TWI425031B - A compound containing silicon, a hardened composition and a hardened product - Google Patents

Description

a compound containing bismuth, a curable composition, and a cured product

The present invention relates to a novel bismuth-containing compound having a specific structure, a curable composition formed by the same, and a cured product formed by thermally hardening the composition. In detail, the present invention relates to a provision. The curable composition containing the bismuth of the curable composition, the curable composition containing the quinone-containing compound, and the cured product excellent in transparency and flexibility, the curable composition is excellent in handleability and curability, and forms transparency. And a cured product excellent in flexibility.

For composite materials that combine organic raw materials and inorganic raw materials, the industry has been conducting various researches. In the industry, the method of compounding inorganic fillers with organic polymers or modifying the surface of metal with organic polymers is also used. Coating method, etc. For these organic/inorganic composite materials, since the raw materials constituting the composite materials have a size of a micron or more, although some physical properties can be increased to a predetermined value or more, most other properties or physical properties are only expressed according to organic raw materials. And the value expected by the addition rule of the performance or physical properties of each of the inorganic raw materials.

On the other hand, in recent years, research on the following organic/inorganic composite materials has become more prevalent: the size of each raw material domain of organic raw materials and inorganic raw materials is nanometer-scale, and then organically combined at a molecular level. /Inorganic composite materials. The manufacturer expects such materials to be the following materials: not only the characteristics of each raw material, but also the advantages of each raw material, and thus the raw materials are unpredictable with the raw materials. A completely different new functionality.

In such an organic/inorganic composite material, there is a chemical bonding type in which one of the raw materials and the other raw material are bonded at a molecular level via a covalent bond, and one of the raw materials is used as a substrate and the other raw material is finely dispersed. A hybrid type that is combined in this matrix. As a method of synthesizing the inorganic raw materials used in the organic/inorganic composite materials, a sol-gel method is used, which means that the hydrolysis by the precursor molecules and the subsequent polymerization are carried out. The condensation reaction, while obtaining a reaction of the crosslinked inorganic oxide at a low temperature. The inorganic raw material obtained by the sol-gel method has a problem of poor storage stability such as gelation in a short period of time.

In Non-Patent Document 1, attempts have been made to improve the storage stability by focusing on the difference in the condensation rate due to the alkyl chain length of the alkyltrialkoxydecane, and the polymerization in methyltrimethoxydecane. After condensation, a long-chain alkyltrialkoxydecane having a slow polycondensation rate is added to block the sterol group in the polyoxyalkylene; further, the polycondensation of methyltrimethoxydecane is carried out using an aluminum catalyst. In the reaction, acetamidine acetone is added at a specific molecular weight, and ligand exchange is carried out in the reaction system. However, these methods are not adequate for improving storage stability. Further, the inorganic raw material obtained by the sol-gel method has a problem of flexibility.

On the other hand, as the chemical bonding type organic/inorganic composite material, a curable composition containing a specific polymer containing ruthenium has been proposed. For example, Patent Document 1 discloses a curable composition containing ruthenium containing a ruthenium-containing polymer (A) having a crosslinked structure and having an alkenyl group and an alkynyl group, and having a crosslinked structure and having a fluorenyl group. Bismuth polymer (B), and platinum It is a catalyst (D) and is excellent in workability and hardenability, and the obtained cured product is also excellent in heat resistance. However, the curable composition containing bismuth has a problem that the hardening property is not necessarily sufficient, and a cured product having sufficient performance cannot be obtained at a low temperature in a short time.

[Non-Patent Document 1] Journal of the Chemical Society of Japan, No. 9, 571 (1998)

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-325174

An object of the present invention is to provide a curable composition which is excellent in workability and curability, and which is excellent in transparency and flexibility of a cured product obtained.

In order to solve the above problems, the present inventors have found that a compound containing ruthenium having a specific structure and a curable composition containing the ruthenium-containing compound can solve the above problems, and the present invention has been completed.

The present invention provides a compound containing ruthenium represented by the following formula (1): (wherein R ^a to R ^d are saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms which may be the same or different; R ^e is a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, or may be saturated fat An aromatic hydrocarbon group having 6 to 12 carbon atoms substituted by a hydrocarbon group, and when there are a plurality of R ^e , the R ^{e may} be the same or different; Y 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 from 2 to 7, T is a number from 1 to 7, and P is a number from 0 to 3; M is a formula (1) The mass average molecular weight of the compound containing ruthenium is 3,000 to 1,000,000.

Furthermore, the present invention provides a curable composition comprising (A1) the above-mentioned compound containing ruthenium wherein Z in the above formula (1) is a hydrogen atom, and (B1) Z in the above formula (1) is carbon The above-mentioned oxime-containing compound having an alkenyl group of 2 to 4 or an alkynyl group and (C) a hydrogenation-reactive catalyst are formed.

Moreover, the present invention provides a cured product containing ruthenium formed by curing the curable composition.

According to the present invention, it is possible to provide a curable composition excellent in workability and curability, a cured product excellent in heat resistance, transparency, and flexibility, and a bismuth-containing compound which provides the curable composition and the cured product.

First, the compound containing ruthenium of the present invention represented by the above formula (1) will be described.

In the above formula (1), the saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms represented by R ^a to R ^e may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group. Dibutyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2- Heptyl, 3-heptyl, isoheptyl, third heptyl, n-octyl, isooctyl, trioctyl, 2-ethylhexyl, decyl, isodecyl, decyl, dodecyl Wait.

Further, the aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted by a saturated aliphatic hydrocarbon group represented by R ^e means that the total number of carbon atoms of the saturated aliphatic hydrocarbon group which is a substituent is 6 to 12. As the substituent, that is, the saturated aliphatic hydrocarbon group, for example, those having a carbon atom number satisfying the above-described saturated aliphatic hydrocarbon group can be used. Therefore, examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted by a saturated aliphatic hydrocarbon group represented by R ^e include a phenyl group, a naphthyl group, a 2-methylphenyl group, and a 3-methylphenyl group. 4-methylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexyl Phenyl, 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, and the like.

Further, examples of the alkylene group having 2 to 4 carbon atoms represented by Y include -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 -, and CH ₂ =C ( CH ₃ )-, CH ₂ =C(CH ₃ )-CH ₂ -, CH ₂ =CH-CH(CH ₃ )-, etc., and an alkynyl group having 2 to 4 carbon atoms represented by Z, for example, The following basis.

A preferred form of the ruthenium-containing compound of the present invention represented by the above formula (1) is a compound containing ruthenium represented by the following formula (2). The compound containing ruthenium represented by the following formula (2) is T=K in the compound containing ruthenium represented by the above formula (1). The compound obtained by the usual synthesis method is a mixture of a compound containing ruthenium represented by the following formula (2) or a plurality of compounds containing ruthenium represented by the above formula (1), which will have the following formula (2) A compound containing ruthenium as a main component. For example, even when a polyfunctional ring polyoxyalkylene represented by (R ^a SiHO) _K is used as a compound introduced into a cyclic polyoxyalkylene ring, the KT of the above formula (1) is a compound having a number greater than 1 The amount generated is also very small. The reason for this is that the formation of a compound in which an acyclic polyoxyalkylene is bonded to two or more Si-H groups of a cyclopolyoxyalkylene via Y is extremely disadvantageous in terms of energy.

(wherein R ^a to R ^d are saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms which may be the same or different, R ^e is a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, or may be saturated fat carbon atoms, a substituted aliphatic hydrocarbon group of an aromatic hydrocarbon group of 6 to 12, when there are plural R ^e, these may be identical or different R ^e .Y carbon atoms, alkyl of 2 to 4 extension, Z Is a hydrogen atom or an alkenyl group or alkynyl group having 2 to 4 carbon atoms, k is a number from 2 to 7, and p is a number from 1 to 4. m is a compound containing ruthenium represented by the general formula (2) The mass average molecular weight is 3,000 to 1 million.

In the above formula (1) or in the formula (2), R ^a to R ^{d are} preferably a methyl group because the obtained cured product has good heat resistance.

Further, R ^e in the above formula (1) or formula (2) is preferably a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, because the cured product obtained has good light resistance, and the above-mentioned pass The R ^e in the formula (1) or the formula (2) is more preferably a methyl group because the heat resistance of the obtained cured product is also good.

Further, k in the above formula (2) is 2 to 7. If k is more than 7, the number of functional groups is too large, and the flexibility required for the obtained cured product cannot be obtained. When k is 2 to 5, it is industrially easy to obtain a raw material, and the number of functional groups is appropriate. Therefore, it is preferable that k is 3.

The ruthenium-containing compound of the present invention has a mass average molecular weight of 3,000 to 1,000,000. If the mass average molecular weight is less than 3,000, the heat resistance of the obtained cured product is insufficient, and if the mass average molecular weight is more than 1,000,000, the viscosity becomes large and the operation is hindered. The average mass molecular weight is preferably 5,000 to 500,000, more preferably 10,000 to 100,000.

The ruthenium-containing compound of the present invention is not particularly limited as long as it is produced by a known method, and can be produced by a known reaction. In the following production method, the compound represented by the above formula (2) of the ruthenium-containing compound of the present invention is represented, and in the above formula (2), Z is a hydrogen atom, and Z is a carbon atom number of 2 to 4. The alkenyl or alkynyl group will be described in order.

In the following, in the above formula (1) or (2), Z is a hydrogen atom, and is represented as a compound (A1) or (A2) containing ruthenium, and the above formula (1) or (2) Z is an alkenyl or alkynyl group having 2 to 4 carbon atoms, respectively Compound (B1) or (B2).

Hereinafter, a method for producing the ruthenium-containing compound (A2) in which Z in the above formula (2) is a hydrogen atom will be described.

The ruthenium-containing compound (A2) can be obtained, for example, by reacting an acyclic polyoxy siloxane compound (a1) having an unsaturated bond as a precursor and reacting it with a cyclic polyoxy siloxane compound (a2). .

The acyclic polysiloxane compound (a1) having an unsaturated bond can be obtained by subjecting one or two or more difunctional decane compounds to a condensation reaction by hydrolysis, and when p is 1, The functional monodecane compound is reacted, reacted with a trifunctional monodecane compound when p is 3, reacted with a tetrafunctional monodecane compound when p is 4, and further reacted with a monofunctional decane compound having an unsaturated group. When p is 2, it can be obtained by reacting with a monofunctional decane compound having an unsaturated group after the condensation reaction. The functional group of the decane compound is typically an alkoxy group, a halogen group or a hydroxyl group. The acyclic polyoxy siloxane compound (a1) having an unsaturated bond and the cyclic polyoxy siloxane compound (a2) are reacted with the unsaturated bonded carbon of (a1) and the Si-H group of (a2) And the key knot.

Examples of the above-mentioned difunctional decane compound used in the production of the above-mentioned acyclic polysiloxane compound (a1) having an unsaturated bond include dimethyldimethoxydecane and dimethyldiethoxylate. Base decane, diethyl dimethoxy decane, diethyl diethoxy decane, dibutyl dimethoxy decane, dibutyl diethoxy decane, dioctyl dimethoxy decane, dioctane a dialkoxy monodecane compound such as bis-ethoxy decane; or one or two alkoxy groups of the above dialkoxy monodecane compounds are selected from the group consisting of fluorine, chlorine, bromine and iodine a monooxane compound having a halogen atom or a hydroxyl group in a group; a dioxane compound and an oligomeric alkoxylate compound obtained by condensing two or more of the monodecane compounds.

Examples of the monofunctional monodecane compound include trimethyl ethoxy decane, trimethyl methoxy decane, triethyl ethoxy decane, triethyl methoxy decane, and tributyl methoxy decane. Tributyl ethoxy decane, trioctyl methoxy decane, trioctyl ethoxy decane, triphenyl ethoxy decane, triphenyl methoxy decane, methyl diphenyl ethoxy decane, a monoalkoxydecane compound such as dimethylphenylethoxysilane; the alkoxy group of the monoalkoxydecane compound is substituted with a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine or a monodecane compound of a hydroxyl group.

The trifunctional monodecane compound may, for example, be triethoxymethyl decane, trimethoxymethyl decane, triethoxyethyl decane, trimethoxyethyl decane, triethoxy butyl decane or the like. a trialkoxy decane compound such as oxybutyl decane, triethoxyoctyl decane, trimethoxyoctyl decane, triethoxyphenyl decane or trimethoxyphenyl decane; The 1-3 alkoxy group of the decane compound is substituted with a monodecane compound selected from a halogen atom or a hydroxyl group in a group consisting of fluorine, chlorine, bromine and iodine.

Examples of the tetrafunctional monodecane compound include a tetraalkoxydecane compound such as tetraethoxysilane or tetramethoxynonane; and 1 to 4 alkoxy groups of the above tetraalkoxydecane compounds are substituted. A halogen atom or a monodecane compound of a hydroxyl group in a group consisting of fluorine, chlorine, bromine and iodine.

Examples of the monofunctional decane compound having an unsaturated group include dimethyl vinyl chlorodecane, dimethyl vinyl methoxy decane, and dimethyl group. Vinyl ethoxy decane, diphenyl vinyl chlorodecane, diphenyl vinyl ethoxy decane, diphenyl vinyl methoxy decane, methyl phenyl vinyl chloro decane, methyl phenyl ethoxylate Base decane, methyl phenyl methoxy decane, and the like.

The cyclic polyaluminoxane compound (a2) may, for example, be 1,3,5-trimethylcyclotrioxane or 1,3,5,7-tetramethylcyclotetraoxane or 1, 3,5,7,9-pentamethylcyclopentaoxane, 1,3,5,7,9,11-hexamethylcyclohexaoxane, 1,3,5,7,9,11, 13-heptamethylcyclopentaoxane, 1,3,5,7,9,11,13,15-octamethylcyclooctadecane, 1,3,5-triethylcyclotrioxane 1,3,5,7-tetraethylcyclotetraoxane, 1,3,5,7,9-pentaethylcyclopentaoxane, 1,3,5,7,9,11-six Ethylcyclohexaoxane, 1,3,5-triphenylcyclotrioxane, 1,3,5,7-tetraphenylcyclotetraoxane, 1,3,5,7,9- Pentaphenylcyclopentaoxane, 1,3,5,7,9,11-hexaphenylcyclohexaoxane, and the like.

Further, the difunctional decane compound, the monofunctional monodecane compound, the trifunctional monodecane compound, the tetrafunctional monodecane compound, the monofunctional decane compound having an unsaturated group, or the cyclic polyoxy siloxane compound (a2) When one or all of the hydrogen atoms of each compound are substituted with hydrazine and/or fluorine, one or all of the hydrogen atoms of the quinone-containing compound of the present invention may be substituted with hydrazine and/or fluorine.

A condensation reaction by hydrolysis to obtain a precursor of the compound (A2) containing ruthenium, that is, a non-cyclic polyoxy siloxane compound (a1) having an unsaturated bond, by a so-called sol-gel reaction get on. The hydrolysis-condensation reaction of the difunctional decane compound is carried out by hydrolyzing an alkoxy group or a halogen group to form a decyl group (Si-OH group), which forms a sterol group and a decyl group. Condensation with an alkoxy group, or a decyl group and a halogen group. To make The hydrolysis reaction proceeds rapidly, and it is preferred to add an appropriate amount of water or to add a catalyst. Further, the condensation reaction is also carried out by moisture in the air or a trace amount of water contained in a solvent other than water. A solvent may be used for the reaction, and the solvent is not particularly limited, and specific examples thereof include water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, and methyl ethyl b. A hydrophilic organic solvent such as a ketone, a dioxane or a tetrahydrofuran may be used alone or in combination of two or more.

Further, as the catalyst, an acid or a base can be used, and specific examples thereof include inorganic acids such as hydrochloric acid, phosphoric acid, and sulfuric acid; organic acids such as acetic acid, p-toluenesulfonic acid, and monoisopropyl phosphate; and sodium hydroxide; An inorganic base such as potassium hydroxide, lithium hydroxide or ammonia; an amine compound (organic base) such as trimethylamine, triethylamine, monoethanolamine or diethanolamine; a titanium compound such as tetraisopropyl titanate or tetrabutyl titanate; a tin compound such as dibutyltin laurate or octylstannic acid; a boron compound such as boron trifluoride; an aluminum compound such as aluminum triacetate; a chloride of a metal such as iron, cobalt, manganese or zinc; A metal carboxylate such as a metal naphthenate or an octanoate; and the like may be used alone or in combination of two or more. Further, when the hydrolysis-condensation reaction is carried out by using two or more kinds of difunctional decane compounds, the hydrolysis may be further carried out by separately mixing the two to some extent, and further mixing all the difunctional decane compounds. The hydrolysis-condensation reaction is carried out together.

As described above, the precursor, that is, the acyclic polyoxy siloxane compound (a1) having an unsaturated bond can be obtained by further converting monofunctional monodecane when p is 1 after the above hydrolysis-condensation reaction. The compound reacts, further reacts with the trifunctional monodecane compound when p is 3, and further with p when The tetrafunctional monodecane compound is reacted, and then obtained by reacting with a monofunctional decane compound having an unsaturated group; when p is 2, it can be obtained by reacting with a monofunctional decane compound having an unsaturated group.

The precursor, that is, the reaction of the acyclic polyoxy siloxane compound (a1) having an unsaturated bond with the cyclic polyoxy siloxane compound (a2), a method using a hydrazine hydrogenation reaction can be used. For example, the ruthenium-containing compound (A2) can be obtained by mixing the acyclic polyoxy siloxane compound (a1) with the cyclic polyoxy siloxane compound (a2), and adding any amount of the platinum catalyst. Heat up.

Hereinafter, a method for producing a ruthenium-containing compound (B2) in which Z in the above formula (2) is an alkenyl group or an alkynyl group having 2 to 4 carbon atoms will be described.

The ruthenium-containing compound (B2) can be, for example, reacted with a cyclic polysiloxane compound (b2) having an unsaturated bond by using the acyclic polyoxy siloxane compound (b1) as a precursor. obtain. The acyclic polyoxy siloxane compound (b1) can be obtained by reacting one or two or more difunctional decane compounds with a hydrolysis reaction, and reacting with a monofunctional monodecane compound when p is 1. When p is 3, it reacts with a trifunctional monodecane compound, and when p is 4, it reacts with a tetrafunctional monodecane compound, and further with a compound which introduces a Si-H group. The acyclic polyaluminoxane compound (b1) and the cyclic polyoxyalkylene compound (b2) having an unsaturated bond are bonded by the reaction of the Si-H group of (b1) with the unsaturated group of (b2). Knot. Representative functional groups of the above difunctional decane compounds are alkoxy groups, halogen groups or hydroxyl groups.

Examples of the above-mentioned difunctional decane compound used in the production of the acyclic polysiloxane compound (b1) include dimethyldimethoxydecane, dimethyldiethoxydecane, and diethyl Dimethoxydecane, diethyl a dialkoxy monodecane compound such as diethoxydecane, dibutyldimethoxydecane, dibutyldiethoxydecane, dioctyldimethoxydecane or dioctyldiethoxydecane; One or two alkoxy groups of the above dialkoxymonodecane compounds are substituted with a monodecane compound selected from a halogen atom or a hydroxyl group in a group consisting of fluorine, chlorine, bromine and iodine; A dioxane compound and an oligomeric alkoxylate compound obtained by condensing a monodecane compound.

Examples of the monofunctional monodecane compound include trimethyl ethoxy decane, trimethyl methoxy decane, triethyl ethoxy decane, triethyl methoxy decane, and tributyl methoxy decane. Tributyl ethoxy decane, trioctyl methoxy decane, trioctyl ethoxy decane, triphenyl ethoxy decane, triphenyl methoxy decane, methyl diphenyl ethoxy decane, a monoalkoxydecane compound such as dimethylphenylethoxysilane; the alkoxy group of the monoalkoxydecane compound is substituted with a halogen atom selected from the group consisting of fluorine, chlorine, bromine and iodine or a monodecane compound of a hydroxyl group.

Examples of the trifunctional monodecane compound include triethoxymethyl decane, trimethoxymethyl decane, triethoxyethyl decane, trimethoxyethyl decane, and triethoxy butyl decane. a trialkoxy decane compound such as trimethoxybutyl decane, triethoxyoctyl decane, trimethoxyoctyl decane, triethoxyphenyl decane or trimethoxyphenyl decane; The 1-3 alkoxy group of the decyl group compound is substituted with a halogen atom or a hydroxy group monodecane compound selected from the group consisting of fluorine, chlorine, bromine and iodine.

Examples of the tetrafunctional monodecane compound include a tetraalkoxydecane compound such as tetraethoxysilane or tetramethoxydecane; and 1 to 4 alkoxy groups of the above tetraalkoxydecane compound are substituted with Free choice of fluorine, chlorine and bromine And a halogen atom or a monodecane compound of a hydroxyl group in the group consisting of iodine.

The cyclic polysiloxane compound (b2) having an unsaturated bond may, for example, be 1,3,5-trimethyl-1,3,5-trivinylcyclotrioxane or 1,3. 5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-five Vinylcyclopentaoxane, 1,3,5,7,9,11-hexamethyl-1,3,5,7,9,11-hexavinylcyclohexaoxane, 1,3,5 , 7,9,11,13-heptamethyl-1,3,5,7,9,11,13-heptavinylcyclopentaoxane, 1,3,5,7,9,11,13, 15-octamethyl-1,3,5,7,9,11,13,15-octavinylcyclooctadecane, 1,3,5-triphenyl-1,3,5-trivinyl Cyclotrioxane, 1,3,5,7-tetraphenyl-1,3,5,7-tetravinylcyclotetraoxane, 1,3,5,7,9-pentaphenyl-1 , 3,5,7,9-pentavinylcyclopentaoxane, and the like.

Examples of the compound into which the Si-H group is introduced include dimethylchloromethane, dimethyl methoxy decane, dimethyl ethoxy decane, diphenyl chlorodecane, diphenyl methoxy decane, and Phenyl ethoxy decane, phenyl methyl chlorodecane, phenyl methyl methoxy decane, phenyl methyl ethoxy decane, hydroxy dimethyl decane, hydroxy diphenyl decane, hydroxy phenyl methyl decane Wait.

Further, the difunctional decane compound, a monofunctional monodecane compound, a trifunctional monodecane compound, a tetrafunctional monodecane compound, a compound into which a Si-H group is introduced, or a cyclic polyoxy siloxane compound having an unsaturated bond (b2) When a part or all of hydrogen atoms of each compound are substituted with hydrazine and/or fluorine, a part or all of hydrogen atoms of the ruthenium-containing compound of the present invention may be substituted with hydrazine and/or fluorine as described later. Compound.

Non-cyclic polyfluorene used to obtain a compound containing ruthenium (B2) The condensation reaction by the hydrolysis of the alkane compound (b1) can be carried out by a so-called sol-gel reaction, which is described in the above-mentioned acyclic polysiloxane compound (a1) having an unsaturated bond. The sol-gel reaction is the same.

The precursor, that is, the reaction of the acyclic polyoxy siloxane compound (b1) with the cyclic polyoxy siloxane compound (b2) having an unsaturated bond, can be carried out by a hydrogenation reaction using hydrazine. For example, the acyclic polyoxy siloxane compound (b1) is mixed with a cyclic polyoxy siloxane compound (b2) having an unsaturated bond, and an arbitrary amount of a platinum catalyst is added and then heated, whereby a bismuth-containing product can be obtained. Compound (B2).

The ruthenium-containing compound of the present invention can be used as a main component of the curable composition as described below, and can be used in combination with other polymer compounds or polymer compositions for use in resins, plastic modifiers, and the like.

Further, in addition to the range of the ruthenium-containing compound of the present invention, boron, magnesium, aluminum, phosphorus, and titanium may be introduced into the acyclic siloxane chain in the above formula (1) or (2). Other than zirconium, hafnium, iron, zinc, antimony, bismuth, tin, antimony and the like. As the method, for example, a method in which a derivative other than the other element is supplied and a hydrolysis-condensation reaction is carried out, and an element other than ruthenium is incorporated in the siloxane chain. Further, some or all of the hydrogen atoms of the above-mentioned compound containing ruthenium may be substituted with ruthenium and/or fluorine.

Next, the curable composition of the present invention will be described.

The curable composition of the present invention contains a ruthenium-containing compound (A1) in which Z in the above formula (1) is a hydrogen atom, and Z in the above formula (1) is an alkene having 2 to 4 carbon atoms. A composition containing a hydrazine compound (B1) or a hydrazine hydrogenation reaction catalyst (C) as an essential component. The curable composition of the present invention contains hydrazine by the action of heat and hydrazine hydrogenation catalyst (C) The Z group of the compound (A1) is hardened by reacting with the Z group of the ruthenium-containing compound (B1). The preferred form of each of the ruthenium-containing compound (A1) and the ruthenium-containing compound (B1) contained in the curable composition of the present invention is the above-mentioned ruthenium-containing compound (A2) and ruthenium-containing compound (B2).

In the curable composition of the present invention, it is preferred to contain 5 to 5000 parts by mass of the compound (B1) containing ruthenium, more preferably 10 to 1000 mass, per 100 parts by mass of the compound (A1) containing ruthenium. Share. In the curable composition of the present invention, the content of the rhodium hydrogenation catalyst (C) is preferably 5% by mass or less, more preferably 0.0001 to 1.0. quality%. When the content of the hydrogenation reaction catalyst (C) is more than 5% by mass, the stability of the curable composition may be affected.

The hydrogenation reaction catalyst (C) of the present invention is a well-known catalyst containing one or more metals selected from the group consisting of platinum, palladium and rhodium which promote the hydrogenation reaction of hydrazine. For example, as the platinum-based catalyst, a platinum-carboxyvinylmethyl complex, a platinum-divinyltetramethyldioxane complex, and a platinum-cyclovinylmethyloxane are exemplified. , platinum-octanal complex, and the like. Examples of the palladium-based catalyst and the ruthenium-based catalyst include a compound such as palladium or rhodium which is a platinum-based metal in place of platinum in the platinum-based catalyst. These hydrogenation catalysts may be used alone or in combination of two or more. Particularly, from the viewpoint of hardenability, it is preferred to contain platinum, and specifically, a platinum-carboxyvinylmethyl complex is preferred. Further, a so-called Wilkinson catalyst containing the above platinum-based metal such as tris(triphenylphosphine)iridium chloride (I) is also contained in the rhodium hydrogenation catalyst (C).

The curable composition of the present invention may contain and contain bismuth as needed. The compound (A1) or the compound (D) which reacts with the ruthenium-containing compound (B1).

This compound (D) can be used, for example, in order to improve adhesion. The compound (D) is a compound which reacts with the Si-H group in the above-mentioned compound (A1) containing ruthenium or a compound which reacts with an alkenyl group or an alkynyl group in the above-mentioned compound (B1) containing ruthenium, and one type can be used. Or a mixture of two or more types. The type of the compound is not particularly limited, and a polyoxyalkylene compound is preferred from the viewpoint of heat resistance of the cured product. Examples of the polyoxyalkylene compound include polyfluorene having a group such as a vinyl group, an ethynyl group, or a Si-H group at both ends of a linear or branched polydimethylsiloxane. a linear or branched dimethyloxane and a diphenyl decane at both ends of a random and/or block, having a polyoxyxylene having a vinyl group, an ethynyl group, a Si-H group or the like; Substituting a part of a methyl group having a linear or branched polydimethyl methoxyalkane with a polyfluorene oxide selected from the group consisting of a vinyl group, an ethynyl group and a Si-H group; having a straight chain or a branched chain a part of a methyl or phenyl group of a random group and/or a block of a methyl oxoxane and a diphenyl siloxane, substituted with a polyoxyl group selected from the group consisting of a vinyl group, an ethynyl group, and a Si-H group. A resin having a base such as a vinyl group, an ethynyl group or a Si-H group.

With respect to the total amount of the compound (A1) containing ruthenium and the compound (B1) containing ruthenium, the amount of the compound (D) to be used is preferably 50% by mass or less. When the amount of the compound (D) used is more than 50% by mass, the softness and light resistance of the cured product obtained may be lowered.

In the curable composition of the present invention, a component such as an inorganic filler or a weather resistance imparting agent may be further added as an optional component.

The inorganic filler may, for example, be an inorganic material such as a filler or a mineral, or may be modified by an organic modification treatment or the like. Adult. Specific examples thereof include cerium oxide such as colloidal cerium oxide, cerium oxide filler, and cerium oxide gel; metal oxides such as alumina, zinc oxide, and titanium oxide; mica, montmorillonite, and cerium; Minerals such as stone, diatomaceous earth, sericite, kaolinite, vermiculite, feldspar powder, vermiculite, erbium, talc, iron talc, and pyrophyllite; these have been modified by organic modification treatment, etc. Quality is the one.

The inorganic filler has a particle diameter of preferably 100 μm or less, more preferably 50 μm or less, from the viewpoint of heat resistance. Further, when the use of the cured product emphasizes transparency, it is preferred to use fine particles having a small amount and a high effect of 1 μm or less. The content of the inorganic filler in the curable composition of the present invention is preferably used as little as possible when transparency is emphasized, so it is preferably from 0 to 10% by mass, which is used for improving heat resistance and viscosity-increasing. When thixotropy is imparted, it is preferably from 10 to 90% by mass.

As the weather resistance imparting agent, a well-known general user such as a light stabilizer, an ultraviolet absorber, a phenol antioxidant, a sulfur-based antioxidant, or a phosphorus-based antioxidant can be used. For example, examples of the light stabilizer include hindered amines, and examples of the ultraviolet absorber include 2-hydroxybenzophenones, 2-(2-hydroxyphenyl)benzotriazoles, and 2-(2-hydroxyphenyl)- 4,6-diaryl-1,3,5-triazines, benzoates, cyanoacrylates, phenolic antioxidants can be cited as triethylene glycol-bis[3-(3-third 5--5-methyl-4-hydroxyphenyl)propionate], dibutylhydroxytoluene (BHT), 2,6-di-t-butyl-p-cresol (DBPC), etc., sulfur-based antioxidants Dialkylthiodipropionates and β-alkylmercaptopropionates are exemplified, and examples of the phosphorus-based antioxidants include organic phosphites.

When the weather resistance imparting agent is used, heat resistance, electrical properties, and hardening are used. The content of the curable composition of the present invention is preferably from 0.0001 to 50% by mass, more preferably from 0.001 to 10% by mass, from the viewpoints of properties, mechanical properties, storage stability, and workability.

In the curable composition of the present invention, various other well-known various resins, additives, fillers and the like can be blended in a range that does not impair the intended properties of the present invention. Examples of various resins which can be optionally formulated include polyether resins such as polyimine resins, polyethylene glycols, and polypropylene glycols, polyurethane resins, epoxy resins, phenol resins, and polyester resins. Examples of the melamine resin, the polyamide resin, the polyphenylene sulfide resin, and the like can be arbitrarily formulated, and examples thereof include an antistatic agent.

In order not to impair the target performance of the present invention, the amount of any component other than the compound containing ruthenium (A1), the compound containing ruthenium (B1), and the ruthenium hydrogenation catalyst (C) is relative to the compound containing ruthenium (A1) With respect to 100 parts by mass of the total amount of the compound (B1) containing ruthenium, it is preferred that the total amount is 10 parts by mass or less.

The curable composition of the present invention has good fluidity at room temperature (25 ° C) and is therefore excellent in handleability. Regarding the fluidity, the viscosity measured by the E-type viscometer at room temperature (25 ° C) in the state without the inorganic filler is preferably 50 Pa. Below S, better is 10 Pa. S below.

Moreover, the cured product of the curable composition of the present invention is excellent in heat resistance, crack resistance, transparency, light resistance and the like. In particular, the curable composition of the present invention can preferably obtain a cured product having a temperature at which the mass of the cured product is reduced by 5% by mass, and is preferably 300 ° C or higher, more preferably 400 ° C or higher. Further, it is possible to obtain a cured product having less occurrence of cracks.

The cured product of the present invention is formed by curing the curable composition of the present invention. The heating temperature at the time of hardening is preferably from 0 to 300 ° C, more preferably from 100 to 200 ° C. The hardening time is preferably 0.1 to 10 hours, more preferably 0.5 to 6 hours. By performing the curing reaction under the curing reaction conditions, a cured product having excellent properties such as heat resistance and crack resistance 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 retardancy, moisture resistance, A material excellent in mechanical properties such as gas barrier properties, flexibility, elongation or strength, electrical insulation properties, low dielectric constant, optical properties, and electrical properties.

The curable composition of the present invention comprising the ruthenium-containing compound of the present invention is excellent in stability, curability, and the like, and further has crack resistance, heat resistance, solvent resistance, alkali resistance, and weather resistance of the cured product. Excellent physical properties such as optical characteristics and electrical characteristics. The curable composition of the present invention can be applied to a display material of an electric/electronic material field, a sealing material for a light material/recording material/semiconductor, a high voltage insulating material, a perfusion for the purpose of insulation/anti-vibration/waterproof/moisture resistance. / Sealing materials, prototypes of plastic parts, coating materials, interlayer insulating films, packaging for insulation, heat shrinkable rubber tubes, O-rings, sealants/protective materials for display devices, optical waveguides, optical fiber protective materials, optical lenses, Adhesive for optical equipment, high heat-resistant adhesive, high heat-dissipating material, high heat-resistant sealing material, solar cell/fuel cell member, solid electrolyte for battery, insulating coating material, photosensitive drum for photocopier, gas separation film, etc. . Also, it can be applied to concrete protection in the field of civil engineering/building materials. Protective materials, linings, soil injecting agents, sealants, cold storage materials, glass coatings, etc., and in medical materials, can also be applied to test tubes, sealing materials, coating materials, sealing materials for sterilization treatment devices, contact lenses, Oxygen-rich membranes, etc.

[Examples]

Hereinafter, the present invention will be further illustrated by the examples, but the present invention is not limited by the examples and the like. Further, the "parts" or "%" in the examples are based on mass.

[Synthesis Example 1]

100 parts of dichlorodimethyl decane was added dropwise to 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-exchanged water, and then the toluene solution was dehydrated, 20 parts of pyridine was added thereto, and 20 parts of dimethylvinyl oxane was further added thereto and stirred at 70 ° C. minute. Thereafter, after washing with 100 parts of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 °C. Then, 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 (gel permeation chromatography) under the following conditions, the molecular weight of the acyclic polysiloxane compound (a1-1) was Mw = 20,000. Furthermore, the following GPCs were carried out under these conditions.

(Measurement conditions for GPC) Pipe column: TSK-GEL MULTIPORE HXLM manufactured by TOSOH Co., Ltd., 7.8 mm × 300 mm Developing solvent: tetrahydrofuran

[Example 1]

100 parts of the acyclic polyaluminoxane compound (a1-1) obtained in Synthesis Example 1 was dissolved in 200 parts of toluene, 0.003 part of platinum catalyst was added, and 10 parts of the cyclic polysiloxane was added. The compound of 1,3,5,7-tetramethylcyclotetraoxane was allowed to react 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 compound (A-1) containing hydrazine. As a result of analysis by GPC, the molecular weight of the compound (A-1) containing ruthenium was Mw = 22,000.

[Synthesis Example 2]

100 parts of dichlorodimethyl decane was added dropwise to 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-exchanged water, and then the toluene solution was dehydrated, 20 parts of pyridine was added thereto, 20 parts of dimethylchloromethane was further added thereto, and the mixture was stirred at 70 ° C for 30 minutes. . Thereafter, the mixture was washed with 100 parts of ion-exchanged water, and then the solvent was evaporated under reduced pressure at 150 °C. Then, it was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C to obtain a non-cyclic polyoxane compound (b1-1). As a result of analysis by GPC, the molecular weight of the acyclic polysiloxane compound (b1-1) was Mw = 20,000.

[Embodiment 2]

100 parts of the acyclic polyaluminoxane compound (b1-1) obtained in Synthesis Example 2 was dissolved in 200 parts of toluene, 0.003 part of platinum catalyst was added, and 10 parts were used as an unsaturated bond. Cyclic polyoxyalkylene compound 1,3,5,7-Tetramethyl-1,3,5,7-tetravinylcyclotetraoxane was allowed to react 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 compound (B-1) containing hydrazine. As a result of analysis by GPC, the molecular weight of the compound (B-1) containing ruthenium was Mw = 22,000.

[Synthesis Example 3]

100 parts of dichlorodimethyl decane was added dropwise to 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 water using 500 parts of ion-exchanged water, and thereafter the toluene solution was dehydrated. 20 parts of pyridine was added, and further 0.5 parts of methyltrichloromethane was added, and the mixture was stirred at room temperature for 30 minutes, and further stirred at 70 ° C for 30 minutes, and then the solution was divided into two equal portions.

To one of the solutions, 2.5 parts of dimethylvinylchloromethane as a monofunctional decane compound having an unsaturated bond was added, and the mixture was stirred at room temperature for 30 minutes, further stirred at 70 ° C for 30 minutes, and then ionized. The exchanged water was washed with water to thereby remove the pyridine hydrochloride to obtain an acyclic polysiloxane compound (a1-2) having an unsaturated bond.

To another solution, 2.5 parts of dimethylchloromethane as a compound into which Si-H group was introduced was added, and the mixture was stirred at room temperature for 30 minutes, further stirred at 70 ° C for 30 minutes, and then washed with ion-exchanged water. Thus, the pyridine hydrochloride was removed to obtain a non-cyclic polyoxyalkylene compound (b1-2).

[Example 3]

100 parts of the non-cyclic poly group having an unsaturated bond obtained in Synthesis Example 3 The oxoxane compound (a1-2) is dissolved in 200 parts of toluene, 0.003 part of a platinum catalyst, and 10 parts of a 1,3,5,7-tetramethyl ring as a cyclic polyoxyalkylene compound are added. The tetraoxane was allowed to react 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 compound (A-2) containing hydrazine. As a result of analysis by GPC, the molecular weight of the compound (A-2) containing ruthenium was Mw = 42,000.

[Example 4]

100 parts of the acyclic polyaluminoxane compound (b1-2) obtained in Synthesis Example 3 was dissolved in 200 parts of toluene, 0.003 part of platinum catalyst was added, and 10 parts were used as an unsaturated bond. The 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane of the cyclic polyoxyalkylene compound was allowed to react 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 evaporated under reduced pressure at 70 ° C to yield Compound (B-2) containing oxime. As a result of analysis by GPC, the molecular weight of the compound (B-2) containing ruthenium was Mw = 42,000.

[Synthesis Example 4]

100 parts of dichlorodimethyl decane was added dropwise to a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide solution, and allowed to react at 105 ° C for 5 hours. The obtained reaction solution was washed with water using 500 parts of ion-exchanged water, and thereafter the toluene solution was dehydrated. 20 parts of pyridine was added, and further 0.5 parts of tetrachloromethane was added, and the mixture was stirred at room temperature for 30 minutes, and further stirred at 70 ° C for 30 minutes, and then the solution was divided into two equal portions.

In one of the solutions, 2.5 parts were added as having an unsaturated bond. Dimethyl vinyl chlorosilane of a monofunctional decane compound, stirred at room temperature for 30 minutes, further stirred at 70 ° C for 30 minutes, and then washed with ion-exchanged water, thereby removing pyridine hydrochloride to obtain an unsaturated state. Acyclic acyclic polyoxane compound (a1-3).

To another solution, 2.5 parts of dimethylchloromethane as a compound into which Si-H group was introduced was added, and the mixture was stirred at room temperature for 30 minutes, further stirred at 70 ° C for 30 minutes, and then washed with ion-exchanged water. Thus, the pyridine hydrochloride is removed to obtain a non-cyclic polyoxyalkylene compound (b1-3).

[Example 5]

100 parts of the acyclic polyoxy siloxane compound (a1-3) having an unsaturated bond obtained in Synthesis Example 4 was dissolved in 200 parts of toluene, 0.003 parts of platinum catalyst was added, and 10 parts were added. 1,3,5,7-tetramethylcyclotetraoxane having a cyclic polyoxyalkylene compound having an unsaturated bond was allowed to react 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 compound (A-3) containing hydrazine. As a result of analysis by GPC, the molecular weight of the compound (A-3) containing ruthenium was Mw = 52,000.

[Embodiment 6]

100 parts of the acyclic polyaluminoxane compound (b1-3) obtained in Synthesis Example 4 was dissolved in 200 parts of toluene, 0.003 part of platinum catalyst was added, and 10 parts were used as an unsaturated bond. The 1,3,5,7-tetramethyl-1,3,5,7-vinylcyclotetraoxane of the cyclic polyoxyalkylene compound was allowed to react 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 hydrazine-containing compound. Compound (B-3). As a result of analysis by GPC, the molecular weight of the compound containing ruthenium (B-3) was Mw = 52,000.

[Embodiment 7]

50 parts of the hydrazine-containing compound (A-1) obtained in Example 1 and 50 parts of the hydrazine-containing compound (B-1) obtained in Example 2 were mixed, and 0.005 parts were mixed. As the platinum-carboxyvinylmethyl complex of the hydrogenation reaction catalyst (C), the curable composition No. 1 was obtained.

[Embodiment 8]

50 parts of the hydrazine-containing compound (A-2) obtained in Example 3 and 50 parts of the hydrazine-containing compound (B-2) obtained in Example 4 were mixed, and 0.005 parts were mixed. As the platinum-carboxyvinylmethyl complex of the hydrogenation reaction catalyst (C), the curable composition No. 2 was obtained.

[Embodiment 9]

50 parts of the hydrazine-containing compound (A-3) obtained in Example 5 and 50 parts of the hydrazine-containing compound (B-3) obtained in Example 6 were mixed, and 0.005 parts were mixed. As the platinum-carboxyvinylmethyl complex of the hydrogenation reaction catalyst (C), the curable composition No. 3 was obtained.

[Comparative Example 1]

50 parts of the acyclic polyfluorene oxide (a1-1) having an unsaturated bond obtained in the above Synthesis Example 1 and 50 parts of the acyclic polyoxyalkylene compound obtained in the above Synthesis Example 2 (b1-1) In the mixture, 0.005 parts of a platinum-carboxyvinylmethyl complex as a curing catalyst was mixed to obtain a curable composition for comparison (ratio-1).

[Comparative Example 2]

Polyoxyalkylene (Mw: 30,000, vinyl amount: 3.5 mmol) obtained by randomly condensing 50 parts of dimethyldimethoxydecane and vinylmethyldimethoxydecane as a monomer /g), polyoxyalkylene which is obtained by randomly condensing 50 parts of dimethyldimethoxydecane and methyldimethoxydecane as a monomer (Mw=30,000, Si-H basis amount) In a mixture of 3.5 mmol/g), 0.005 parts of a platinum-carboxyvinylmethyl complex as a curing catalyst was mixed to obtain a comparatively curable composition (ratio-2).

[Comparative Example 3]

50 parts of vinyl trimethoxy decane, methyl trimethoxy decane and dimethyl dimethoxy decane were randomly condensed in a molar ratio of 1:4:5. Polyoxyalkylene resin (Mw: 30,000, vinyl amount: 3.5 mmol/g), with 50 parts of trimethoxydecane, methyltrimethoxydecane and dimethyldimethoxydecane as monomers and A mixture of a polyoxane resin (Mw: 30,000, Si-H basis amount: 3.5 mmol/g) in which the ratio of molar ratio is 1:4:5 is mixed, and 0.005 parts is mixed as hardening. The platinum-carboxyvinylmethyl complex of the catalyst was used to obtain a comparatively curable composition (ratio-3).

[Comparative Example 4]

50 parts of the compound (A-1) containing ruthenium obtained in Example 1 and 50 parts of polydimethyl methoxy oxane (Mw: 20,000) having a vinyl group at both ends, mixed 0.005 parts of a platinum-carboxyvinylmethyl complex as a curing catalyst was used to obtain a comparatively curable composition (ratio-4).

[Comparative Example 5]

50 parts of the compound (B-1) containing ruthenium obtained in Example 2 and 50 parts of a mixture of Si-H-based polydimethyl siloxane (MW: 20,000), 0.005 parts of a platinum-carboxyvinylmethyl complex as a hardening catalyst was obtained. A comparatively hardening composition (ratio-5).

[Comparative Example 6]

Mixing 90 parts of dichlorodimethyl decane with 9 parts of dichlorodiphenyl decane, and adding dropwise to a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide solution, Polymerization was carried out at 105 ° C for 5 hours. The obtained reaction solution was washed with 500 parts of ion-exchanged water, and then the toluene solution was dehydrated, 20 parts of pyridine was added thereto, and 20 parts of dimethylvinylchloromethane was further added thereto, and the mixture was stirred at 70 ° C. 30 minutes. Then, after washing with 100 parts of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 °C. Then, 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 polyoxane compound having an unsaturated bond (ratio a1-1).

100 parts of the obtained non-cyclic polyoxyalkylene compound having an unsaturated bond (ratio a1-1) was dissolved in 200 parts of toluene, 0.003 part of platinum catalyst was added, and 10 parts were used as a cyclic poly The 1,3,5,7-tetramethylcyclotetraoxane of the siloxane compound was allowed to react 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 compound containing hydrazine (ratio A-1). As a result of analysis by GPC, the molecular weight of the compound containing ruthenium (compared with A-1) was Mw = 22,000.

On the other hand, 90 parts of dichlorodimethyl decane and 10 parts of dichlorodiphenyl decane were mixed and added dropwise to 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide solution. In the mixture, it is polymerized at 105 ° C 5 hours. The obtained reaction solution was washed with 500 parts of ion-exchanged water, and then the toluene solution was dehydrated, 20 parts of pyridine was added thereto, 20 parts of dimethylchloromethane was further added thereto, and the mixture was stirred at 70 ° C for 30 minutes. . Then, after washing with 100 parts of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 °C. Then, it was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C to obtain a non-cyclic polyoxane compound (ratio b1-1).

100 parts of the obtained acyclic polyaluminoxane compound (than b1-1) was dissolved in 200 parts of toluene, 0.003 part of platinum catalyst was added, and 10 parts of the cyclic poly group having an unsaturated bond was added. The 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane of the siloxane compound was allowed to react 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 compound containing hydrazine (ratio B-1). As a result of analysis by GPC, the molecular weight of the compound containing ruthenium (compared with B-1) was Mw = 22,000.

50 parts of the above-mentioned compound containing ruthenium (compared with A-1) and 50 parts of the above-mentioned compound containing ruthenium (compared with B-1) are mixed, and 0.005 part of platinum-carboxyethylene as a hardening catalyst is mixed. A methyl group complex obtained a comparatively hardenable composition (ratio-6).

[Comparative Example 7]

Mixing 75 parts of dichlorodimethyl decane with 24 parts of dichlorodiphenyl decane, and adding dropwise to a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide solution, Polymerization was carried out at 105 ° C for 5 hours. The obtained reaction solution was washed with 500 parts of ion-exchanged water, and then the toluene solution was dehydrated, and 20 parts of pyridine was added thereto, and further added thereto. 20 parts of dimethylvinylchloromethane was stirred at 70 ° C for 30 minutes. Then, after washing with 100 parts of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 °C. Then, 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 polyoxane compound having an unsaturated bond (ratio a1-2).

100 parts of the obtained acyclic polysiloxane compound having an unsaturated bond (ratio a1-2) was dissolved in 200 parts of toluene, 0.003 part of platinum catalyst was added, and 10 parts were used as a cyclic polymerization. The 1,3,5,7-tetramethylcyclotetraoxane of the siloxane compound was allowed to react 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 compound containing hydrazine (ratio A-2). As a result of analysis by GPC, the molecular weight of the compound containing ruthenium (compared with A-2) was Mw = 22,000.

On the other hand, 75 parts of dichlorodimethyl decane and 24 parts of dichlorodiphenyl decane were mixed and added dropwise to 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide solution. The mixture was polymerized at 105 ° C for 5 hours. The obtained reaction solution was washed with 500 parts of ion-exchanged water, and then the toluene solution was dehydrated, 20 parts of pyridine was added thereto, 20 parts of dimethylchloromethane was further added thereto, and the mixture was stirred at 70 ° C for 30 minutes. . Then, after washing with 100 parts of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 °C. Then, it was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C to obtain a non-cyclic polyoxane compound (ratio b1-2).

100 parts of the obtained acyclic polyaluminoxane compound (than b1-2) was dissolved in 200 parts of toluene, 0.003 part of platinum catalyst was added, and 10 parts of the cyclic poly group having an unsaturated bond was added. 1,3,5,7-tetramethyl-methoxane compound 1,3,5,7-Tetravinylcyclotetraoxane was allowed to react 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 compound containing hydrazine (ratio B-2). As a result of analysis by GPC, the molecular weight of the compound containing ruthenium (compared to B-2) was Mw = 22,000.

50 parts of the above-mentioned compound containing ruthenium (compared with A-2) and 50 parts of the above-mentioned compound containing ruthenium (compared to B-2) are mixed, and 0.005 part of platinum-carboxyethylene as a hardening catalyst is mixed. A methyl group complex obtained a comparatively hardenable composition (ratio-7).

[Examples 10 to 12, Comparative Examples 8 to 12]

The curable composition for comparison (ratio -1) to (ratio -5) obtained in the curable compositions Nos. 1 to 3 and the comparative examples 1 to 5 obtained in the above Examples 7 to 9 on an aluminum plate. Films having a film thickness of about 1 mm were respectively formed and cured by heating at 150 ° C for 30 minutes to obtain cured products No. 1 to 3 and a cured product ratio of 1 to 5. Further, the number of the curable composition used corresponds to the number of the cured product obtained. The hardened materials were evaluated for the hardened state and the 180 degree bending test in the following manner.

The hardened state is judged based on whether or not the cured film has a feeling of adhesion after a specific hardening time, and the state having fluidity is evaluated as ×, and there is no fluidity but the degree of adhesion is evaluated as Δ~ When the adhesiveness was not felt, it was evaluated as ◎.

In the 180-degree bending test, the state of the film when the film was bent at 180 degrees was observed on a cured film obtained by forming a film having a film thickness of about 1 mm on an aluminum plate. The sample with no crack and peeling when the film was bent at 180 degrees was evaluated as The sample which was cracked when it was bent at 180 degrees and cracked and peeled at 90 degrees was evaluated as Δ, and the sample which was cracked at 90 degrees was evaluated as ×.

The results are shown in Table 1.

As shown in Table 1, the cured products Nos. 1 to 3 of Examples 10 to 12 and the cured products of Comparative Examples 9 to 12 were in the same state or improved as compared with 2 to 5, and the 180-degree bending test was performed. The evaluation results have been improved. Further, a sufficient solid cured product could not be obtained from the curable composition (ratio-1). From this, it was confirmed that the cured state and the flexibility were improved by adopting the constitution of the present invention.

[Examples 13 to 15, Comparative Examples 13 and 14]

The curable composition Nos. 1 to 3 obtained in the above Examples 7 to 9 and the curable compositions (ratio -6) and (ratio -7) obtained in the above Comparative Examples 6 and 7 were respectively injected into 20 In a mold of mm × 20 mm × 3 mm, it was heated at 150 ° C for 1 hr to obtain a cured product No. 4 to 6 having a thickness of 3 mm, a ratio of 6, and a ratio of 7. The photo-deterioration test was carried out using a high-pressure mercury lamp for the hardened material, and the photo-deterioration test was carried out by irradiating the radiation of 9.96 W/cm at 365 nm for 2 hours. The transmittance at 400 nm before and after the photodegradation test is shown in Table 2.

As shown in Table 2, the cured products Nos. 4 to 6 of Examples 13 to 15 and the cured products of Comparative Examples 11 and 12 had a light resistance higher than that of Comparative Examples 6 and 6. From this, it was confirmed that the cured product obtained by curing the curable composition composed of only the aliphatic group of R ^a to R ^e has good light resistance.

Claims (9)

A compound containing ruthenium represented by the following formula (1): (wherein R ^a to R ^d are saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms which may be the same or different; R ^e is a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, or may be saturated fat An aromatic hydrocarbon group having 6 to 12 carbon atoms substituted by a hydrocarbon group, and when there are a plurality of R ^e , the R ^{e may} be the same or different; Y is an alkylene group having 2 to 4 carbon atoms, Z Is an alkenyl or alkynyl group having 2 to 4 carbon atoms, K is a number from 2 to 7, T is a number from 1 to 7, and P is a number from 0 to 3; M is represented by the formula (1) The mass average molecular weight of the compound containing ruthenium is 3,000 to 1,000,000. A compound containing ruthenium represented by the following formula (2): (wherein R ^a to R ^d are saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms which may be the same or different; R ^e is a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, or may be saturated fat An aromatic hydrocarbon group having 6 to 12 carbon atoms substituted by a hydrocarbon group, and when there are a plurality of R ^e , the R ^{e may} be the same or different; Y is an alkylene group having 2 to 4 carbon atoms, Z Is an alkenyl group or alkynyl group having 2 to 4 carbon atoms, k is a number from 2 to 7, and p is a number from 1 to 4; m is a mass average molecular weight of a compound containing ruthenium represented by the general formula (2) It is 3,000 to 1 million). A compound containing hydrazine according to claim 1 or 2, wherein R ^e is a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms. A compound containing hydrazine as claimed in claim 1 or 2, wherein all of R ^a to R ^e are methyl groups. A curable composition containing (A1) a compound containing ruthenium of claim 1 in which Z in the following formula (1) is a hydrogen atom, (B1) Z in the following formula (1) is The alkylene or alkynyl group having 2 to 4 carbon atoms is formed by the ruthenium-containing compound of claim 1 and (C) hydrazine hydrogenation catalyst. (wherein R ^a to R ^d are saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms which may be the same or different; R ^e is a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, or may be saturated fat An aromatic hydrocarbon group having 6 to 12 carbon atoms substituted by a hydrocarbon group, and when there are a plurality of R ^e , the R ^{e may} be the same or different; Y is an alkylene group having 2 to 4 carbon atoms, Z Is an alkenyl or alkynyl group having 2 to 4 carbon atoms, K is a number from 2 to 7, T is a number from 1 to 7, and P is a number from 0 to 3; M is represented by the formula (1) The mass average molecular weight of the compound containing ruthenium is 3,000 to 1,000,000. A curable composition comprising (A2) a compound containing ruthenium of claim 2 in which Z in the following formula (2) is a hydrogen atom, (B2) Z in the following formula (2) is A ruthenium-containing compound of claim 2 having an alkenyl group or an alkynyl group having 2 to 4 carbon atoms, and (C) a hydrogenation reaction catalyst. (wherein R ^a to R ^d are saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms which may be the same or different; R ^e is a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, or may be saturated fat An aromatic hydrocarbon group having 6 to 12 carbon atoms substituted by a hydrocarbon group, and when there are a plurality of R ^e , the R ^{e may} be the same or different; Y is an alkylene group having 2 to 4 carbon atoms, Z Is an alkenyl group or alkynyl group having 2 to 4 carbon atoms, k is a number from 2 to 7, and p is a number from 1 to 4; m is a mass average molecular weight of a compound containing ruthenium represented by the general formula (2) It is 3,000 to 1 million). The sclerosing composition of claim 5, wherein R ^a to R ^e in the above formula (1) of any one of the above-mentioned (A1) component-containing compound and the above-mentioned (B1) component-containing compound All are methyl. The sclerosing composition of claim 6, wherein R ^a to R ^e in the above formula (2) of any one of the above-mentioned (A2) component-containing compound and the above-mentioned (B2) component-containing compound All are methyl. A cured product formed by hardening a curable composition according to any one of claims 5 to 8.