JP5248032B2 - Silicon-containing compound, curable composition, and cured product - Google Patents

Description

  The present invention relates to a novel silicon-containing compound having a specific structure, a curable composition containing the compound, and a cured product obtained by thermally curing the composition, and more particularly to handling properties and curability. The present invention relates to a silicon-containing compound that provides a curable composition that forms a cured product excellent in transparency, flexibility, and a curable composition containing the same, and a cured product excellent in transparency and flexibility.

  Various researches have been conducted on composite materials combining organic and inorganic materials, and industrially, techniques for combining inorganic fillers with organic polymers, and coatings that modify metal surfaces with organic polymers. These methods are 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 an organic / inorganic composite material includes a chemical bond type in which one material and the other material are bonded at a molecular level through 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. The sol-gel method is often used as a method for synthesizing inorganic materials used in these organic-inorganic composite materials. This sol-gel method involves hydrolysis of precursor molecules followed by polycondensation. This reaction is a reaction in which a crosslinked inorganic oxide is 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 the alkyltrialkoxysilane, after the polycondensation of methyltrimethoxysilane, a long-chain alkyltrialkoxysilane having a slow polycondensation rate is added, Sealing the silanol groups in the polysiloxane, and further performing a polycondensation reaction of methyltrimethoxysilane using an aluminum catalyst, adding acetylacetone when the molecular weight is reached, and distributing it in the reaction system. We are trying to improve storage stability by exchanging ligands. However, these methods have been insufficient in improving storage stability. In addition, the inorganic material obtained by the sol-gel method has a problem in flexibility.

  On the other hand, a curable composition containing a specific silicon-containing polymer has been proposed as a chemically bonded organic / inorganic composite material. For example, Patent Document 1 discloses a silicon-containing polymer (A) having a crosslinked structure and an alkenyl or alkynyl group, a silicon-containing polymer (B) having a crosslinked structure and a silane group, and a platinum-based polymer. A silicon-containing curable composition containing a catalyst (D), excellent in handling properties and curability, and excellent in heat resistance of the resulting cured product is disclosed. However, this silicon-containing curable composition does not necessarily have sufficient curing characteristics, and has a problem that a cured product having sufficient performance cannot be obtained at a low temperature in a short time.

The Chemical Society of Japan, No. 9, 571 (1998) JP 2005-325174 A

  The objective of this invention is providing the curable composition which is excellent in handling property and sclerosis | hardenability, and the obtained hardened | cured material is excellent in transparency and flexibility.

  As a result of investigations to solve the above-mentioned problems, the present inventors have found that a silicon-containing compound having a specific structure and a curable composition containing the same solve the above-mentioned problems. The invention has been completed.

  The present invention provides a silicon-containing compound represented by the following general formula (1).

（式中、Ｒ^a〜Ｒ^dは、同一でも異なっていてもよい炭素原子数１〜１２の飽和脂肪族炭化水素基であり、Ｒ^eは、炭素原子数１〜１２の飽和脂肪族炭化水素基、又は、飽和脂肪族炭化水素基で置換されていてもよい炭素原子数６〜１２の芳香族炭化水素基であり、Ｒ^eが複数ある場合は、それらは同一でも異なってもよい。Ｙは炭素原子数２〜４のアルキレン基であり、Ｚは、炭素原子数２〜４のアルケニル基又はアルキニル基であり、Ｋは２〜７の数であり、Ｔは１〜７の数であり、Ｋ及びＴはＫ−Ｔ≦１を満たし、Ｐは０〜３の数である。Ｍは一般式（１）で表されるケイ素含有化合物の質量平均分子量を３０００〜１００万とする数である。）

(Wherein, R ^{a to} R ^d are the same or different saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms, and R ^e is a saturated aliphatic hydrocarbon having 1 to 12 carbon atoms) Group or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted with a saturated aliphatic hydrocarbon group, and when there are a plurality of R ^e , they may be the same or different. is an alkylene group having 2 to 4 carbon atoms, Z is, or alkenyl group of carbon atom number 2-4 alkynyl group, K is the number of 2 to 7, T is the number of 1 to 7 K and T satisfy KT ≦ 1, and P is a number from 0 to 3. M represents a mass average molecular weight of the silicon-containing compound represented by the general formula (1) of 3000 to 1,000,000. Number.)

（式中、Ｒ ^a 〜Ｒ ^d は、同一でも異なっていてもよい炭素原子数１〜１２の飽和脂肪族炭化水素基であり、Ｒ ^e は、炭素原子数１〜１２の飽和脂肪族炭化水素基、又は、飽和脂肪族炭化水素基で置換されていてもよい炭素原子数６〜１２の芳香族炭化水素基であり、Ｒ ^e が複数ある場合は、それらは同一でも異なってもよい。Ｙは炭素原子数２〜４のアルキレン基であり、Ｋは２〜７の数であり、Ｔは１〜７の数であり、Ｋ及びＴはＫ−Ｔ≦１を満たし、Ｐは０〜３の数である。Ｍは一般式（１’）で表されるケイ素含有化合物の質量平均分子量を３０００〜１００万とする数である。）
Further, the present invention is, (A1) a silicon-containing compound represented by the following general formula (1 '), (B1) the upper Symbol silicon-containing compound, and (C) curable composition containing the hydrosilylation catalyst Is to provide.

(Wherein, R ^{a to} R ^d are the same or different saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms, and R ^e is a saturated aliphatic hydrocarbon having 1 to 12 carbon atoms) Group or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted with a saturated aliphatic hydrocarbon group, and when there are a plurality of R ^e , they may be the same or different. Is an alkylene group having 2 to 4 carbon atoms, K is a number of 2 to 7, T is a number of 1 to 7, K and T satisfy KT ≦ 1, and P is 0 to 3 M is a number that sets the mass average molecular weight of the silicon-containing compound represented by the general formula (1 ′) to 3000 to 1,000,000.)

  The present invention also provides a silicon-containing cured product obtained by curing the above curable composition.

  ADVANTAGE OF THE INVENTION According to this invention, the curable composition excellent in handling property and sclerosis | hardenability, the hardened | cured material excellent in heat resistance, transparency, and a softness | flexibility, and the silicon-containing compound which gives these can be provided.

First, the silicon-containing compound of the present invention represented by the general formula (1) will be described.
In the general formula (1), the saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms represented by R ^{a to} R ^e is methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl. , Isobutyl, amyl, isoamyl, tertiary amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, Tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl and the like can be mentioned.

Further, the aromatic hydrocarbon group having a saturated aliphatic hydrocarbon group carbon atoms which may be substituted with 6-12 represented by R ^e is a whole, including the saturated aliphatic hydrocarbon group that is a substituent The number of carbon atoms is 6-12. As a saturated aliphatic hydrocarbon group which is a substituent, what can satisfy | fill the said carbon atom number can be employ | adopted among the saturated aliphatic hydrocarbon groups illustrated above, for example. Therefore, the aromatic hydrocarbon group having a saturated aliphatic hydrocarbon group carbon atoms which may be substituted with 6-12 represented by R ^e, phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 2,3-dimethylphenyl, 2 , 4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl, etc. It is done.

Further, the alkylene group having 2 to 4 carbon atoms represented by _{Y, -CH 2 CH 2 -,} - CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH (CH _{3) CH 2 -, - CH} 2 CH (CH 3) - , and the like.
Examples of the alkenyl group having 2 to 4 carbon atoms represented by Z include CH ₂ ═CH—, CH ₂ ═CH—CH ₂ —, CH ₂ ═CH—CH ₂ —CH ₂ —, CH ₂ ═C (CH ₃ )-, CH ₂ ═C (CH ₃ ) —CH ₂ —, CH ₂ ═CH—CH (CH ₃ ) — and the like, and examples of the alkynyl group having 2 to 4 carbon atoms represented by Z include For example, the following groups are mentioned.

A preferred form of the silicon-containing compound of the present invention represented by the general formula (1) is a silicon-containing compound represented by the following general formula (2). The silicon-containing compound represented by the following general formula (2) is T = K among the silicon-containing compounds represented by the above general formula (1). What is obtained by the usual synthesis method is a silicon-containing compound represented by the following general formula (2) or a mixture of a plurality of silicon-containing compounds represented by the above general formula (1), The main component is the silicon-containing compound represented by (2). For example, the compound in which KT in the general formula (1) is a number larger than 1 uses a polyfunctional (R ^a SiHO) _K cyclopolysiloxane as a compound for introducing a cyclopolysiloxane ring. Even in cases, production is negligible. This is because the formation of a compound in which an acyclic polysiloxane is bonded to two or more Si—H of cyclopolysiloxane via Y is greatly disadvantageous in terms of energy.

（式中、Ｒ^a〜Ｒ^dは、同一でも異なっていてもよい炭素原子数１〜１２の飽和脂肪族炭化水素基であり、Ｒ^eは、炭素原子数１〜１２の飽和脂肪族炭化水素基、又は、飽和脂肪族炭化水素基で置換されていてもよい炭素原子数６〜１２の芳香族炭化水素基であり、Ｒ^eが複数ある場合は、それらは同一でも異なってもよい。Ｙは炭素原子数２〜４のアルキレン基であり、Ｚは、水素原子又は炭素原子数２〜４のアルケニル基若しくはアルキニル基であり、ｋは２〜７の数であり、ｐは１〜４の数である。ｍは一般式（２）で表されるケイ素含有化合物の質量平均分子量を３０００〜１００万とする数である。）

(Wherein, R ^{a to} R ^d are the same or different saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms, and R ^e is a saturated aliphatic hydrocarbon having 1 to 12 carbon atoms) Group or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted with a saturated aliphatic hydrocarbon group, and when there are a plurality of R ^e , they may be the same or different. Is an alkylene group having 2 to 4 carbon atoms, Z is a hydrogen atom or an alkenyl group or alkynyl group having 2 to 4 carbon atoms, k is a number of 2 to 7, and p is 1 to 4 M is a number that makes the mass average molecular weight of the silicon-containing compound represented by the general formula (2) 3000 to 1,000,000.)

R ^{a to} R ^d in the general formula (1) or the general formula (2) are preferably methyl groups because the resulting cured product has good heat resistance.

In addition, R ^e in the above general formula (1) or general formula (2) is preferably a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms because the cured product obtained has good light resistance. Since the cured product has good heat resistance, a methyl group is more preferable.

  Moreover, k in the said General formula (2) is 2-7. When it is larger than 7, the flexibility required for the cured product obtained by having too many functional groups cannot be obtained. The k is preferably 2 to 5, since it can be easily obtained industrially and the number of functional groups is appropriate, and 3 is most preferable.

  The mass average molecular weight of the silicon-containing compound of the present invention is 3,000 to 1,000,000. If it is less than 3000, the resulting cured product has insufficient heat resistance, and if it is greater than 1 million, the viscosity increases and hinders handling. The mass average molecular weight is preferably 5,000 to 500,000, and more preferably 10,000 to 100,000.

The silicon-containing compound of the present invention is not particularly limited by the production method, and can be produced by applying a known reaction. Subsequent production methods are represented by the general formula (2) of the silicon-containing compound of the present invention as a representative. In the general formula (2), Z is a hydrogen atom, and Z is 2 carbon atoms. What is -4 alkenyl group or alkynyl group is demonstrated in order.
Hereinafter, those in which Z in the above general formula (1) or (2) is a hydrogen atom, respectively, the silicon-containing compound (A1) or (A2), Z in the above general formula (1) or (2) is carbon. What is an alkenyl group or alkynyl group having 2 to 4 atoms is defined as a silicon-containing compound (B1) or (B2), respectively.

A method for producing the silicon-containing compound (A2) in which Z in the general formula (2) is a hydrogen atom will be described below.
The silicon-containing compound (A2) can be obtained, for example, by reacting the cyclic polysiloxane compound (a2) with the acyclic polysiloxane compound (a1) having an unsaturated bond as a precursor.
The acyclic polysiloxane compound (a1) having an unsaturated bond is obtained by subjecting one or two or more types of bifunctional silane compounds to a condensation reaction by hydrolysis. When p is 3, it can be obtained by reacting with a trifunctional monosilane compound, when p is 4, it is reacted with a tetrafunctional monosilane compound, and further reacted with a monofunctional silane compound having an unsaturated group. When p is 2, it can be obtained by reacting with a monofunctional silane compound having an unsaturated group after the condensation reaction. A typical functional group of these silane compounds is an alkoxy group, a halogen group or a hydroxyl group. The acyclic polysiloxane compound (a1) and the cyclic polysiloxane compound (a2) having an unsaturated bond are bonded by a reaction between the unsaturated bond carbon of (a1) and the Si—H group of (a2).

  Examples of the bifunctional silane compound used for the production of the acyclic polysiloxane compound (a1) having the unsaturated bond include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, and dibutyldimethoxy. Dialkoxymonosilane compounds such as silane, dibutyldiethoxysilane, dioctyldimethoxysilane, dioctyldiethoxysilane; one or two alkoxy groups of these dialkoxymonosilane compounds are selected from the group consisting of fluorine, chlorine, bromine and iodine. Monosilane compounds substituted with selected halogen atoms or hydroxyl groups; disiloxane compounds and oligosiloxane compounds in which two or more of these monosilane compounds are condensed.

Examples of the monofunctional monosilane compound include trimethylethoxysilane, trimethylmethoxysilane, triethylethoxysilane, triethylmethoxysilane, tributylmethoxysilane, tributylethoxysilane, trioctylmethoxysilane, trioctylethoxysilane, triphenylethoxysilane, tri Monoalkoxysilane compounds such as phenylmethoxysilane, methyldiphenylethoxysilane, dimethylphenylethoxysilane; the alkoxy groups of these monoalkoxysilane compounds are replaced with halogen atoms or hydroxyl groups selected from the group consisting of fluorine, chlorine, bromine and iodine And monosilane compounds.
Examples of the trifunctional monosilane compound include trisethoxymethylsilane, trismethoxymethylsilane, trisethoxyethylsilane, trismethoxyethylsilane, trisethoxybutylsilane, trismethoxybutylsilane, trisethoxyoctylsilane, trismethoxyoctylsilane, and trisethoxy. Trisalkoxysilane compounds such as phenylsilane and trismethoxyphenylsilane; 1 to 3 alkoxy groups of these trisalkoxysilane compounds are replaced with halogen atoms or hydroxyl groups selected from the group consisting of fluorine, chlorine, bromine and iodine And monosilane compounds.
The tetrafunctional monosilane compound is selected from the group consisting of tetrakisalkoxysilane compounds such as tetrakisethoxysilane and tetrakismethoxysilane; 1-4 alkoxy groups of these tetrakisalkoxysilane compounds are composed of fluorine, chlorine, bromine and iodine. And monosilane compounds substituted with halogen atoms or hydroxyl groups.

  Examples of the monofunctional silane compound having an unsaturated group include dimethylvinylchlorosilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, diphenylvinylchlorosilane, diphenylvinylethoxysilane, diphenylvinylmethoxysilane, methylphenylvinylchlorosilane, and methylphenyl. Examples include ethoxysilane and methylphenylmethoxysilane.

  Examples of the cyclic polysiloxane compound (a2) include 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopenta. Siloxane, 1,3,5,7,9,11-hexamethylcyclohexasiloxane, 1,3,5,7,9,11,13-heptamethylcycloheptasiloxane, 1,3,5,7,9, 11,13,15-octamethylcyclooctasiloxane, 1,3,5-triethylcyclotrisiloxane, 1,3,5,7-tetraethylcyclotetrasiloxane, 1,3,5,7,9-pentaethylcyclopenta Siloxane, 1,3,5,7,9,11-hexaethylcyclohexasiloxane, 1,3,5-triphenylcyclotrisiloxane, , 5,7-tetraphenyl cyclotetrasiloxane, 1,3,5,7,9 penta phenyl cyclopentasiloxane, 1,3,5,7,9,11 hexaphenyl cyclohexasiloxane and the like.

  In addition, each compound has as said bifunctional silane compound, monofunctional monosilane compound, trifunctional monosilane compound, tetrafunctional monosilane compound, monofunctional silane compound having an unsaturated group, or cyclic polysiloxane compound (a2). When a hydrogen atom in which part or all of the hydrogen atom is substituted with deuterium and / or fluorine is used, part or all of the hydrogen atom of the silicon-containing compound of the present invention described later is deuterium and / or fluorine. A compound substituted with can be obtained.

  The condensation reaction by hydrolysis for obtaining an acyclic polysiloxane compound (a1) having an unsaturated bond which is a precursor of the silicon-containing compound (A2) may be carried out by a so-called sol-gel reaction. In the hydrolysis / condensation reaction of the bifunctional silane compound, an alkoxy group or a halogen group is hydrolyzed with water to generate a silanol group (Si-OH group), and the generated silanol groups, the silanol group and the alkoxy group, or the silanol It proceeds by the condensation of the group and the halogen group. In order to advance this hydrolysis reaction quickly, it is preferable to add an appropriate amount of water, and a catalyst may be added. In addition, this condensation reaction proceeds also with a minute amount of water contained in water or a solvent other than water. A solvent may be used for this reaction, and the solvent is not particularly limited. Specifically, for example, water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone are used. And hydrophilic organic solvents such as dioxane, tetrahydrofuran and the like. These may be used alone or in combination of two or more.

  Moreover, as said catalyst, an acid or a base can be used, Specifically, for example, inorganic acids, such as hydrochloric acid, phosphoric acid, a sulfuric acid; Acetic acid, p-toluenesulfonic acid, monoisopropyl phosphate, etc. Organic acids; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia; amine compounds (organic bases) such as triethylamine, triethylamine, monoethanolamine and diethanolamine; tetraisopropyl titanate, tetrabutyl titanate, etc. Titanium compounds; tin compounds such as dibutyltin laurate and octyl stannic acid; boron compounds such as trifluoroborane; aluminum compounds such as aluminum trisacetylacetate; chlorides of metals such as iron, cobalt, manganese and zinc; As well as naphthenates and esters of these metals. Metal carboxylates such as chill salts and the like, which can be used in combination one kind or two or more types. In addition, when performing a hydrolysis / condensation reaction from two or more types of bifunctional silane compounds, each of them may be hydrolyzed to some extent, and then both may be mixed for further hydrolysis-condensation reaction. You may mix and perform a hydrolysis and a condensation reaction at once.

  As described above, the acyclic polysiloxane compound (a1) having an unsaturated bond as a precursor is further subjected to the hydrolysis / condensation reaction described above, and when p is 1, a monofunctional monosilane compound and p is When 3 is a trifunctional monosilane compound and when p is 4, it can be obtained by reacting with a monofunctional silane compound having an unsaturated group after reacting with a tetrafunctional monosilane compound. Can be obtained by reacting with a monofunctional silane compound having an unsaturated group.

  The reaction between the precursor acyclic polysiloxane compound (a1) having an unsaturated bond and the cyclic polysiloxane compound (a2) may be a method based on a hydrosilylation reaction. For example, the silicon-containing compound (A2) can be obtained by mixing an acyclic polysiloxane compound (a1) and a cyclic polysiloxane compound (a2), adding an arbitrary amount of platinum catalyst, and heating.

  A method for producing the silicon-containing compound (B2) in which Z in the general formula (2) is an alkenyl group or alkynyl group having 2 to 4 carbon atoms will be described below.

  The silicon-containing compound (B2) can be obtained, for example, by reacting the cyclic polysiloxane compound (b2) having an unsaturated bond with the acyclic polysiloxane compound (b1) as a precursor. The acyclic polysiloxane compound (b1) is obtained by subjecting one or more bifunctional silane compounds to a condensation reaction by hydrolysis. When p is 1, the monofunctional monosilane compound and p is 3. Can be obtained by reacting a trifunctional monosilane compound with a tetrafunctional monosilane compound when p is 4, and further reacting with a Si—H group-introducing compound. The acyclic polysiloxane compound (b1) and the cyclic polysiloxane compound (b2) having an unsaturated bond are bonded together by a reaction between the Si—H group of (b1) and the unsaturated group of (b2). A typical functional group of the bifunctional silane compound is an alkoxy group, a halogen group or a hydroxyl group.

  Examples of the bifunctional silane compound used in the production of the acyclic polysiloxane compound (b1) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dibutyldimethoxysilane, and dibutyldiethoxy. Dialkoxymonosilane compounds such as silane, dioctyldimethoxysilane, dioctyldiethoxysilane; halogen atoms selected from the group consisting of fluorine, chlorine, bromine and iodine for one or two alkoxy groups of these dialkoxymonosilane compounds; Or monosilane compounds substituted with hydroxyl groups; disiloxane compounds and oligosiloxane compounds in which two or more of these monosilane compounds are condensed.

Examples of the monofunctional monosilane compound include trimethylethoxysilane, trimethylmethoxysilane, triethylethoxysilane, triethylmethoxysilane, tributylmethoxysilane, tributylethoxysilane, trioctylmethoxysilane, trioctylethoxysilane, triphenylethoxysilane, tri Monoalkoxysilane compounds such as phenylmethoxysilane, methyldiphenylethoxysilane, dimethylphenylethoxysilane; the alkoxy groups of these monoalkoxysilane compounds are replaced with halogen atoms or hydroxyl groups selected from the group consisting of fluorine, chlorine, bromine and iodine And monosilane compounds.
Examples of the trifunctional monosilane compound include trisethoxymethylsilane, trismethoxymethylsilane, trisethoxyethylsilane, trismethoxyethylsilane, trisethoxybutylsilane, trismethoxybutylsilane, trisethoxyoctylsilane, trismethoxyoctylsilane, Trisalkoxysilane compounds such as trisethoxyphenylsilane and trismethoxyphenylsilane; 1 to 3 alkoxy groups of these trisalkoxysilane compounds are halogen atoms or hydroxyl groups selected from the group consisting of fluorine, chlorine, bromine and iodine And monosilane compounds replaced by.
Examples of the tetrafunctional monosilane compound include tetrakisalkoxysilane compounds such as tetrakisethoxysilane and tetrakismethoxysilane; 1-4 alkoxy groups of these tetrakisalkoxysilane compounds are composed of fluorine, chlorine, bromine and iodine. And monosilane compounds substituted with a halogen atom or a hydroxyl group selected from the group.

  Examples of the cyclic polysiloxane compound (b2) having an unsaturated bond include 1,3,5-trimethyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5,7-tetramethyl-1, 3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinylcyclopentasiloxane, 1,3,5,7,9, 11-hexamethyl 1,3,5,7,9,11-hexavinylcyclohexasiloxane, 1,3,5,7,9,11,13-heptamethyl-1,3,5,7,9,11,13 -Heptavinylcycloheptasiloxane, 1,3,5,7,9,11,13,15-octamethyl-1,3,5,7,9,11,13,15-octavinylcyclooctasiloxane, 1,3 , 5-Triffe 1,3,5-trivinylcyclotrisiloxane, 1,3,5,7-tetraphenyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7,9-penta Examples include phenyl-1,3,5,7,9-pentavinylcyclopentasiloxane.

  Examples of the Si-H group-introducing compound include dimethylchlorosilane, dimethylmethoxysilane, dimethylethoxysilane, diphenylchlorosilane, diphenylmethoxysilane, diphenylethoxysilane, phenylmethylchlorosilane, phenylmethylmethoxysilane, phenylmethylethoxysilane, hydroxydimethylsilane, Examples thereof include hydroxydiphenylsilane and hydroxyphenylmethylsilane.

  In addition, as said bifunctional silane compound, 1 functional monosilane compound, 3 functional monosilane compound, 4 functional monosilane compound, Si-H group introduction | transduction compound, or cyclic polysiloxane compound (b2) which has an unsaturated bond, each compound is as follows. When a hydrogen atom having part or all of hydrogen atoms substituted by deuterium and / or fluorine is used, part or all of the hydrogen atoms of the silicon-containing compound of the present invention described later are deuterium and / or fluorine. A compound substituted with can be obtained.

  The condensation reaction by hydrolysis for obtaining the acyclic polysiloxane compound (b1) which is the precursor of the silicon-containing compound (B2) may be carried out by a so-called sol-gel reaction. This is the same as the sol-gel reaction described in the acyclic polysiloxane compound (a1).

  For the reaction between the precursor acyclic polysiloxane compound (b1) and the cyclic polysiloxane compound (b2) having an unsaturated bond, a method based on a hydrosilylation reaction may be used. For example, the silicon-containing compound (B2) can be obtained by mixing the acyclic polysiloxane compound (b1) and the cyclic polysiloxane compound (b2) having an unsaturated bond, adding an arbitrary amount of platinum catalyst, and then heating. .

  The silicon-containing compound of the present invention can be used as a main component of a curable composition as will be described later, and is mixed with other polymer compounds or polymer compositions to be used for resins, plastic modifiers, etc. It can also be used.

  Although not within the scope of the silicon-containing compound of the present invention, in the acyclic siloxane chain in the general formula (1) or (2), boron, magnesium, aluminum, phosphorus, titanium, zirconium, hafnium, Elements other than silicon, such as iron, zinc, niobium, tantalum, tin and tellurium, can be introduced. As the method, for example, a method of carrying out hydrolysis / condensation reaction using these other element supply derivatives in combination and incorporating an element other than silicon into the siloxane chain can be mentioned. There may also be those in which part or all of the hydrogen atoms of the silicon-containing compound are substituted with deuterium and / or fluorine.

Next, the curable composition of this invention is demonstrated.
The curable composition of the present invention includes a silicon-containing compound (A1) in which Z in the general formula (1) is a hydrogen atom, and Z in the general formula (1) is an alkenyl group or alkynyl group having 2 to 4 carbon atoms. The silicon-containing compound (B1) and the hydrosilylation reaction catalyst (C) are essential components. The curable composition of the present invention is cured by reacting the Z group of the silicon-containing compound (A1) and the Z group of the silicon-containing compound (B1) by the action of heat and the hydrosilylation reaction catalyst (C). Preferred forms of the silicon-containing compound (A1) and the silicon-containing compound (B1) contained in the curable composition of the present invention are the silicon-containing compound (A2) and the silicon-containing compound (B2) described above.
The curable composition of the present invention preferably contains 5 to 5000 parts by mass of the silicon-containing compound (B1), more preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the silicon-containing compound (A1). In addition, the content of the hydrosilylation reaction catalyst (C) is preferably 5% by mass or less in the curable composition of the present invention in terms of curability and storage stability, and is 0.0001 to 1.0% by mass. More preferred. If it is more than 5% by mass, the stability of the curable composition may be affected.

  The hydrosilylation reaction catalyst (C) according to the present invention is a known catalyst containing one or more metals selected from the group consisting of platinum, palladium and rhodium that promote the hydrosilylation reaction. For example, examples of the platinum-based catalyst include a platinum-carbonylvinylmethyl complex, a platinum-divinyltetramethyldisiloxane complex, a platinum-cyclovinylmethylsiloxane complex, and a platinum-octylaldehyde complex. Examples of the palladium-based catalyst and the rhodium-based catalyst include compounds containing palladium or rhodium, which are also platinum-based metals, instead of platinum in the platinum-based catalyst. These may be used alone or in combination of two or more. In particular, those containing platinum are preferable from the viewpoint of curability, and specifically, platinum-carbonylvinylmethyl complex is preferable. In addition, so-called Wilkinson catalysts containing the above platinum-based metals such as chlorotristriphenylphosphine rhodium (I) are also included in the hydrosilylation reaction catalyst (C).

You may make the curable composition of this invention contain the compound (D) which can react with a silicon containing compound (A1) or a silicon containing compound (B1) as needed.
The compound (D) can be used, for example, for the purpose of improving adhesion. The compound (D) is a compound that reacts with the Si—H group in the silicon-containing compound (A1) or a compound that reacts with the alkenyl group or alkynyl group in the silicon-containing compound (B1). It is used by type or by mixing two or more types. Although it does not specifically limit as a compound seed | species, A polysiloxane compound is preferable from a heat resistant viewpoint of hardened | cured material. Examples of the polysiloxane compound include linear or branched polydimethylsiloxanes having silicone groups having vinyl groups, acetylene groups, Si-H groups, etc. at both ends; linear or branched dimethylsiloxanes and diphenylsiloxanes. Random and / or silicone having a vinyl group, acetylene group, Si-H group or the like at both ends of the block body; a part of methyl group of a linear or branched polydimethylsiloxane is a vinyl group or an acetylene group And a silicone substituted with a group selected from Si-H groups; a methyl group or a phenyl group in a random and / or block body of a linear or branched dimethylsiloxane and diphenylsiloxane is a vinyl group, an acetylene group, and Silicone substituted with a group selected from Si-H groups; vinyl group, acetylene , Resin or the like having a group such as Si-H group.

  The amount of the compound (D) to be used is preferably 50% by mass or less based on the total amount of the silicon-containing compound (A1) and the silicon-containing compound (B1) that are the reaction partners. When it is more than 50% by mass, the flexibility and light resistance of the obtained cured product may be lowered.

  The curable composition of the present invention may further contain components such as an inorganic filler and a weather resistance imparting agent as optional components.

  Examples of the inorganic filler include so-called fillers, inorganic materials such as minerals, and those modified by organic modification treatment or the like. Specifically, for example, silicon dioxides such as colloidal silica, silica filler, silica gel; metal oxides such as aluminum oxide, zinc oxide, titanium oxide; mica, montmorillonite, silica, diatomaceous earth, sericite, kaolinite, Minerals such as flint, feldspar powder, meteorite, attapulgite, talc, minnesotite, pyrophyllite; those obtained by modifying these by organic modification or the like.

  The particle size of the inorganic filler is preferably 100 μm or less and more preferably 50 μm or less from the viewpoint of heat resistance. Further, when the use of the cured product places importance on transparency, fine particles of 1 μm or less having a large effect with a small amount of use are preferable. The content of the inorganic filler in the curable composition of the present invention is preferably 0 to 10% by mass because it is preferably not used or used as little as possible when importance is placed on transparency. When used for imparting thixotropy, 10 to 90% by mass is preferable.

  As the weather resistance imparting agent, well-known and commonly used materials such as a light stabilizer, an ultraviolet absorber, a phenolic antioxidant, a sulfurous antioxidant, and a phosphorus antioxidant can be used. Examples of the light stabilizer include hindered amines, and examples of the ultraviolet absorber include 2-hydroxybenzophenones, 2- (2-hydroxyphenyl) benzotriazoles, 2- (2-hydroxyphenyl) -4,6- And diaryl-1,3,5-triazines, benzoates, and cyanoacrylates. Examples of phenolic antioxidants include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxy). Phenyl) propionate], dibutylhydroxytoluene (BHT), 2,6-di-t-butyl-paracresol (DBPC) and the like, and as the sulfur-based antioxidant, dialkylthiodipropionates, β-alkyl Mercaptopropionic acid esters can be mentioned, and phosphorus antioxidants include Machine phosphites, and the like.

  When the weather resistance imparting agent is used, the content thereof is 0.0001 to in the curable composition of the present invention in terms of heat resistance, electrical properties, curability, mechanical properties, storage stability, and handling properties. 50 mass% is preferable and 0.001-10 mass% is further more preferable.

In the curable composition of the present invention, other known various resins, additives, fillers, and the like can be blended within a range that does not impair the target performance of the present invention. Examples of various resins that can be arbitrarily blended include polyimide resins, polyether resins such as polyethylene glycol and polypropylene glycol, polyurethane resins, epoxy resins, phenol resins, polyester resins, melamine resins, polyamide resins, polyphenylene sulfide resins, and the like. Examples of additives that can be optionally blended include antistatic agents.
In order that the usage-amount of arbitrary components other than a silicon-containing compound (A1), a silicon-containing compound (B1), and a hydrosilylation reaction catalyst (C) does not impair the target performance of this invention, silicon-containing compound (A1) and The total amount is preferably 10 parts by mass or less with respect to the total amount of 100 parts by mass with the silicon-containing compound (B1).

The curable composition of the present invention has good fluidity at room temperature (25 ° C.) and excellent handling properties. Regarding fluidity, the viscosity measured with an E-type viscometer at room temperature (25 ° C.) without containing an inorganic filler is preferably 50 Pa · S or less, more preferably 10 Pa · S or less. .
Moreover, the hardened | cured material of the curable composition of this invention is excellent in heat resistance, crack resistance, transparency, light resistance, etc. In detail, from the curable composition of this invention, the temperature which brings about the mass reduction of 5 mass% of hardened | cured material is 300 degreeC or more, More preferably, hardened | cured material more preferably 400 degreeC or more is obtained. Moreover, the hardened | cured material with few crack generations is obtained suitably.

  The cured product of the present invention is obtained by curing the curable composition of the present invention. The heating temperature for curing is preferably 0 to 300 ° C, more preferably 100 to 200 ° C. The curing time is preferably 0.1 to 10 hours, more preferably 0.5 to 6 hours. By performing a curing reaction under these curing reaction conditions, a cured product having performance excellent in heat resistance, crack resistance and the like can be obtained from the curable composition of the present invention.

  The cured product of the present invention has excellent physical properties, in particular, transparency, heat resistance, crack resistance, light resistance, solvent resistance, alkali resistance, weather resistance, stain resistance, flame resistance, moisture resistance, It is a material excellent in mechanical properties such as gas barrier properties, flexibility, elongation and strength, electrical insulation, low dielectric constant, optical properties, electrical properties and the like.

  The curable composition of the present invention comprising the silicon-containing compound of the present invention is excellent in stability, curability and the like, and further, the cured product has crack resistance, heat resistance, solvent resistance, alkali resistance, weather resistance. Excellent in various physical properties such as properties, optical properties, and electrical properties. The curable composition of the present invention is a sealing material for display materials, optical materials, recording materials, semiconductors, etc. in the field of electrical and electronic materials, high voltage insulating materials, potting for insulation, vibration proofing, waterproofing and moisture proofing purposes. Sealing material, prototype mold for plastic parts, coating material, interlayer insulation film, insulating packing, heat shrink rubber tube, O-ring, sealant / protective material for display device, optical waveguide, optical fiber protective material, optical lens, optical Application to equipment adhesives, high heat resistant adhesives, high heat dissipation materials, high heat resistant sealing materials, solar and fuel cell materials, solid electrolytes for batteries, insulation coating materials, photosensitive drums for copying machines, gas separation membranes, etc. it can. It can also be applied to concrete protection materials, linings, soil injection agents, sealing agents, cold storage materials, glass coatings, etc. in the civil engineering / building materials field, and in the medical materials field, tubes, sealing materials, The present invention can be applied to coating materials, sterilization apparatus sealing materials, contact lenses, oxygen-enriched films, and the like.

EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further, this invention is not limited by these Examples. In the examples, “parts” and “%” are based on mass. Of the following Examples 1 to 15, Examples 1, 3 and 5 are reference examples.

[Synthesis Example 1]
100 parts of dichlorodimethylsilane was dropped into a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide solution and polymerized at 105 ° C. for 5 hours. The obtained reaction solution was washed with 500 parts of ion exchange water, and then this toluene solution was dehydrated, 20 parts of pyridine was added, 20 parts of dimethylvinylchlorosilane was further added, and the mixture was stirred at 70 ° C. for 30 minutes. Then, after washing with 100 parts of ion exchange water, the solvent was distilled off under reduced pressure at 150 ° C. Next, it was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C. to obtain an acyclic polysiloxane compound (a1-1) having an unsaturated bond. As a result of analysis by GPC under the following conditions, the molecular weight of the acyclic polysiloxane compound (a1-1) was Mw = 20,000. All subsequent GPCs were performed under these conditions.
(GPC measurement conditions)
Column: TSK-GEL MULTIPORE HXL M, 7.8mm X 300mm, manufactured by Tosoh Corporation
Developing solvent: Tetrahydrofuran

[Example 1]
100 parts of the acyclic polysiloxane compound (a1-1) obtained in Synthesis Example 1 is dissolved in 200 parts of toluene, 0.003 part of a platinum catalyst, and 1,3,5,7-tetramethylcyclo which is a cyclic polysiloxane compound. 10 parts of tetrasiloxane was added and reacted at 105 ° C. for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C. and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 ° C. to obtain a silicon-containing compound (A-1). As a result of analysis by GPC, the molecular weight of the silicon-containing compound (A-1) was Mw = 22,000.

[Synthesis Example 2]
100 parts of dichlorodimethylsilane was dropped into a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide solution and polymerized at 105 ° C. for 5 hours. The obtained reaction solution was washed with 500 parts of ion exchange water, and then this toluene solution was dehydrated, 20 parts of pyridine was added, 20 parts of dimethylchlorosilane was further added thereto, and the mixture was stirred at 70 ° C. for 30 minutes. Then, after washing with 100 parts of ion exchange water, the solvent was distilled off under reduced pressure at 150 ° C. Next, it was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C. to obtain an acyclic polysiloxane compound (b1-1). As a result of analysis by GPC, the molecular weight of the acyclic polysiloxane compound (b1-1) was Mw = 20,000.

[Example 2]
100 parts of the acyclic polysiloxane compound (b1-1) obtained in Synthesis Example 2 is dissolved in 200 parts of toluene, 0.003 part of a platinum catalyst, and 1, 3, 5, which are cyclic polysiloxane compounds having an unsaturated bond. 10 parts of 7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane was added and reacted at 105 ° C. for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C. and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 ° C. to obtain a silicon-containing compound (B-1). As a result of analysis by GPC, the molecular weight of the silicon-containing compound (B-1) was Mw = 22,000.

[Synthesis Example 3]
100 parts of dichlorodimethylsilane was dropped into a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide solution and polymerized at 105 ° C. for 5 hours. The obtained reaction solution was washed with 500 parts of ion exchange water, and then this toluene solution was dehydrated. After adding 20 parts of pyridine and 0.5 part of methyltrichlorosilane and stirring at room temperature for 30 minutes and further at 70 ° C. for 30 minutes, the solution was divided in half.
On the other hand, 2.5 parts of dimethylvinylchlorosilane, which is a monofunctional silane compound having an unsaturated bond, is added, stirred at room temperature for 30 minutes and further at 70 ° C. for 30 minutes, and then washed with ion-exchanged water to wash pyridine hydrochloride. Was removed to obtain an acyclic polysiloxane compound (a1-2) having an unsaturated bond.
On the other hand, 2.5 parts of dimethylchlorosilane, which is a Si—H group-introducing compound, was added, stirred at room temperature for 30 minutes and further at 70 ° C. for 30 minutes, and then washed with ion-exchanged water to remove pyridine hydrochloride, A non-cyclic polysiloxane compound (b1-2) was obtained.

[Example 3]
100 parts of an acyclic polysiloxane compound (a1-2) having an unsaturated bond obtained in Synthesis Example 3 is dissolved in 200 parts of toluene, 0.003 part of a platinum catalyst, and 1,3,5 which is a cyclic polysiloxane compound. , 7-tetramethylcyclotetrasiloxane (10 parts) was added and reacted at 105 ° C. for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C. and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 ° C. to obtain a silicon-containing compound (A-2). As a result of analysis by GPC, the molecular weight of the silicon-containing compound (A-2) was Mw = 42,000.

[Example 4]
100 parts of the acyclic polysiloxane compound (b1-2) obtained in Synthesis Example 3 is dissolved in 200 parts of toluene, and 0.003 part of a platinum catalyst and 1,3, 5, which are cyclic polysiloxane compounds having an unsaturated bond 10 parts of 7-tetramethyl-1,3,5,7-tetravinylcyclotetraloxane was added and reacted at 105 ° C. for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C. and then washed with 100 parts of acetonitrile. Then, the solvent was distilled off under reduced pressure at 70 ° C. to obtain a silicon-containing compound (B-2). As a result of analysis by GPC, the molecular weight of the silicon-containing compound (B-2) was Mw = 42,000.

[Synthesis Example 4]
100 parts of dichlorodimethylsilane was dropped into a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide, and reacted at 105 ° C. for 5 hours. The obtained reaction solution was washed with 500 parts of ion exchange water, and then this toluene solution was dehydrated. After adding 20 parts of pyridine and 0.5 part of tetrachlorosilane and stirring at room temperature for 30 minutes and further at 70 ° C. for 30 minutes, the solution was divided in half.
On the other hand, 2.5 parts of dimethylvinylchlorosilane, which is a monofunctional silane compound having an unsaturated bond, is added, stirred at room temperature for 30 minutes and further at 70 ° C. for 30 minutes, and then washed with ion-exchanged water to wash pyridine hydrochloride. Was removed to obtain an acyclic polysiloxane compound (a1-3) having an unsaturated bond.
On the other hand, 2.5 parts of dimethylchlorosilane, which is a Si—H group-introducing compound, was added, stirred for 30 minutes at room temperature, and further for 30 minutes at 70 ° C. An acyclic polysiloxane compound (b1-3) was obtained.

[Example 5]
100 parts of an acyclic polysiloxane compound (a1-3) having an unsaturated bond obtained in Synthesis Example 4 is dissolved in 200 parts of toluene, 0.003 part of a platinum catalyst, and 1 is a cyclic polysiloxane compound having an unsaturated bond , 3,5,7-tetramethylcyclotetrasiloxane was added and reacted at 105 ° C. for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C. and then washed with 100 parts of acetonitrile. Then, the solvent was distilled off under reduced pressure at 70 ° C. to obtain a silicon-containing compound (A-3). As a result of analysis by GPC, the molecular weight of the silicon-containing compound (A-3) was Mw = 52,000.

[Example 6]
100 parts of the acyclic polysiloxane compound (b1-3) obtained in Synthesis Example 4 is dissolved in 200 parts of toluene, and 0.003 part of a platinum catalyst and 1,3, 5, which are cyclic polysiloxane compounds having an unsaturated bond 10 parts of 7-tetramethyl-1,3,5,7-vinylcyclotetraloxane was added and reacted at 105 ° C. for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C. and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 ° C. to obtain a silicon-containing compound (B-3). As a result of analysis by GPC, the molecular weight of the silicon-containing compound (B-3) was Mw = 52,000.

[Example 7]
A mixture of 50 parts of the silicon-containing compound (A-1) obtained in Example 1 and 50 parts of the silicon-containing compound (B-1) obtained in Example 2 was mixed with platinum as a hydrosilylation reaction catalyst (C). Mixing 0.005 part of carbonyl vinyl methyl complex, the curable composition No. 1 was obtained.

[Example 8]
A mixture of 50 parts of the silicon-containing compound (A-2) obtained in Example 3 and 50 parts of the silicon-containing compound (B-2) obtained in Example 4 was mixed with platinum as a hydrosilylation reaction catalyst (C). Mixing 0.005 part of carbonyl vinyl methyl complex, the curable composition No. 2 was obtained.

[Example 9]
A mixture of 50 parts of the silicon-containing compound (A-3) obtained in Example 5 and 50 parts of the silicon-containing compound (B-3) obtained in Example 6 was mixed with platinum as a hydrosilylation reaction catalyst (C). Mixing 0.005 part of carbonyl vinyl methyl complex, the curable composition No. 3 was obtained.

[Comparative Example 1]
To a mixture of 50 parts of the acyclic polysiloxane (a1-1) having an unsaturated bond obtained in Synthesis Example 1 and 50 parts of the acyclic polysiloxane compound (b1-1) obtained in Synthesis Example 2, As a curing catalyst, 0.005 part of a platinum-carbonylvinylmethyl complex was mixed to obtain a comparative curable composition (ratio-1).

[Comparative Example 2]
50 parts of polysiloxane (Mw: 30,000, vinyl group content: 3.5 mmol / g) randomly condensed with dimethyldimethoxysilane and vinylmethyldimethoxysilane as monomers, and random condensation with dimethyldimethoxysilane and methyldimethoxysilane as monomers To a mixture of 50 parts of polysiloxane (Mw: 30,000, Si—H group amount: 3.5 mmol / g) mixed with 0.005 part of platinum-carbonylvinylmethyl complex as a curing catalyst, A comparative curable composition (ratio-2) was obtained.

[Comparative Example 3]
Polysiloxane resin (Mw: 30,000, vinyl group content: 3.5 mmol / m) obtained by random condensation at a molar ratio of 1: 4: 5 using vinyltrimethoxysilane, methyltrimethoxysilane and dimethyldimethoxysilane as monomers. g) Polysiloxane resin (Mw: 30,000, Si-H) obtained by random condensation at a molar ratio of 1: 4: 5 using 50 parts of trimethoxysilane, methyltrimethoxysilane and dimethyldimethoxysilane as monomers. (Base amount: 3.5 mmol / g) 50 parts of a mixture is mixed with 0.005 parts of a platinum-carbonylvinylmethyl complex as a curing catalyst to obtain a comparative curable composition (ratio-3). It was.

[Comparative Example 4]
A platinum-carbonylvinylmethyl complex as a curing catalyst was prepared by mixing 50 parts of the silicon-containing compound (A-1) obtained in Example 1 and 50 parts of both terminal vinyl group polydimethylsiloxane (Mw: 20,000). 0.005 part was mixed and the curable composition for comparison (ratio-4) was obtained.

[Comparative Example 5]
A mixture of 50 parts of the silicon-containing compound (B-1) obtained in Example 2 and 50 parts of Si-H group polydimethylsiloxane (Mw: 20,000) at both ends was mixed with platinum-carbonylvinyl as a curing catalyst. 0.005 part of a methyl complex was mixed to obtain a comparative curable composition (ratio-5).

[Comparative Example 6]
90 parts of dichlorodimethylsilane and 9 parts of dichlorodiphenylsilane are mixed and dropped into a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide, and polymerized at 105 ° C. for 5 hours. I let you. The obtained reaction solution was washed with 500 parts of ion exchange water, and then this toluene solution was dehydrated, 20 parts of pyridine was added, 20 parts of dimethylvinylchlorosilane was further added, and the mixture was stirred at 70 ° C. for 30 minutes. Then, after washing with 100 parts of ion exchange water, the solvent was distilled off under reduced pressure at 150 ° C. Next, it was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C. to obtain an acyclic polysiloxane compound having an unsaturated bond (ratio a1-1).
100 parts of the obtained acyclic polysiloxane compound having an unsaturated bond (ratio a1-1) was dissolved in 200 parts of toluene, 0.003 part of a platinum catalyst, and 1,3,5,7- 10 parts of tetramethylcyclotetrasiloxane was added and reacted at 105 ° C. for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C. and then washed with 100 parts of acetonitrile. Then, the solvent was distilled off under reduced pressure at 70 ° C. to obtain a silicon-containing compound (Ratio A-1). As a result of analysis by GPC, the molecular weight of the silicon-containing compound (ratio A-1) was Mw = 22,000.

On the other hand, 90 parts of dichlorodimethylsilane and 10 parts of dichlorodiphenylsilane were mixed and dropped into a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide solution at 105 ° C. Polymerized for hours. The obtained reaction solution was washed with 500 parts of ion exchange water, and then this toluene solution was dehydrated, 20 parts of pyridine was added, 20 parts of dimethylchlorosilane was further added thereto, and the mixture was stirred at 70 ° C. for 30 minutes. Then, after washing with 100 parts of ion exchange water, the solvent was distilled off under reduced pressure at 150 ° C. Next, it was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C. to obtain an acyclic polysiloxane compound (ratio b1-1).
100 parts of the obtained acyclic polysiloxane compound (ratio b1-1) is dissolved in 200 parts of toluene, 0.003 part of a platinum catalyst, and 1,3,5,7- which is a cyclic polysiloxane compound having an unsaturated bond 10 parts of tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane was added and reacted at 105 ° C. for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C. and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 ° C. to obtain a silicon-containing compound (ratio B-1). As a result of analysis by GPC, the molecular weight of the silicon-containing compound (ratio B-1) was Mw = 22,000.

  A mixture of 50 parts of the silicon-containing compound (ratio A-1) and 50 parts of the silicon-containing compound (ratio B-1) is mixed with 0.005 part of a platinum-carbonylvinylmethyl complex as a curing catalyst. A comparative curable composition (ratio-6) was obtained.

[Comparative Example 7]
75 parts of dichlorodimethylsilane and 24 parts of dichlorodiphenylsilane are mixed and dropped into a mixture of 100 parts of ion exchange water, 50 parts of toluene and 450 parts of 48% sodium hydroxide aqueous solution, and polymerized at 105 ° C. for 5 hours. I let you. The obtained reaction solution was washed with 500 parts of ion exchange water, and then this toluene solution was dehydrated, 20 parts of pyridine was added, 20 parts of dimethylvinylchlorosilane was further added, and the mixture was stirred at 70 ° C. for 30 minutes. Then, after washing with 100 parts of ion exchange water, the solvent was distilled off under reduced pressure at 150 ° C. Next, it was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C. to obtain an acyclic polysiloxane compound having an unsaturated bond (ratio a1-2).
100 parts of the obtained acyclic polysiloxane compound having an unsaturated bond (ratio a1-2) is dissolved in 200 parts of toluene, 0.003 part of a platinum catalyst, and 1,3,5,7- which is a cyclic polysiloxane compound 10 parts of tetramethylcyclotetrasiloxane was added and reacted at 105 ° C. for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C. and then washed with 100 parts of acetonitrile. Then, the solvent was distilled off under reduced pressure at 70 ° C. to obtain a silicon-containing compound (Ratio A-2). As a result of analysis by GPC, the molecular weight of the silicon-containing compound (ratio A-2) was Mw = 22,000.

On the other hand, 75 parts of dichlorodimethylsilane and 24 parts of dichlorodiphenylsilane were mixed and dropped into a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide solution at 105 ° C. Polymerized for hours. The obtained reaction solution was washed with 500 parts of ion exchange water, and then this toluene solution was dehydrated, 20 parts of pyridine was added, 20 parts of dimethylchlorosilane was further added thereto, and the mixture was stirred at 70 ° C. for 30 minutes. Then, after washing with 100 parts of ion exchange water, the solvent was distilled off under reduced pressure at 150 ° C. Next, it was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C. to obtain an acyclic polysiloxane compound (ratio b1-2).
100 parts of the obtained acyclic polysiloxane compound (ratio b1-2) is dissolved in 200 parts of toluene, 0.003 part of a platinum catalyst, and 1,3,5,7- which is a cyclic polysiloxane compound having an unsaturated bond 10 parts of tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane was added and reacted at 105 ° C. for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C. and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 ° C. to obtain a silicon-containing compound (ratio B-2). As a result of analysis by GPC, the molecular weight of the silicon-containing compound (ratio B-2) was Mw = 22,000.

  A mixture of 50 parts of the silicon-containing compound (ratio A-2) and 50 parts of the silicon-containing compound (ratio B-2) was mixed with 0.005 part of a platinum-carbonylvinylmethyl complex as a curing catalyst. A comparative curable composition (ratio-7) was obtained.

[Examples 10 to 12, Comparative Examples 8 to 12]
The curable composition No. obtained in Examples 7-9 above. 1 to 3 and Comparative Examples 1 to 5 and Comparative curable compositions (Ratio-1) to (Ratio-5) were each formed on an aluminum plate to a film thickness of about 1 mm, and 150 ° C. for 30 minutes. It is cured by heating, and cured product No. 1-3 and hardened | cured material ratio 1-5 were obtained. In addition, the number of the used curable composition and the number of the obtained hardened | cured material respectively respond | correspond. About these hardened | cured material, the evaluation of the hardening state and the 180 degree | times bending test were done as follows.

The cured state is judged based on the presence or absence of tackiness of the cured film after a predetermined curing time. The fluidity state is X, the one with tackiness even without fluidity is Δ to ○, and tack free. ◎.
In the 180-degree bending test, the state of the film was observed when a cured film obtained by forming a film with a thickness of about 1 mm on an aluminum plate was bent 180 degrees. Samples with no cracks or peeling on the film when bent at 180 degrees are marked as ◯, cracks are generated at 180 degrees, samples with no cracks or peeling at 90 degrees are marked with Δ, and samples with cracks at 90 degrees are marked with x. .
The results are shown in Table 1.

  As apparent from Table 1, the cured product Nos. 1 to 3, compared with the cured products ratios 2 to 5 of Comparative Examples 9 to 12, the cured state is the same or improved, and the 180 degree bending test is improved. Moreover, sufficient solid hardened | cured material was not obtained from the curable composition (ratio-1). From these facts, it was confirmed that the cured state and flexibility were improved by adopting the configuration of the present invention.

[Examples 13 to 15, Comparative Examples 13 and 14]
The curable composition No. obtained in Examples 7-9 above. 1-3, and the curable compositions (Ratio-6) and (Ratio-7) obtained in Comparative Examples 6 and 7 were each poured into a 20 mm × 20 mm × 3 mm mold and heated at 150 ° C. for 1 hr. , 3 mm thick cured product No. 4-6, ratio 6, and ratio 7 were obtained. About these hardened | cured material, the optical deterioration test by the irradiation for 2 hours of radiation of the output of 9.96 W / cm in 365 nm was done using the high pressure mercury lamp. Table 2 shows the transmittance at 400 nm before and after the light degradation test.

As is clear from Table 2, the cured product Nos. Of Examples 13 to 15 were obtained. In all of 4 to 6, the light resistance is improved as compared with the cured product ratios 6 and 7 of Comparative Examples 11 and 12. From this, it was confirmed that a cured product obtained by curing a curable composition in which R ^{a to} R ^e consist only of an aliphatic group has good light resistance.

Claims (9)

A silicon-containing compound represented by the following general formula (1).

(Wherein, R ^{a to} R ^d are the same or different saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms, and R ^e is a saturated aliphatic hydrocarbon having 1 to 12 carbon atoms) Group or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted with a saturated aliphatic hydrocarbon group, and when there are a plurality of R ^e , they may be the same or different. is an alkylene group having 2 to 4 carbon atoms, Z is, or alkenyl group of carbon atom number 2-4 alkynyl group, K is the number of 2 to 7, T is the number of 1 to 7 K and T satisfy KT ≦ 1, and P is a number from 0 to 3. M represents a mass average molecular weight of the silicon-containing compound represented by the general formula (1) of 3000 to 1,000,000. Number.) A silicon-containing compound represented by the following general formula (2).

(Wherein, R ^{a to} R ^d are the same or different saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms, and R ^e is a saturated aliphatic hydrocarbon having 1 to 12 carbon atoms) Or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted with a saturated aliphatic hydrocarbon group, and R ^e
When there are a plurality of these, they may be the same or different. Y is an alkylene group having 2 to 4 carbon atoms, Z is, or alkenyl group of carbon atom number 2-4 alkynyl group, k is the number of 2 to 7, p is 1 to 4 Is a number. m is a number that makes the mass average molecular weight of the silicon-containing compound represented by the general formula (2) 3000 to 1,000,000. ) The silicon-containing compound according to claim 1 or 2 R ^e is a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms. The silicon-containing compound according to claim 1 or 2, wherein R ^{a to} R ^e are all methyl groups. (A1) a silicon-containing compound represented by the following general formula (1 '), (B 1 ) 請 Motomeko 1 silicon-containing compound as described, and (C) curable composition containing the hydrosilylation catalyst.

(Wherein, R ^{a to} R ^d are the same or different saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms, and R ^e is a saturated aliphatic hydrocarbon having 1 to 12 carbon atoms) Group or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted with a saturated aliphatic hydrocarbon group, and when there are a plurality of R ^e , they may be the same or different. Is an alkylene group having 2 to 4 carbon atoms, K is a number of 2 to 7, T is a number of 1 to 7, K and T satisfy KT ≦ 1, and P is 0 to 3 M is a number that sets the mass average molecular weight of the silicon-containing compound represented by the general formula (1 ′) to 3000 to 1,000,000.) (A2) the silicon-containing compound represented by the following general formula (2 '), (B2) 請 Motomeko 2 silicon-containing compound as described, and (C) curable composition containing the hydrosilylation catalyst.

(Wherein, R ^{a to} R ^d are the same or different saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms, and R ^e is a saturated aliphatic hydrocarbon having 1 to 12 carbon atoms) Group or an aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted with a saturated aliphatic hydrocarbon group, and when there are a plurality of R ^e , they may be the same or different. Is an alkylene group having 2 to 4 carbon atoms, k is a number of 2 to 7, p is a number of 1 to 4. m is the mass of the silicon-containing compound represented by the general formula (2 ′) (The number is an average molecular weight of 3000 to 1 million.) Above (A1) a silicon-containing compound of the component, R ^a to R ^e in the general formula (1 ') are all methyl groups, the (B1) a silicon-containing compound of the component, in the above following general formula 1 The curable composition according to claim 5, wherein R ^{a to} R ^e are all methyl groups. Above (A2) the silicon-containing compound of the component, R ^a to R ^e in the general formula (2 ') are all methyl groups, the (B2) a silicon-containing compound of the component, in the above following general formula (2) the curable composition according to claim 6 R ^a to R ^e are all methyl groups. A cured product obtained by curing the curable composition according to any one of claims 5-8.