cited also include those in which the alkoxy group or chloro group of these chlorosilanes of these alkoxysilanes has a hydrolyzed silanol groups in addition. Further, deuterated compounds in which all or part of the hydrogen atoms of these alkoxysilanes and chlorosilanes are substituted with deuterium, and fluorinated compounds in which fluorine atoms are substituted are also included. These alkoxysilanes and chlorosilanes can be used alone or in combination of two or more. From the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability and handling properties, it is preferable to use vinyltrimethoxysilane and / or methacryloxymethyltrimethoxysilane. In addition, alkoxysilane and / or chlorosilane so that at least one other atom bonded to the silicon atom in the reactive group (A ′) when the silicon-containing polymer of component (A) is an oxygen atom. Is preferably selected. Moreover, when using the silicon-containing curable composition of this invention for an optical material etc., a deuteride or a fluorinated material is preferable.

  Two or more kinds of the alkoxysilane and / or chlorosilane used for obtaining the silicon-containing polymer precursor (1) may be used. In addition, as the alkoxysilane and / or chlorosilane, those treated with an alcoholate or complex of other metals can be used as desired, and only those treated or used together with those not treated. Then, hydrolysis / condensation reaction is performed, and an element other than silicon, such as boron, magnesium, aluminum, phosphorus, titanium, iron, zinc, zirconium, niobium, tin, tellurium, tantalum, etc. is added to the silicon-containing polymer (A). It can also be incorporated.

Hereinafter, the silicon-containing polymer precursor (2) will be described.
The silicon-containing polymer precursor (2) is a linear polysiloxane having a reactive group (2 ′) at its terminal. This reactive group (2 ′) may be any reactive group that can react with the reactive group (1 ′) of the silicon-containing polymer precursor (1) to form a covalent bond. Examples of the reactive group (2 ′) include a Si—OH group, a Si—R ³ —OH group, a Si—O—R ⁴ group, a Si—X group [wherein R ³ has 1 to 9 carbon atoms. An alkylene group or a phenylene group, R ⁴ is an alkyl group having 1 to 5 carbon atoms, and X is a halogen atom].

  The silicon-containing polymerization precursor (2) is a linear polysiloxane and hydrolyzes dialkyldichlorosilane, diphenyldichlorosilane, alkylphenyldichlorosilane, dialkyl dialkoxysilane, diphenyl dialkoxysilane, alkylphenyl dialkoxysilane, and the like. It can be obtained by hydrolysis / condensation reaction of a bifunctional alkoxysilane or chlorosilane having two functional alkoxy groups or chloro groups.

  Specific examples of the bifunctional alkoxysilane or chlorosilane that can be used for the silicon-containing polymerization precursor (2) include dimethyldichlorosilane, diphenyldichlorosilane, and methylphenyldichlorosilane. Organic silanes having chlorosilyl groups at both ends of the benzene ring (para-positions), such as 1,4-bis (dimethylchlorosilyl) benzene, can also be used. In addition, deuterated compounds in which all or a part of hydrogen atoms of these alkoxysilanes, chlorosilanes, and organosilanes are substituted with deuterium, or fluorinated compounds in which fluorine atoms are substituted can be used. One or two or more of these can be used for the silicon-containing polymerization precursor (2). Moreover, when using the silicon-containing curable composition of this invention for an optical material etc., it is preferable to use these deuterated or fluorinated materials.

  Further, the molecular weight (weight average molecular weight) of the silicon-containing polymer precursor (2) is preferably about 1,000 to 1,000,000, and more preferably 1,000 to 100,000. In addition, the silicon-containing polymer precursor (2) includes at least two types selected from dialkyldichlorosilane and diphenyldichlorosilane from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability, and handling properties. What was obtained by mixing and using is preferable.

Below, the manufacturing method of a silicon containing polymer precursor (1) and a silicon containing polymer precursor (2) is explained in full detail.
The hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane for obtaining the silicon-containing polymer precursor (1) and the silicon-containing polymer precursor (2), respectively, may be carried out by so-called sol-gel reaction. Examples of the sol-gel reaction method include a method of performing a hydrolysis / condensation reaction using a catalyst such as an acid or a base in the absence of a solvent or in a solvent. The solvent used at this time is not particularly limited, and specifically, water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran These can be used, and one of these can be used, or two or more can be mixed and used.

  In the hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane, alkoxysilane and / or chlorosilane generates silanol groups (Si-OH groups) by hydrolysis with water, and the generated silanol groups or silanol groups and The process proceeds by condensation of the alkoxy group. In order to advance this hydrolysis reaction, it is preferable to add an appropriate amount of water to the reaction system. Water may be added as a solvent alone or together with other solvents, or may be added after dissolving the catalyst. Moreover, this hydrolysis reaction also proceeds by a minute amount of moisture contained in moisture in the air or a solvent other than water.

  The catalyst such as acid and base used in the hydrolysis / condensation reaction is not particularly limited as long as it promotes the hydrolysis / condensation reaction, and specifically, inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, etc. Organic acids such as acetic acid, p-toluenesulfonic acid and monoisopropyl phosphate; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia; trimethylamine, triethylamine, monoethanolamine, diethanolamine, pyridine, etc. Amine compounds (organic bases); titanium compounds such as tetraisopropyl titanate and tetrabutyl titanate; tin compounds such as dibutyltin laurate and octylstannic acid; boron compounds such as trifluoroborane; aluminum such as aluminum trisacetylacetate Compounds: iron, cobalt, manganese, zinc Metal chlorides, and metal carboxylates such as naphthenate and octoate salts of these metals, and the like, also the use of these kind may be used in combination of two or more. The hydrolysis / condensation reaction is preferably performed by a method in which an acid catalyst is added and the reaction is allowed to proceed under acidic conditions (less than pH 7), and then a basic catalyst is added to perform further reaction under neutral to basic conditions.

  The order of the above hydrolysis / condensation reaction is not particularly limited, and when performing hydrolysis / condensation reaction of two or more kinds of alkoxysilane and / or chlorosilane, the hydrolysis / condensation reaction is carried out to some extent individually. These may be mixed and further subjected to hydrolysis / condensation reaction, or all may be mixed and subjected to hydrolysis / condensation reaction at once.

Hereinafter, a method for producing a silicon-containing polymer (A) using the silicon-containing polymer precursor (1) and the silicon-containing polymer precursor (2) will be described.
The silicon-containing polymer of component (A) is a silicon-containing polymer having no reactive group (A ′) and no reactive group (A ′) in the silicon-containing polymer precursor (1). By performing a condensation reaction between the reactive groups (2 ′) of the polymer precursor (2) to form a covalent bond, a silicon-containing polymer precursor (3) having no reactive group (A ′) is obtained. After being obtained, it can be obtained by introducing a reactive group (A ′) into the silicon-containing polymer precursor (3).
In addition, the silicon-containing polymer of the component (A) is prepared by introducing a reactive group (A ′) in advance into the silicon-containing polymer precursor (1) and / or (2), and the silicon-containing polymer precursor. It can also be obtained by performing a condensation reaction between the reactive group (1 ′) of (1) and the reactive group (2 ′) of the silicon-containing polymer precursor (2) to form a covalent bond.
Of course, the reactive group (A ′) may be further introduced into the silicon-containing polymer (A) having the reactive group (A ′).
Thus, the type and timing of the introduction reaction of the reactive group (A ′) are not particularly limited. For example, the reactive group (A ′) has one reactive group (A ′) with respect to the Si—OH group in the silicon-containing polymer precursor. A chlorine-substituted (monochloro) silane such as dimethylvinylchlorosilane or diphenylvinylchlorosilane may be reacted. This reaction can be performed, for example, at a reaction temperature of 0 to 100 ° C. and for a reaction time of 0.1 to 4 hours.

  The reaction ratio of the silicon-containing polymer precursors (1) and (2) is 1:99 to 99 in terms of molar ratio from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability and handling properties. A range of: 1 is preferred. In the condensation reaction of the silicon-containing polymer precursors (1) and (2), the reaction temperature is preferably 0 to 150 ° C., and the reaction time is preferably 0.1 to 4 hours.

  The molecular weight of the silicon-containing polymer (A) is, in terms of polystyrene, a weight average molecular weight of 100 to 1,000,000, preferably 1,000 to 100,000. If it is less than 100, desirable physical properties cannot be obtained, and if it is greater than 1 million, it cannot be combined at the nanometer order or molecular level, and the resulting cured product becomes non-uniform or opaque, Sufficiently good physical properties cannot be obtained.

The concentration of the reactive group (A ′) of the silicon-containing polymer (A) is preferably from 0.0001 to 100 mmol / g, more preferably from 0.001 to 10 mmol / g, from the viewpoints of curability and storage stability. preferable.
Further, the number of reactive groups (A ′) in the silicon-containing polymer of the component (A) is not particularly limited depending on the molecular weight of the silicon-containing polymer (A), but the silicon-containing polymer ( A) One or more per molecule, and preferably one or less per one silicon atom in the silicon-containing polymer (A).

  Further, when the silicon-containing polymer precursors (1) and (2) used for the component (A) have Si—OH groups, Si—OH groups are reacted with alkylchlorosilanes to react with Si—OH groups. Storage stability and the like can be improved by adjusting the number of OH groups. As the alkylchlorosilane, monochlorinated (monochloro) silane such as trimethylchlorosilane can be used. Moreover, the number of Si-OH groups can be adjusted also by processing with a hydrolysable ester compound. As the hydrolyzable ester compound, orthoformate ester, orthoacetate ester, tetraalkoxymethane, carbonate ester and the like can be used.

  In addition, in the silicon-containing curable composition of the present invention, the content of the silicon-containing polymer (A) is preferably 1 to 99% by weight, preferably 10 to 90% by weight, from the viewpoint of heat resistance and flexibility. Is more preferable.

Next, the silicon-containing polymer (B) component (hereinafter also referred to as silicon-containing polymer (B)) will be described. As will be apparent from the following description, the silicon-containing polymer (B) conforms to the silicon-containing polymer (A), and has a Si—H group instead of the reactive group (A ′). Is.
The silicon-containing polymer as the component (B) has a Si—H group, has one or more cross-linked structures with Si—O—Si bonds, and has a molecular weight of 100 to 1,000,000. The molecular weight is a weight average molecular weight.

  In view of heat resistance, electrical properties, curability, mechanical properties, storage stability, and handling properties, at least one other bonded to the silicon atom in the Si-H group of the silicon-containing polymer of component (B) It is preferable that the atom is an oxygen atom.

  The component (B) can be obtained by forming a Si—O—Si siloxane bond by hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane having a functional group Si—H group. In addition, the component (B) is obtained by performing a hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane having no Si—H group to obtain a polymer having a Si—O—Si siloxane bond. It can also be obtained by introducing Si—H groups using reactive functional groups such as Si—OH and Si—Cl in the polymer. Moreover, you may obtain (B) component by using both together.

  The silicon-containing polymer as component (B) is obtained by further adding Si to the silicon-containing polymer precursor (3) obtained by reacting the silicon-containing polymer precursor (1) and the silicon-containing polymer precursor (2). Those obtained by introducing a -H group are preferred.

The silicon-containing polymer precursor (1) used for the silicon-containing polymer as the component (B) will be described below.
The silicon-containing polymer precursor (1) has at least one kind of reactive group (1 ′) that can react with the reactive group (2 ′) of the silicon-containing polymer precursor (2). This reactive group (1 ′) is a functional group that reacts with the reactive group (2 ′) to form a covalent bond. Examples thereof include Si—OH, Si—R ³ —OH, and Si—O—R. ⁴ , Si-X [wherein R ³ is an alkylene group having 1 to 9 carbon atoms or a phenylene group, R ⁴ is an alkyl group having 1 to 5 carbon atoms, and X is a halogen atom] Can do. This reactive group (1 ′) is preferably a Si—OH group, a Si—Cl group, a Si—O—CH ₃ group, or a Si—O—C ₂ H ₅ group, particularly a Si—OH group, from the viewpoint of reactivity. Si-Cl groups are preferred.

  The molecular weight (weight average molecular weight) of the silicon-containing polymer precursor (1) is preferably from 1,000 to 1,000,000, more preferably from 500 to 100,000, from the viewpoint of handleability.

  Moreover, the silicon-containing polymer precursor (1) has one or more cross-linked structures with Si—O—Si bonds. In the silicon-containing polymer precursor (1), the bridge structure by Si—O—Si bonds may be any of ladder-like (ladder-like), cage-like, annular, etc., as long as it is formed by Si—O—Si bonds. The bridge structure, ladder shape, cage shape, ring shape, etc. may all be composed of Si—O—Si bonds, and part of them may be formed of Si—O—Si bonds. May be. Of course, a plurality of Si—O—Si bonds may be repeated continuously.

  Moreover, the silicon-containing polymer precursor (1) may or may not have a Si—H group.

The silicon-containing polymer precursor (1) can be obtained by hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane.
As alkoxysilane and chlorosilane that can obtain the silicon-containing polymer precursor (1) by hydrolysis / condensation reaction, alkoxysilane or chlorosilane that already has Si-H group, alkoxysilane that does not have Si-H group, or A chlorosilane is mentioned.

  Examples of alkoxysilanes and chlorosilanes having no Si-H groups that can be used to synthesize the silicon-containing polymer precursor (1) include acetoxymethyltrimethoxysilane, benzyltriethoxysilane, bis (triethoxy Silyl) methane, bis (triethoxysilyl) ethane, bis (triethoxysilyl) hexane, 3-bromopropyltrimethoxysilane, butyltrimethoxysilane, chloromethyltriethoxysilane, chlorophenyltriethoxysilane, 3-chloropropyltrimethoxy Silane, diethyldiethoxysilane, dimethyldiethoxysilane, dimethyldimethoxylane, dodecyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, methoxypropyltri Toxisilane, methyltriethoxysilane, methyltrimethoxysilane, octyltrimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, tetramethoxysilane, tolyltrimethoxysilane , Diphenyl dimethoxy silane, diphenyl diethoxy silane, trimethyl methoxy silane, trimethyl ethoxy silane, triethyl ethoxy silane, triphenyl ethoxy silane etc. Chlorosilane, etc., in addition, the alkoxy group of these alkoxysilanes or the chloro group of these chlorosilanes is hydrolyzed. Also include those that are a silanol group. Furthermore, deuterated compounds in which all or part of the hydrogen atoms of these alkoxysilanes and chlorosilanes are substituted with deuterium, or fluorinated compounds in which fluorine atoms are substituted are also included. These alkoxysilanes and chlorosilanes can be used alone or in combination of two or more. In particular, it is preferable to use phenyltrimethoxysilane and / or methyltriethoxysilane from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability, and handling properties. Moreover, when using the silicon-containing curable composition of this invention for an optical material etc., a deuteride or a fluorinated material is preferable.

  Examples of alkoxysilanes and chlorosilanes already having Si-H groups that can be used to synthesize the silicon-containing polymer precursor (1) include dimethylchlorosilane, diethylchlorosilane, diphenylchlorosilane, and the like. In particular, dimethylchlorosilane is preferred from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability, and handling properties. In addition, it is preferable to select alkoxysilane and / or chlorosilane so that at least one other atom bonded to the silicon atom in the Si—H group when the component (B) is an oxygen atom. Moreover, when using the silicon-containing curable composition of this invention for an optical material etc., a deuteride or a fluorinated material is preferable.

  Two or more kinds of the alkoxysilane and / or chlorosilane used for obtaining the silicon-containing polymer precursor (1) may be used. Moreover, as said alkoxysilane and / or chlorosilane, what was processed with the alcoholate and complex of other elements as needed can also be used, and it uses together only with what was processed, or what has not been processed. Then, hydrolysis / condensation reaction is performed, and an element other than silicon, such as boron, magnesium, aluminum, phosphorus, titanium, iron, zinc, zirconium, niobium, tin, tellurium, tantalum, etc. is added to the silicon-containing polymer (B). It can also be incorporated.

The silicon-containing polymer precursor (2) used for the component (B) will be described below.
The silicon-containing polymer precursor (2) is a linear polysiloxane having a reactive group (2 ′) at its terminal. The reactive group (2 ′) may be any reactive group that can react with the reactive group (1 ′) of the silicon-containing polymer precursor (1) to form a covalent bond. Examples of the reactive group (2 ′) include a Si—OH group, a Si—R ³ —OH group, a Si—O—R ⁴ group, a Si—X group [wherein R ³ has 1 to 9 carbon atoms. An alkylene group or a phenylene group, R ⁴ is an alkyl group having 1 to 5 carbon atoms, and X is a halogen atom].

  The silicon-containing polymerization precursor (2) is a linear polysiloxane, and alkoxy groups such as dialkyldichlorosilane, diphenyldichlorosilane, alkylphenyldichlorosilane, dialkyldialkoxysilane, diphenyl dialkoxysilane, and alkylphenyl dialkoxysilane. Alternatively, it can be obtained by hydrolysis / condensation reaction of bifunctional hydrolyzable alkoxysilane having two chloro groups or chlorosilane.

  As the bifunctional hydrolyzable alkoxysilane or chlorosilane that can be used in the silicon-containing polymerization precursor (2), specifically, dimethyldichlorosilane, diphenyldichlorosilane, and methylphenyldichlorosilane are preferably used. Furthermore, organic silanes having chlorosilanes at both ends of the benzene rings (para positions), such as 1,4-bis (dimethylchlorosilyl) benzene, can also be used. In addition, deuterated compounds in which all or a part of hydrogen atoms of these alkoxysilanes, chlorosilanes, and organosilanes are substituted with deuterium, or fluorinated compounds in which fluorine atoms are substituted can be used. One or two or more of these can be used for the silicon-containing polymerization precursor (2). Moreover, when using the silicon-containing curable composition of this invention for an optical material etc., it is preferable to use these deuterated or fluorinated materials.

  Further, the molecular weight (weight average molecular weight) of the silicon-containing polymerization precursor (2) is preferably about 1,000 to 1,000,000, and more preferably 1,000 to 100,000. The silicon-containing polymerization precursor (2) is a mixture of two or more selected from dialkyldichlorosilane and diphenyldichlorosilane from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability and handling properties. What was obtained by using is preferable.

Below, the manufacturing method of a silicon containing polymer precursor (1) and a silicon containing polymer precursor (2) is explained in full detail.
Hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane to obtain silicon-containing polymer precursors (1) and (2) used for component (B) is a silicon-containing polymer used for component (A). What is necessary is just to perform by the so-called sol-gel reaction similar to the hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane to obtain the precursors (1) and (2), respectively. In order to advance this reaction, it is preferable to add an appropriate amount of water as described above. In addition, various catalysts for promoting the hydrolysis / condensation reaction may be used. For example, an acid catalyst that promotes hydrolysis / condensation reaction is added and the reaction is allowed to proceed under acidic conditions (less than pH 7), and then a base catalyst that promotes hydrolysis / condensation reaction is added to neutral or basic reaction. A method in which the reaction is carried out is preferred. The order of the hydrolysis / condensation reaction is not particularly limited as described above.

Hereinafter, a method for producing a silicon-containing polymer (B) using the silicon-containing polymer precursor (1) and the silicon-containing polymer precursor (2) will be described.
The silicon-containing polymer of component (B) is a silicon-containing polymer precursor having no reactive group (1 ′) and no Si—H group in the silicon-containing polymer precursor (1) having no Si—H group. A silicon-containing polymer precursor (3) having no Si—H group is obtained by performing a condensation reaction between the reactive groups (2 ′) of (2) to form a covalent bond, and then the silicon It can be obtained by introducing Si-H groups into the containing polymer precursor (3).
In addition, the silicon-containing polymer as the component (B) is obtained by introducing Si—H groups in advance into the silicon-containing polymer precursor (1) and / or (2), and the silicon-containing polymer precursor (1). ) And a reactive group (2 ′) of the silicon-containing polymer precursor (2) to form a covalent bond.
Of course, Si-H groups may be further introduced into the silicon-containing polymer (B) having Si-H groups.
Thus, the type and timing of the Si—H group introduction reaction are not particularly limited. For example, the Si—OH group in the silicon-containing polymer precursor is substituted with a monochlorine group (monochloro group having a Si—H group). ) Silane such as dimethylchlorosilane, diphenylchlorosilane, etc. may be reacted. This reaction can be performed, for example, at a reaction temperature of 0.1 to 100 ° C. and a reaction time of 0.1 to 4 hours.

  The reaction ratio of the silicon-containing polymer precursors (1) and (2) is 1:99 to 99 in terms of molar ratio from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability and handling properties. A range of: 1 is preferred. In the condensation reaction of the silicon-containing polymer precursors (1) and (2), the reaction temperature is preferably 0 to 150 ° C., and the reaction time is preferably 0.1 to 4 hours.

  The weight average molecular weight of the silicon-containing polymer (B) is from 1,000 to 1,000,000, preferably from 1,000 to 100,000, in terms of polystyrene. If it is less than 100, desirable physical properties cannot be obtained, and if it is greater than 1 million, it cannot be combined at the nanometer order and molecular level, and the resulting cured product becomes non-uniform or opaque. Sufficiently good physical properties cannot be obtained.

Finally, the concentration of Si-H groups of the silicon-containing polymer (B) is 0.001 to 100 mmol / g from the viewpoint of heat resistance, electrical properties, curability, mechanical properties, storage stability and handling properties. Preferably, 0.01 to 10 mmol / g is more preferable.
Further, the number of Si—H groups in the silicon-containing polymer of the component (B) is not particularly limited by the molecular weight of the silicon-containing polymer (B) to be obtained, but the silicon-containing polymer ( 1 or more per molecule of B), and preferably 1 or less per silicon atom in the silicon-containing polymer (B).

  In addition, when the silicon-containing polymer precursors (1) and (2) used for the component (B) have Si—OH groups, the Si—OH group is reacted with alkylchlorosilane to react with Si— Storage stability and the like can be improved by adjusting the number of OH groups. As the alkylchlorosilane, monochlorinated (monochloro) silane such as trimethylchlorosilane can be used. Moreover, the number of Si-OH groups can be adjusted also by processing with a hydrolysable ester compound. As the hydrolyzable ester compound, orthoformate ester, orthoacetate ester, tetraalkoxymethane, carbonate ester and the like can be used.

  In the silicon-containing curable composition of the present invention, the content of the silicon-containing polymer as the component (B) is preferably 1 to 99% by weight, more preferably 10 to 90% by weight from the viewpoint of heat resistance and mechanical properties. .

In the silicon-containing curable composition of the present invention, the content ratio of the silicon-containing polymer (A) and the silicon-containing polymer (B) (the former: the latter, on a weight basis) is curable and heat resistant. In view of the mechanical properties, 1:99 to 99: 1 is preferable, and 10:90 to 90:10 is more preferable.
In the silicon-containing curable composition of the present invention, the ratio of the reactive group (A ′) and the Si—H group (the former: the latter, on a molar basis) is 20: from the viewpoint of curability, heat resistance, and mechanical properties. 80-80: 20 is preferable and 40: 60-60: 40 is more preferable.

Next, the silicon-containing polymer (C) (hereinafter also referred to as silicon-containing polymer (C)) will be described. As will be apparent from the following description, the silicon-containing polymer (C) conforms to the silicon-containing polymer (A), and in addition to the reactive group (A ′), Si—H groups are also present. It is what you have.
The silicon-containing polymer (C) is composed of Si—CH═CH ₂ , Si—R ¹ —CH═CH ₂ and Si—R ¹ —OCOC (R ² ) ═CH ₂ [wherein R ¹ is the number of carbon atoms. 1 to 9 alkylene groups or phenylene groups, and R ² is hydrogen or a methyl group]. One or more reactive groups (A ′) selected from the group consisting of And it has one or more bridge | crosslinking structures by Si-O-Si bond, and the molecular weight is 1 million. The molecular weight is a weight average molecular weight.

R ¹ is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of heat resistance and electrical properties of the cured product.
The reactive group (A ′) is particularly preferably Si—CH═CH ₂ from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability, and handling properties.
In addition, from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability and handling properties, it is bonded to the silicon atom in the reactive group (A ′) of component (C) or the silicon atom in the Si—H group. The other at least one atom is preferably an oxygen atom.

  The component (C) is composed of an alkoxysilane and / or chlorosilane having a reactive group (A ′), and a Si—O—Si siloxane by hydrolysis / condensation reaction of an alkoxysilane and / or chlorosilane having a Si—H group. It can be obtained by forming a bond. Of course, alkoxysilane and / or chlorosilane having both reactive group (A ′) and Si—H group may be used, and those having both and those having only one may be used in combination. Moreover, (C) component performs the hydrolysis and condensation reaction of the alkoxysilane which does not have a reactive group (A ') and / or Si-H group, and / or chlorosilane, and carries out the siloxane bond of Si-O-Si. Having a reactive group (A ′) and / or a polymer having no Si—H group, and using a reactive functional group such as Si—OH or Si—Cl in the polymer, It can also be obtained by introducing reactive groups (A ′) and / or Si—H groups. Moreover, you may obtain (C) component using these methods together.

  In particular, the silicon-containing polymer of component (C) is obtained by reacting the silicon-containing polymer precursor (3) obtained by reacting the silicon-containing polymer precursor (1) and the silicon-containing polymer precursor (2). Furthermore, what was obtained by introduce | transducing a reactive group (A ') and / or Si-H group is preferable.

  The silicon-containing polymer precursor (1) used for the component (C) will be described below.

The silicon-containing polymer precursor (1) has at least one kind of reactive group (1 ′) that can react with the reactive group (2 ′) of the silicon-containing polymer precursor (2). This reactive group (1 ′) is a functional group that reacts with the reactive group (2 ′) to form a covalent bond. Examples thereof include Si—OH, Si—R ³ —OH, and Si—O—R. ⁴ , Si-X [wherein R ³ is an alkylene group having 1 to 9 carbon atoms or a phenylene group, R ⁴ is an alkyl group having 1 to 5 carbon atoms, and X is a halogen atom] Can do. This reactive group (1 ′) is preferably a Si—OH group, a Si—Cl group, a Si—O—CH ₃ group, or a Si—O—C ₂ H ₅ group, particularly a Si—OH group, from the viewpoint of reactivity. Si-Cl groups are preferred.

  Further, the molecular weight (weight average molecular weight) of the silicon-containing polymer precursor (1) is preferably about 1,000 to 1,000,000, more preferably 500 to 100,000, from the viewpoint of handleability.

  Moreover, the silicon-containing polymer precursor (1) has one or more cross-linked structures with Si—O—Si bonds. In the silicon-containing polymer precursor (1), the bridge structure by Si—O—Si bonds may be any of ladder-like (ladder-like), cage-like, annular, etc., as long as it is formed by Si—O—Si bonds. The bridge structure, ladder shape, cage shape, ring shape, etc. may all be composed of Si—O—Si bonds, and part of them may be formed of Si—O—Si bonds. May be. Of course, a plurality of Si—O—Si bonds may be repeated continuously.

In addition, the silicon-containing polymer precursor (1) includes Si—CH═CH ₂ , Si—R ¹ —CH═CH ₂ and Si—R ¹ —OCOC (R ² ) = CH ₂ [wherein R ¹ is It is a C1-C9 alkylene group or a phenylene group, and R < ² > is hydrogen or a methyl group], and may have one or more reactive groups (A ') selected from the group consisting of, or It may not have. Moreover, the silicon-containing polymer precursor (1) may or may not have a Si—H group.

The silicon-containing polymer precursor (1) can be obtained by hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane.
As alkoxysilane and chlorosilane that can obtain the silicon-containing polymer precursor (1) by hydrolysis / condensation reaction, alkoxysilane or chlorosilane having neither reactive group (A ′) nor Si—H group, reaction Examples include alkoxysilane or chlorosilane having a group (A ′) and / or a Si—H group.

  Examples of alkoxysilanes and chlorosilanes that have no reactive groups (A ′) and Si—H groups that can be used to synthesize the silicon-containing polymer precursor (1) of the present invention include acetoxymethyltri Methoxysilane, benzyltriethoxysilane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, bis (triethoxysilyl) hexane, 3-bromopropyltrimethoxysilane, butyltrimethoxysilane, chloromethyltriethoxysilane Chlorophenyltriethoxysilane, 3-chloropropyltrimethoxysilane, diethyldiethoxysilane, dimethyldiethoxysilane, dimethyldimethoxylane, dodecyltrimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, butyltrimethyl Xysilane, methoxypropyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, octyltrimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, tetramethoxy Silane, tolyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylethoxysilane, and other alkoxysilanes, and some or all of the alkoxy groups of these alkoxysilanes Chlorosilane substituted with chloro group, etc., in addition to the alkoxy group of these alkoxysilanes or Chloro group Roshiran also include those that are a hydrolyzed to silanol groups. Furthermore, deuterated compounds in which all or part of the hydrogen atoms of these alkoxysilanes and chlorosilanes are substituted with deuterium, or fluorinated compounds in which fluorine atoms are substituted are also included. These alkoxysilanes and chlorosilanes can be used alone or in combination of two or more. In particular, it is preferable to use phenyltrimethoxysilane and / or methyltriethoxysilane from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability, and handling properties. Moreover, when using the silicon-containing curable composition of this invention for an optical material etc., a deuteride or a fluorinated material is preferable.

  Examples of alkoxysilanes and chlorosilanes already having a reactive group (A ′) include (3-acryloxypropyl) methyldimethoxysilane, (3-acryloxypropyl) trimethoxysilane, allyldimethoxysilane, allyltrimethoxysilane, allyl Triethoxysilane, butenyltriethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyltrimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinyl Examples include alkoxysilanes such as triethoxysilane and vinyltrimethoxysilane, and chlorosilanes in which some or all of the alkoxy groups of these alkoxysilanes are substituted with chloro groups. Also include those in which the alkoxy group or chloro group of these chlorosilanes of these alkoxysilanes has a hydrolyzed silanol groups in addition. Further, deuterated compounds in which all or part of the hydrogen atoms of these alkoxysilanes and chlorosilanes are substituted with deuterium, and fluorinated compounds in which fluorine atoms are substituted are also included. These alkoxysilanes and chlorosilanes can be used alone or in combination of two or more. From the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability and handling properties, it is preferable to use triethoxyvinylsilane and / or trimethoxyvinylsilane. Moreover, it is preferable to select alkoxysilane and / or chlorosilane so that at least one other atom bonded to the silicon atom in the reactive group (A ′) is an oxygen atom. Moreover, when using the silicon-containing curable composition of this invention for an optical material etc., a deuteride or a fluorinated material is preferable.

  Examples of alkoxysilanes and chlorosilanes already having Si-H groups that can be used to synthesize the silicon-containing polymer precursor (1) include dimethylchlorosilane, diethylchlorosilane, diphenylchlorosilane, and the like. In particular, dimethylchlorosilane is preferred from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability, and handling properties. Moreover, it is preferable to select alkoxysilane and / or chlorosilane so that at least one other atom bonded to the silicon atom in the Si—H group is an oxygen atom when the component (C) is used. Moreover, when using the silicon-containing curable composition of this invention for an optical material etc., the deuterated or fluorinated thing of alkoxysilane or chlorosilane is preferable.

  Examples of alkoxysilanes or chlorosilanes that already have both reactive groups (A ′) and Si—H groups that can be used to synthesize the silicon-containing polymer precursor (1) include dimethoxyvinylsilane, diethoxyvinylsilane, Methyl methoxy vinyl silane, phenyl methoxy vinyl silane, methyl ethoxy vinyl silane, phenyl ethoxy vinyl silane, dimethoxy allyl silane, diethoxy allyl silane, methyl methoxy allyl silane, phenyl methoxy allyl silane, methyl ethoxy allyl silane, phenyl ethoxy allyl silane, and some alkoxy groups of these alkoxy silanes Or, chlorosilane or the like in which all are substituted with chloro groups, and in addition, the alkoxy group of alkoxysilane or the chloro group of chlorosilane is hydrolyzed. Also include those that are a silanol group. Furthermore, deuterated compounds in which all or part of the hydrogen atoms of these alkoxysilanes and chlorosilanes are substituted with deuterium, or fluorinated compounds in which fluorine atoms are substituted are also included. These alkoxysilanes and chlorosilanes can be used alone or in combination of two or more. In particular, from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability, handling properties, and the like, methylmethoxyvinylsilane, phenylmethoxyvinylsilane, dimethoxyvinylsilane, and silane compounds in which these alkoxy groups are substituted with chloro groups are preferable.

  Two or more kinds of the alkoxysilane and / or chlorosilane used for obtaining the silicon-containing polymer precursor (1) may be used. Moreover, as said alkoxysilane and / or chlorosilane, what was processed with the alcoholate and complex of other elements as needed can also be used, and it uses together only with what was processed, or what has not been processed. Then, a hydrolysis / condensation reaction is performed, and an element other than silicon, for example, boron, magnesium, aluminum, phosphorus, titanium, iron, zinc, zirconium, niobium, tin, tellurium, tantalum, etc. is added to the silicon-containing polymer (C). It can also be incorporated.

The silicon-containing polymer precursor (2) used for the component (C) will be described below.
The silicon-containing polymer precursor (2) is a linear polysiloxane having a reactive group (2 ′) at its terminal. The reactive group (2 ′) may be any reactive group that can react with the reactive group (1 ′) of the silicon-containing polymer precursor (1) to form a covalent bond. Examples of the reactive group (2 ′) include a Si—OH group, a Si—R ³ —OH group, a Si—O—R ⁴ group, a Si—X group [wherein R ³ has 1 to 9 carbon atoms. An alkylene group or a phenylene group, R ⁴ is an alkyl group having 1 to 5 carbon atoms, and X is a halogen atom].

  The silicon-containing polymerization precursor (2) is a linear polysiloxane, and alkoxy groups such as dialkyldichlorosilane, diphenyldichlorosilane, alkylphenyldichlorosilane, dialkyldialkoxysilane, diphenyl dialkoxysilane, and alkylphenyl dialkoxysilane. Alternatively, it can be obtained by hydrolysis / condensation reaction of bifunctional hydrolyzable alkoxysilane having two chloro groups or chlorosilane.

  Specific examples of the bifunctional alkoxysilane or chlorosilane that can be used for the silicon-containing polymerization precursor (2) include dimethyldichlorosilane, diphenyldichlorosilane, and methylphenyldichlorosilane. Organic silanes having chlorosilanes at both ends (para positions) of the benzene ring, such as 1,4-bis (dimethylchlorosilyl) benzene, can also be used. In addition, deuterated compounds in which all or a part of hydrogen atoms of these alkoxysilanes, chlorosilanes, and organosilanes are substituted with deuterium, or fluorinated compounds in which fluorine atoms are substituted can be used. One or two or more of these can be used for the silicon-containing polymerization precursor (2). Moreover, when using the silicon-containing curable composition of this invention for an optical material etc., these deuterides or fluorinated compounds are preferable.

  The silicon-containing polymerization precursor (2) preferably has a molecular weight of about 100 to 1,000,000, more preferably 1,000 to 100,000. In addition, the silicon-containing polymerization precursor (2) is a mixture of two or more selected from dialkyldichlorosilane and diphenyldichlorosilane from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability and handling properties. What was obtained by using as a thing is preferable.

Below, the manufacturing method of a silicon containing polymer precursor (1) and a silicon containing polymer precursor (2) is explained in full detail.
Hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane to obtain silicon-containing polymer precursors (1) and (2) used in component (C) is a silicon-containing polymer used in component (A). What is necessary is just to perform by the so-called sol-gel reaction similar to the hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane to obtain the precursors (1) and (2), respectively. In order to advance this reaction, it is preferable to add an appropriate amount of water as described above. In addition, various catalysts for promoting the hydrolysis / condensation reaction may be used. For example, an acid catalyst that promotes hydrolysis / condensation reaction is added and the reaction is allowed to proceed under acidic conditions (less than pH 7), and then a base catalyst that promotes hydrolysis / condensation reaction is added to neutral or basic reaction. A method in which the reaction is carried out is preferred. The order of the hydrolysis / condensation reaction is not particularly limited as described above.

Hereinafter, a method for producing a silicon-containing polymer (C) using the silicon-containing polymer precursor (1) and the silicon-containing polymer precursor (2) will be described.
The silicon-containing polymer of component (C) includes a reactive group (A ′) and a reactive group (1 ′) and reactive group (A ′) of the silicon-containing polymer precursor (1) having no Si—H group. By performing a condensation reaction between the reactive groups (2 ′) of the silicon-containing polymer precursor (2) having no Si—H group to form a covalent bond, the reactive group (A ′) and the Si—H are formed. After obtaining a silicon-containing polymer precursor (3) having no group, it can be obtained by introducing a Si—H group and a reactive group (A ′) into the silicon-containing polymer precursor (3).
In addition, the silicon-containing polymer of component (C) is obtained by introducing either reactive group (A ′) or Si—H group into silicon-containing polymer precursor (1) and / or (2), The silicon-containing polymer precursor (3) having only one of the reactive group (A ′) and the Si—H group by performing a condensation reaction of the containing polymer precursors (1) and (2) to form a covalent bond. ), And then the silicon-containing polymer precursor (3) can be obtained by introducing either a Si—H group or a reactive group (A ′) that has not yet been introduced.
Further, the silicon-containing polymer of component (C) includes the reactive group (1 ′) and the reactive group (A ′) of the silicon-containing polymer precursor (1) having a reactive group (A ′) and an Si—H group. It can also be obtained by performing a condensation reaction between the reactive groups (2 ′) of the silicon-containing polymer precursor (2) having a Si—H group to form a covalent bond. Further, the reactive group (1 ′) of the silicon-containing polymer precursor (1) having only one of the reactive group (A ′) or the Si—H group, and the silicon-containing polymer precursor (1) do not have. It can also be obtained by performing a condensation reaction between reactive groups (2 ′) of the silicon-containing polymer precursor (2) having a reactive group (A ′) or Si—H group to form a covalent bond.
Of course, a reactive group (A ′) and / or a Si—H group may be further introduced into the silicon-containing polymer (C) having a reactive group (A ′) and a Si—H group.
Thus, the type and timing of the reactive group (A ′) and Si—H group introduction reaction are not particularly limited. For example, the reactive group (A ′) is a monochlorinated (monochloro) silane having a reactive group (A ′) such as dimethylvinylchlorosilane or diphenylchlorosilane with respect to the Si—OH group in the silicon-containing polymer precursor. The Si—H group can be introduced by reaction, and the Si—H group in the silicon-containing polymer precursor is substituted with a monochlorine (monochloro group) having a Si—H group such as dimethylchlorosilane or diphenylchlorosilane. ) It can be introduced by reacting silane. These reactions can be performed under the conditions (reaction temperature, reaction time) described in the description of the silicon-containing polymers (A) and (B).

  In addition, the reaction ratio of the silicon-containing polymer precursors (1) and (2) is from 1:99 to a molar ratio in terms of heat resistance, electrical properties, curability, mechanical properties, storage stability, and handling properties. 99: 1 is preferred. In the condensation reaction of the silicon-containing polymer precursors (1) and (2), the reaction temperature is preferably 0 to 150 ° C., and the reaction time is preferably 0.1 to 4 hours.

  The weight average molecular weight of the silicon-containing polymer (C) used in the present invention is from 1,000 to 1,000,000, preferably from 1,000 to 100,000, in terms of polystyrene. If it is less than 100, desirable physical properties cannot be obtained, and if it is greater than 1 million, it cannot be combined at the nanometer order and molecular level, and the resulting cured product becomes non-uniform or opaque. Sufficiently good physical properties cannot be obtained.

  The concentration of the reactive group (A ′) of the silicon-containing polymer (C) is preferably 0.0001 to 100 mmol / g, more preferably 0.001 to 10 mmol / g, from the viewpoint of curability and storage stability. Is preferred. The concentration of the reactive group Si-H group contained in the silicon-containing polymer of component (C) is preferably 0.0001 to 100 mmol / g, more preferably 0.001 to 10 mmol, from the viewpoint of curability and storage stability. / G is preferred.

  In addition, the number of reactive groups (A ′) in the silicon-containing polymer of component (C) is one or more on average per molecule of silicon-containing polymer (C) from the viewpoint of curability and storage stability. One or less is preferable per one silicon atom in the silicon-containing polymer (C). In addition, the number of reactive group Si—H groups in the silicon-containing polymer of component (C) is one or more on average per molecule of silicon-containing polymer, and one silicon atom in silicon-containing polymer (C). The number is preferably 1 or less.

  Further, when the silicon-containing polymer precursors (1) and (2) used for the component (C) have Si—OH groups, the Si—OH groups are reacted with alkylchlorosilanes to react with Si— Storage stability and the like can be improved by adjusting the number of OH groups. As the alkylchlorosilane, monochlorinated (monochloro) silane such as trimethylchlorosilane can be used. Moreover, the number of Si-OH groups can be adjusted also by processing with a hydrolysable ester compound. As the hydrolyzable ester compound, orthoformate ester, orthoacetate ester, tetraalkoxymethane, carbonate ester and the like can be used.

  The component (C) in the silicon-containing curable composition of the present invention may not be contained when both the component (A) and the component (B) are contained, but the content thereof is (C) The number of reactive groups (A ′) and functional groups Si—H groups in the component, and when they contain the component (A) and / or the component (B), those reactive groups (A ′) and / or functional groups What is necessary is just to select suitably considering the number of group Si-H groups. When both (A) component and (B) component are not contained, the preferable content of (C) component is the amount excluding the preferable content of (D) component and the preferable content of (E) component described later. It is. When the component (A) and / or the component (B) is contained, the content of the component (C) is the ratio of the reactive group (A ′) and the Si—H group in the silicon-containing polymer (the former: the latter, the mole). Is selected from the range of 20:80 to 80:20, particularly 40:60 to 60:40, in which case the content of component (C) is preferably in the range of 0 to 99% by weight. Is selected so as to satisfy the above molar ratio.

  Moreover, in the silicon-containing curable composition of the present invention, the total content of the silicon-containing polymer has a preferable upper limit excluding a preferable content of the component (D) and a preferable content of the component (E) described later. The preferred lower limit is 5% by weight.

Next, the platinum catalyst of component (D), which is an essential component of the present invention, will be described.
The (D) component platinum-based catalyst is a curing reaction catalyst. The platinum-based catalyst of component (D) is a catalyst that contains one or more metals of platinum, palladium, and rhodium and promotes the hydrosilylation reaction, and a known one can be used. Examples of the platinum catalyst used as a catalyst for hydrosilylation include platinum-carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde complex, etc. The compounds in which platinum in these catalysts is replaced with palladium or rhodium, which are also platinum-based metals, may be used, and these may be used alone or in combination of two or more. From the viewpoint of curability, those containing platinum are preferred, and specifically, platinum-carbonylvinylmethyl complexes are particularly preferred. In addition, so-called Wilkinson catalysts containing the above platinum-based metals, such as chlorotristriphenylphosphine rhodium (I), are also included in the platinum catalyst of component (D).

  The content of the component (D) in the silicon-containing curable composition of the present invention is preferably 0.000001 to 5% by weight, and 0.0001 to 1.0% by weight in terms of curability and storage stability. More preferred. If the amount is more than 5% by weight, the stability of the silicon-containing curable composition tends to be poor, and if it is less than 0.000001% by weight, it does not cure even when heat is applied.

Next, the iron group-containing complex of the component (E), which is an essential component of the present invention, will be described.
The iron group-containing complex (E) improves the heat resistance (5% weight loss temperature). The (E) component iron group-containing complex is not particularly limited as long as it is a complex containing at least one of iron, ruthenium, and osmium. Specific examples thereof include iron (III) acetylacetonate, hemin derivatives, Examples thereof include iron (III) diphenylpropane dionate, iron (III) acrylate, iron (III) meso-tetraphenylporphyrin chloride, iron (III) trifluoropentanedionate, iron carbonyl complex, ruthenium carbonyl complex and the like. Iron (III) acetylacetonate is preferred from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability and handling properties.

  The content of the iron group-containing complex of the component (E) in the silicon-containing curable composition of the present invention is 0.0001 in terms of heat resistance, electrical properties, curability, mechanical properties, storage stability, and handling properties. % By weight to 20% by weight is preferable, and 0.001% by weight to 1% by weight is more preferable.

  In addition, the content ratio of the platinum catalyst of component (D) to the iron group-containing complex of component (E) is a weight ratio in terms of heat resistance, electrical properties, curability, mechanical properties, storage stability, and handling properties. (The former: the latter) is preferably 1000: 1 to 1: 1000, more preferably 100: 1 to 1: 100.

  Moreover, you may mix | blend the free radical scavenger of (F) component as an arbitrary component with the silicon-containing curable composition of this invention. The free radical scavenger may be any antioxidant substance such as an antioxidant or a stabilizer, and specific examples thereof include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4- Hydroxyphenyl) propionate], dibutylhydroxytoluene (BHT), 2,6-di-t-butyl-paracresol (DBPC) and the like.

  The content of the free radical scavenger of the component (F) in the silicon-containing cured composition of the present invention is 0.1% by weight from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability, and handling properties. -50% by weight is preferable, and 1% by weight to 30% by weight is more preferable.

  In addition to the components (A) to (E), the silicon-containing curable composition of the present invention includes any components other than the component (F) as long as they do not impair the intended performance of the present invention. Other known various resins, fillers, additives and the like can be blended. Moreover, various organic functional groups can be bonded to any one or more of the component (A), the component (B), and the component (C) to further impart functions. In addition, a highly functional composite material in which the silicon-containing curable composition of the present invention or a cured product thereof is used as a matrix and other useful compounds are dispersed therein can also be produced.

Examples of various resins that can be arbitrarily blended include polyimide resins, polyalkylene glycol resins such as polyethylene glycol and polypropylene glycol, polyurethane resins, epoxy resins, phenol resins, polyester resins, melamine resins, and polyamide resins.
Examples of fillers that can be optionally blended include colloidal silica, silica filler, silica gel, minerals such as mica and montmorillonite, metal oxides such as aluminum oxide, zinc oxide, and silicon dioxide fine powder, silicon oxide fine powder, silicon nitride And ceramics such as aluminum nitride, boron nitride, silicon carbide, etc., which may be modified by organic modification treatment or the like.
Examples of the additive that can be optionally blended include an ultraviolet absorber, an antistatic agent, an antioxidant, a thermally conductive substance, and the like.

  The silicon-containing curable composition of the present invention comprises at least one silicon-containing polymer of the components (A), (B), and (C) (provided that (A) Both the component and the component (B)), the platinum catalyst of the component (D), and the iron group-containing complex of the component (E) are mixed and can be cured by heating. The curing method may be any of a method in which those components are mixed immediately before use and cured by heating, a method in which all components are mixed in advance and cured by heating when used.

The heating temperature for curing is preferably 0 to 300 ° C., and the curing reaction time (heating time) is preferably 1 to 6 hours. By performing a curing reaction under these suitable curing reaction conditions, a cured product having even better performance can be obtained from the silicon-containing curable composition of the present invention.

A cured product obtained by curing the silicon-containing curable composition of the present invention is particularly excellent in performance such as heat resistance, crack resistance, and electrical characteristics.
Regarding the heat resistance, it is preferable that the temperature causing a weight loss of 5% by weight of the cured product is 380 ° C. or higher, particularly 400 ° C. or higher. However, from the silicon-containing curable composition of the present invention, A cured product having properties can be obtained.
Moreover, the hardened | cured material which does not generate | occur | produce a crack can be obtained from the silicon-containing curable composition of this invention.
As for electrical characteristics, it is preferable that the leakage current of 2 microamperes is not more than 30000 volts at 25 ° C., and it is preferable that the leakage current of 2 microamperes is not more than 13000 volts at 300 ° C. However, a cured product having such excellent electrical properties can be obtained from the silicon-containing curable composition of the present invention.

  The silicon-containing curable composition of the present invention has a curing reaction due to the reaction of the reactive group (A ′) and the Si—H group due to the effects of the curing reaction catalyst (D) and the iron group-containing complex (E) which are platinum-based catalysts. Proceeds rapidly, and thus the obtained cured product has excellent physical properties. Excellent heat resistance, crack resistance and electrical properties, especially solvent resistance, alkali resistance, weather resistance, hardness, contamination resistance, flame resistance, moisture resistance, gas barrier properties, flexibility, elongation and strength, electrical insulation In addition, it is possible to obtain a material excellent in mechanical properties, optical properties, electrical properties and the like such as properties and low dielectric constant properties.

  Furthermore, since the silicon-containing curable composition of the present invention is uniform and transparent, it has good light transmittance such as ultraviolet rays, and can be photocured by adding a photoreactive catalyst. When photocuring, of course, a photoreactive monomer or resin may be further blended, and at least one of the (A) component, the (B) component, and the (C) component has a photoreactive group. You may do it.

  The silicon-containing curable composition of the present invention is excellent in storage stability, transparency, handling properties, curability, etc., and the cured product has crack resistance, heat resistance, solvent resistance, alkali resistance, weather resistance, optical properties, etc. The silicon-containing curable composition and the cured product of the present invention are excellent in various physical properties such as characteristics and electrical properties. It can be suitably used for applications such as films and building materials.

  Specifically, sealing materials such as display materials, optical materials, recording materials, and semiconductors in the field of electrical and electronic materials, high-voltage insulating materials, potting and sealing materials for the purpose of insulation, vibration proofing, waterproofing, and moisture proofing, plastics Prototype mold for parts, coating material, interlayer insulation film, insulation packing, heat shrink rubber tube, O-ring, sealant / protective material for display device, optical waveguide, optical fiber protective material, optical lens, adhesive for optical equipment It can be applied to high heat-resistant adhesives, high heat dissipation materials, high heat-resistant sealing materials, members for solar cells and fuel cells, solid electrolytes for batteries, insulating coating materials, photosensitive drums for copying machines, and gas separation membranes. It can also be applied to concrete protective materials, linings, soil injecting agents, sealing agents, cold storage materials, glass coatings, etc. in the civil engineering / building materials field. Furthermore, in the medical material field, the present invention can be applied to tubes, sealing materials, coating materials, sterilization device sealing materials, contact lenses, oxygen-enriched membranes, and the like.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further, this invention is not limited by these Examples. Note that “parts” and “%” in the following examples and the like are based on weight.

[Synthesis Example 1]
75 parts of phenyltrimethoxysilane and 25 parts of methyltriethoxysilane were mixed, and further 86 parts of 0.4% phosphoric acid aqueous solution was added, and the mixture was kept at 10 to 15 ° C. and stirred for 3 hours. 80 parts of ethanol was added to the reaction solution, and the reaction solution was neutralized with an aqueous sodium hydroxide solution, and then stirred at 60 ° C. for 30 minutes. After the reaction, ethanol and water were distilled off while adding 900 parts of toluene (azeotropic) to obtain a silicon-containing polymer precursor (1). As a result of analysis by GPC, the obtained silicon-containing polymer precursor (1) had a weight average molecular weight (Mw) of 5,000.

[Synthesis Example 2]
90 parts of dichlorodimethylsilane and 9 parts of dichlorodiphenylsilane were mixed and dropped into 100 parts of ion exchange water. After removing the aqueous layer from the reaction solution, polymerization was carried out at 250 ° C. for 2 hours while distilling off the remaining solvent (water). 20 parts of pyridine was added to the obtained reaction solution, and 20 parts of dichlorodimethylsilane was further added thereto, followed by stirring for 30 minutes. Thereafter, the resulting solution was depressurized while being heated at 250 ° C. to remove the low molecular weight component and pyridine hydrochloride to obtain a silicon-containing polymer precursor (2). As a result of analysis by GPC, the molecular weight (Mw) of this silicon-containing polymer precursor (2) was 50,000.

[Synthesis Example 3]
Using toluene as a solvent, 5 parts of the silicon-containing polymer precursor (1) obtained in Synthesis Example 1, 10 parts of pyridine, and 1.5 parts of trimethylchlorosilane were added and stirred at room temperature for 30 minutes. To this solution, 100 parts of the silicon-containing polymer precursor (2) obtained in Synthesis Example 2 was added, copolymerization was further performed for 4 hours with stirring, and ion exchange water was added to stop the copolymerization reaction. The silicon-containing polymer precursor (3) was obtained by removing pyridine hydrochloride and the like by washing with water. As a result of analysis by GPC, the molecular weight (Mw) was 92,000.

[Synthesis Example 4]
Using toluene as a solvent, 50 parts of the silicon-containing polymer precursor (3) obtained in Synthesis Example 3 and 5 parts of pyridine were added and mixed uniformly, and then the mixture was divided in half.
One part of the above mixture was added with 5 parts of dimethylvinylchlorosilane, stirred for 30 minutes at room temperature and further for 30 minutes at 70 ° C., and then washed with ion-exchanged water to remove pyridine hydrochloride, and a silicon-containing polymer ( A) was obtained. The obtained silicon-containing polymer (A) had a Si—CH═CH ₂ group, had one or more bridged structures by Si—O—Si bonds, and had a molecular weight (Mw) of 93,000. It was.
In addition, 5 parts of dimethylchlorosilane was added to the other of the above mixture, and after stirring at room temperature for 30 minutes and further at 70 ° C. for 30 minutes, pyridine hydrochloride was removed by washing with ion-exchanged water to remove the silicon-containing polymer. (B) was obtained. The obtained silicon-containing polymer (B) had an Si—H group, had one or more bridged structures by Si—O—Si bonds, and had a molecular weight (Mw) of 93,000.

[Synthesis Example 5]
Using toluene as a solvent, 50 parts of the silicon-containing polymer precursor (3) obtained in Synthesis Example 3 and 5 parts of pyridine were added, 5 parts of dimethylchlorosilane and 5 parts of dimethylvinylchlorosilane were further added, and 30 minutes at room temperature. Furthermore, after stirring for 30 minutes at 70 ° C., pyridine hydrochloride was removed by washing with ion-exchanged water to obtain a silicon-containing polymer (C). The obtained silicon-containing polymer (C) has a Si—CH═CH ₂ group and a Si—H group, has one or more cross-linked structures by Si—O—Si bonds, and has a molecular weight (Mw). 93,000.

[Example 1]
To a mixture of 50 parts of the silicon-containing polymer (A) obtained in the synthesis example and 50 parts of the silicon-containing polymer (B), 0.005 part of a platinum-carbonylvinylmethyl complex as a curing reaction catalyst (D), And 0.002 part of iron (III) acetylacetonate was mixed as an iron group containing complex (E), and silicon-containing curable composition-1 was obtained. This was subjected to a curing reaction at 250 ° C. for 3 hours to obtain a cured product-1.

[Example 2]
To a mixture of 50 parts of the silicon-containing polymer (A) obtained in Synthesis Example and 50 parts of the silicon-containing polymer (B), 0.005 part of a platinum-carbonylvinylmethyl complex as a curing reaction catalyst (D), And 0.01 part of iron (III) acetylacetonate was mixed as an iron group containing complex (E), and silicon-containing curable composition-2 was obtained. This was subjected to a curing reaction at 250 ° C. for 3 hours to obtain a cured product-2.

[Example 3]
To a mixture of 50 parts of the silicon-containing polymer (A) obtained in the synthesis example and 50 parts of the silicon-containing polymer (B), 0.005 part of a platinum-carbonylvinylmethyl complex as a curing reaction catalyst (D), And 0.05 part of iron (III) acetylacetonate was mixed as an iron group containing complex (E), and the silicon containing curable composition-3 was obtained. This was subjected to a curing reaction at 250 ° C. for 3 hours to obtain a cured product-3.

[Example 4]
To a mixture of 50 parts of the silicon-containing polymer (A) obtained in the synthesis example and 50 parts of the silicon-containing polymer (B), 0.005 part of a platinum-carbonylvinylmethyl complex as a curing reaction catalyst (D), And 0.1 part of iron (III) acetylacetonate was mixed as an iron group containing complex (E), and silicon-containing curable composition-4 was obtained. This was subjected to a curing reaction at 250 ° C. for 3 hours to obtain a cured product-4.

[Example 5]
To a mixture of 50 parts of the silicon-containing polymer (A) obtained in the synthesis example and 50 parts of the silicon-containing polymer (B), 0.005 part of a platinum-carbonylvinylmethyl complex as a curing reaction catalyst (D), And 0.25 part of iron (III) acetylacetonate was mixed as an iron group containing complex (E), and silicon-containing curable composition-5 was obtained. This was subjected to a curing reaction at 250 ° C. for 3 hours to obtain a cured product-5.

[Example 6]
To a mixture of 50 parts of the silicon-containing polymer (A) obtained in the synthesis example and 50 parts of the silicon-containing polymer (B), chlorotristriphenylphosphine rhodium (I) 0. 005 parts and 0.05 part of iron (III) acetylacetonate as an iron group-containing complex (E) were mixed to obtain a silicon-containing curable composition-6. This was subjected to a curing reaction at 250 ° C. for 3 hours to obtain a cured product-6.

[Example 7]
To a mixture of 50 parts of the silicon-containing polymer (A) obtained in the synthesis example and 50 parts of the silicon-containing polymer (B), 0.005 part of a platinum-carbonylvinylmethyl complex as a curing reaction catalyst (D), And 0.05 part of ruthenium carbonyl complexes were mixed as an iron group containing complex (E), and silicon-containing curable composition-7 was obtained. This was subjected to a curing reaction at 250 ° C. for 3 hours to obtain a cured product-7.

[Example 8]
To 100 parts of the silicon-containing polymer (C) obtained in the synthesis example, 0.005 part of a platinum-carbonylvinylmethyl complex as a curing reaction catalyst (D) and iron (III) acetylacetate as an iron group-containing complex (E) 0.05 part of the acidate was mixed to obtain a silicon-containing curable composition-8. This was subjected to a curing reaction at 250 ° C. for 3 hours to obtain a cured product-8.

[Comparative Example 1]
To a mixture of 50 parts of the silicon-containing polymer (A) obtained in the synthesis example and 50 parts of the silicon-containing polymer (B), 0.005 part of a platinum-carbonylvinylmethyl complex is used as a curing reaction catalyst (D). The mixture was mixed and subjected to a curing reaction at 250 ° C. for 3 hours, and the resulting cured product was designated as comparative cured product-1.

[Comparative Example 2]
To a mixture of 50 parts of the silicon-containing polymer (A) obtained in the synthesis example and 50 parts of the silicon-containing polymer (B), chlorotristriphenylphosphine rhodium (I) 0. 005 parts were mixed and cured at 250 ° C. for 3 hours, and the resulting cured product was designated as comparative cured product-2.

[Comparative Example 3]
To a mixture of 50 parts of the silicon-containing polymer (A) obtained in the synthesis example and 50 parts of the silicon-containing polymer (B), 0.005 part of a platinum-carbonylvinylmethyl complex as a curing reaction catalyst (D), Then, 0.01 part of nickel (II) acetylacetonate was mixed and cured at 250 ° C. for 3 hours, and the resulting cured product was designated as comparative cured product-3.

<Heat resistance test>
A heat resistance test was performed for each of the cured products -1 to 8 and comparative cured products -1 to 3 obtained in Examples 1 to 8 and Comparative Examples 1 to 3. Moreover, the heat resistance test was done also about the comparative hardened | cured material-4 obtained from the commercially available silicone rubber.
The heat resistance test was performed by heating each cured product in air at a heating rate of 10 ° C./min and measuring the temperature at which the weight was reduced by 5%.
The results are shown in Table 1. From the results of Table 1, it was found that the cured product obtained from the silicon-containing curable composition of the present invention had higher heat resistance than the cured product cured without using the component (E).

<Electrical characteristics (leakage current) test>
After fixing one side of a glass cylindrical tube having an inner diameter of 20 mm and a height of 20 mm to a 40 mm square aluminum plate, and adding the silicon-containing curable composition to almost half of the glass cylindrical tube, a copper wire Is immersed in a silicon-containing curable composition so that the distance from the aluminum plate to the tip of the copper wire is 2 mm in the vertical direction in the glass cylindrical tube, and then at 200 ° C. And cured for 6 hours to obtain a test sample. The cured test sample is put in an oven, and a copper wire is placed on the positive electrode and an aluminum plate is placed on the negative electrode, and voltage is applied. At each temperature condition of 25 ° C. and 300 ° C., the leakage current is 2 The voltage (V) when the microampere was reached was measured.
The test was conducted on the silicon-containing curable compositions 1 to 3 and 8 obtained in Examples 1 to 3 and 8, respectively. Further, a commercially available silicone rubber was also tested as Comparative Example 4.
The results are shown in Table 2. In Table 2, “30000 ↑” indicates that it exceeded 30000 volts.

Claims (8)

Contains at least one silicon-containing polymer among the following (A) component, (B) component, and (C) component (however, when (C) component is not included, both (A) component and (B) component) And a silicon-containing curable composition containing the following components (D) and (E).
Component (A): Si—CH═CH ₂ , Si—R ¹ —CH═CH ₂ and Si—R ¹ —OCOC (R ² ) ═CH ₂ [wherein R ¹ is an alkylene group having 1 to 9 carbon atoms. Or a phenylene group, and R ² is hydrogen or a methyl group], having one or more reactive groups (A ′) selected from the group consisting of one group and a cross-linked structure with a Si—O—Si bond. A silicon-containing polymer having a molecular weight of 1,000,000 to 1,000,000 (excluding those having a Si-H group);
Component (B): A silicon-containing polymer having Si—H groups, having one or more cross-linked structures by Si—O—Si bonds, and having a molecular weight of 1,000,000 to 1,000,000 (however, the above reactive groups ( Except those having A ′);
Component (C): One or more of the above reactive groups (A ′), a Si—H group, one or more cross-linked structures with Si—O—Si bonds, and a molecular weight of 100 A silicon-containing polymer of ~ 1 million;
(D) component: a curing reaction catalyst which is a platinum-based catalyst;
(E) Component: Iron group-containing complex The component (A) is Si—OH, Si—R ³ —OH, Si—O—R ⁴ and Si—X [wherein R ³ is an alkylene group having 1 to 9 carbon atoms or a phenylene group; ⁴ is an alkyl group having 1 to 5 carbon atoms, and X is a halogen atom], a silicon-containing polymer precursor (1) having one or more reactive groups (1 ′) selected from the group consisting of In addition, the silicon-containing polymer precursor (2), which is a linear polysiloxane having a reactive group (2 ′) that can react with the reactive group (1 ′) to form a covalent bond at the terminal, is obtained. The silicon-containing curable composition according to claim 1, which is obtained by further introducing the reactive group (A ') into the silicon-containing polymer precursor (3).   The silicon-containing curable composition according to claim 1 or 2, wherein the component (B) is obtained by further introducing Si-H groups into the silicon-containing polymer precursor (3).   The component (C) is obtained by further introducing the reactive group (A ′) and / or Si—H group into the silicon-containing polymer precursor (3). The silicon-containing curable composition according to any one of the above.   5. The silicon-containing curability according to claim 1, wherein at least one other atom bonded to the silicon atom in the reactive group (A ′) of the component (A) is an oxygen atom. Composition.   The silicon-containing curable composition according to any one of claims 1 to 5, wherein at least one other atom bonded to the silicon atom in the Si-H group of the component (B) is an oxygen atom. .   The silicon atom in the reactive group (A ') of the component (C) or at least one other atom bonded to the silicon atom in the Si-H group is an oxygen atom. The silicon-containing curable composition according to claim 1. Hardened | cured material formed by thermosetting the silicon-containing curable composition of any one of Claims 1-7.