KR101478803B1 - Silicon-containing compound, curable composition and cured product - Google Patents

Abstract

The silicon-containing compound of the present invention is represented by the following general formula (1). The curable composition of the present invention contains the silicon-containing compound in which Z in the general formula (1) is a hydrogen atom, the silicon-containing compound in which Z is a C _2-4 alkenyl group or an alkynyl group, and a hydrosilylation reaction catalyst And is excellent in handleability and curability, and the resulting cured product is excellent in transparency and flexibility.

Wherein R ^a to R ^d are C _1-12 saturated aliphatic hydrocarbon groups, R ^e is a C _1-12 saturated aliphatic hydrocarbon group or a C _6-12 aromatic hydrocarbon group, and Y is a C _2-4 carbon atom number 2 And Z is a hydrogen atom or a C _2-4 alkenyl group or an alkynyl group, K is a number of 2 to 7, T is a number of 1 to 7, P is a number of 0 to 3, And M is a number obtained by setting the mass average molecular weight of the silicon-containing compound to 3,000 to 1,000,000.)

Silicon-containing compounds, curable compositions, alkenyl groups, alkynyl groups, hydrosilylation

Description

TECHNICAL FIELD [0001] The present invention relates to a silicon-containing compound, a curable composition and a cured product,

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. More specifically, the present invention relates to a cured product which is excellent in handleability and curability, a curable composition containing the same, and a cured product excellent in transparency and flexibility. The present invention also relates to a curable composition containing the same.

A variety of studies have been made on composite materials obtained by combining organic materials and inorganic materials, and industrially, a method of combining an inorganic filler with an organic polymer or a coating method of modifying a metal surface with an organic polymer has been used. In these organic-inorganic composite materials, since the material constituting the organic-inorganic composite material has a size larger than the order of micrometer, it is possible to improve the physical properties of a part more than expected, but various other properties and properties are merely organic materials and inorganic And only the expected value from the performance rule of the performance or physical properties of each of the cast materials.

On the other hand, recently, organic-inorganic composite materials in which domains of respective materials of organic and inorganic materials are combined in nanometer order and molecular level are actively researched. Such a material is expected to be a material having not only the characteristics of each material, but also the merits of each material, and further having a novel functionality which is unpredictable as a rational rule and is completely different from each material itself.

Such organic-inorganic composite materials include a chemical bond type in which one material and the other material are bonded at a molecular level through covalent bonding, and a hybrid type in which one material is used as a matrix and the other material is finely dispersed / have. The sol-gel method is frequently used as a method for synthesizing an inorganic material used in these organic-inorganic composite materials. The sol-gel method is a method in which hydrolysis of a precursor molecule and subsequent polycondensation reaction are carried out, Is a reaction 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, attention is paid to the difference in the condensation rate depending on the chain length of the alkyl group of the alkyltrialkoxysilane, and after the polycondensation of methyltrimethoxysilane, a long chain alkyltrialkoxysilane having a slow polycondensation rate And then a silanol group in the polysiloxane is sealed. Further, a polycondensation reaction of methyltrimethoxysilane is carried out by using an aluminum catalyst. Acetyl acetone is added when the molecular weight reaches a predetermined value, And attempts to improve the storage stability by performing ligand exchange. However, these methods have insufficient improvement in 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 as a chemically bonded organic-inorganic composite material has been proposed. For example, Patent Document 1 discloses a method for producing a silicon-containing polymer (A) containing a silicon-containing polymer (A) having a crosslinking structure and having an alkenyl or alkynyl group, a silicon- Containing curable composition excellent in handleability and curability, and excellent in heat resistance of the obtained cured product. However, this silicon-containing curable composition can not be said to have a sufficient curing property and has a problem that a cured product having sufficient performance at a low temperature and in a short time can not be obtained.

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

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

An object of the present invention is to provide a curable composition which is excellent in handling properties and curability, and has excellent transparency and flexibility.

DISCLOSURE OF THE INVENTION As a result of conducting studies to solve the above problems, the present inventors have found that a silicon-containing compound having a specific structure and a curing composition containing the same solve the above problems and have completed the present invention.

The present invention provides 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 of 1 to 12 carbon atoms and R ^e is a saturated aliphatic hydrocarbon group of 1 to 12 carbon atoms or a carbon atom number which may be substituted with a saturated aliphatic hydrocarbon group Y is an alkylene group having 2 to 4 carbon atoms, and Z is a hydrogen atom or an alkenyl group or an alkynyl group having 2 to 4 carbon atoms, and R < ^e > , K is a number of from 2 to 7, T is a number of from 1 to 7, and P is a number of from 0 to 3. M represents a weight average molecular weight of the silicon-containing compound represented by the general formula (1) .

The present invention also relates to (A1) the silicon-containing compound wherein Z is a hydrogen atom in the general formula (1), (B1) a compound represented by the general formula (1) wherein Z is an alkenyl group or an alkynyl group having 2 to 4 carbon atoms A silicon-containing compound, and (C) a hydrosilylation reaction catalyst.

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

First, the silicon-containing compound of the present invention represented by the above general formula (1) will be explained.

Examples of the saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms represented by R ^a to R ^e in the above general formula (1) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert- Cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, iso Octyl, 3-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl and the like.

The aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted with a saturated aliphatic hydrocarbon group represented by R ^e has 6 to 12 carbon atoms in total including the saturated aliphatic hydrocarbon group as a substituent. As the saturated aliphatic hydrocarbon group which is a substituent, for example, among the saturated aliphatic hydrocarbon groups exemplified above, those capable of satisfying the carbon atom number can be employed. Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted with a saturated aliphatic hydrocarbon group represented by R ^e include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, Isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4- tert -butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl and the like.

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 -, CH ₂ ═C (CH ₃ ) - , CH ₂ ═C (CH ₃ ) -CH ₂ -, and CH ₂ ═CH-CH (CH ₃ ) -. Examples of the alkynyl group having 2 to 4 carbon atoms represented by Z include the following groups .

A preferred form of the silicon-containing compound of the present invention represented by the above 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 a common synthetic method is a silicon-containing compound represented by the following general formula (2), or a mixture of plural kinds of silicon-containing compounds represented by the general formula (1), and is represented by the following general formula (2) Containing compound as a main component. For example, a compound having a KT of greater than 1 in the above-mentioned general formula (1) can be produced even when ^a cyclopolysiloxane represented by ^a polyfunctional (R ^a SiHO) _K is used as a compound introducing ^a cyclopolysiloxane ring do. This is because the production of a compound in which two or more Si-H of the cyclopolysiloxane is bound to the non-cyclic polysiloxane through Y is energetically significant.

(Wherein R ^a to R ^d are the same or different saturated aliphatic hydrocarbon groups of 1 to 12 carbon atoms and R ^e is a saturated aliphatic hydrocarbon group of 1 to 12 carbon atoms or a carbon atom number which may be substituted with a saturated aliphatic hydrocarbon group Y is an alkylene group having 2 to 4 carbon atoms, Z is a hydrogen atom or an alkenyl group or an alkynyl group having 2 to 4 carbon atoms, and R < ^e > , k is a number of 2 to 7, and p is a number of 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) 3,000 to 1,000.

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

The R ^e in the general formula (1) or the general formula (2) is preferably a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms since the resulting cured product has good light resistance, and since the resulting cured product has good heat resistance, desirable.

In the above general formula (2), k is 2 to 7. If it is larger than 7, the number of functional groups is too large, and flexibility required for the obtained cured product is not obtained. k is preferably from 2 to 5 since it is industrially easy to obtain a raw material and the number of functional groups is appropriate, and most preferably 3.

The silicon-containing compound of the present invention has a weight average molecular weight of 3,000 to 1,000,000. If it is less than 3000, the heat resistance of the obtained cured product becomes insufficient, and if it is more than 1 million, the viscosity becomes large, which causes a problem in handling. The mass average molecular weight is preferably 5,000 to 50,000, more preferably 10,000 to 100,000.

The silicon-containing compound of the present invention is not particularly limited by the production method thereof, and can be produced by applying a well-known reaction. The following production method is a method in which Z in the general formula (2) is a hydrogen atom and Z is an alkane having 2 to 4 carbon atoms, as represented by the general formula (2) of the silicon- Or an alkynyl group.

In the following description, Z in the general formula (1) or (2) is a hydrogen atom, and Z in the general formula (1) or (2) An alkenyl group having 2 to 4 carbon atoms or an alkynyl group, respectively, is referred to as a silicon-containing compound (B1) or (B2).

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 a cyclic polysiloxane compound (a2) with a non-cyclic polysiloxane compound (a1) having an unsaturated bond as a precursor.

The above-mentioned non-cyclic polysiloxane compound (a1) having an unsaturated bond is obtained by condensation reaction of one kind or two or more kinds of bifunctional silane compounds by hydrolysis, then when p is 1, it is a monofunctional monosilane compound, and when p is 3 Is reacted with a trifunctional monosilane compound, when p is 4, with a tetrafunctional monosilane compound, and further reacted with a monofunctional silane compound having an unsaturated group. When p is 2, the condensation reaction can be followed by reaction with a monofunctional silane compound having an unsaturated group. Representative examples of the functional groups of these silane compounds are an alkoxy group, a halogen group or a hydroxyl group. The cyclic polysiloxane compound (a1) having an unsaturated bond and the cyclic polysiloxane compound (a2) are bonded by the reaction between the unsaturated bond carbon of (a1) and the Si-H group of (a2).

Examples of the bifunctional silane compound used for preparing the above-mentioned unsaturated bond-containing cyclic polysiloxane compound (a1) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dibutyl Dialkoxymonosilane compounds such as dimethoxysilane, dibutyldiethoxysilane, dioctyldimethoxysilane and dioctyldiethoxysilane; A monosilane compound in which one or two alkoxy groups of these dialkoxymonosilane compounds are substituted with a halogen atom or a hydroxyl group selected from the group consisting of fluorine, chlorine, bromine and iodine; And a disiloxane compound and an oligosiloxane compound in which two or more of these monosilane compounds are condensed.

Examples of the monofunctional monosilane compound include trimethylethoxysilane, trimethylmethoxysilane, triethylethoxysilane, triethylmethoxysilane, tributylmethoxysilane, tributylethoxysilane, trioctylmethoxy Monoalkoxysilane compounds such as silane, trioctylethoxysilane, triphenylethoxysilane, triphenylmethoxysilane, methyldiphenylethoxysilane, and dimethylphenylethoxysilane; And monosilane compounds in which the alkoxy groups of these monoalkoxysilane compounds are substituted with a halogen atom or a hydroxyl group selected from the group consisting of fluorine, chlorine, bromine and iodine.

Examples of the trifunctional monosilane compound include trisethoxymethylsilane, trismethoxymethylsilane, trisethoxyethylsilane, trismethoxyethylsilane, trisethoxybutylsilane, trismethoxybutylsilane, trisethoxyoctylsilane, Trisalkoxysilane compounds such as trismethoxyoctylsilane, trisethoxyphenylsilane, and trismethoxyphenylsilane; And monosilane compounds in which one to three alkoxy groups of these trisalkoxysilane compounds are substituted with a halogen atom or a hydroxyl group selected from the group consisting of fluorine, chlorine, bromine and iodine.

Examples of the tetrafunctional monosilane compound include tetrakisalkoxysilane compounds such as tetrakisethoxysilane and tetrakismethoxysilane; And monosilane compounds in which one to four alkoxy groups of these tetrakisalkoxysilane compounds are substituted with a halogen atom or a hydroxyl group selected from the group consisting of fluorine, chlorine, bromine and iodine.

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

Examples of the cyclic polysiloxane compound (a2) include 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, 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, 1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3, 5,7,9-pentaphenylcyclopentasiloxane, 1,3,5,7,9,11-hexaphenylcyclohexasiloxane, and the like.

On the other hand, as the above-mentioned 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 part or all of the hydrogen atoms are substituted with deuterium and / or fluorine, a compound in which some or all of the hydrogen atoms of the silicon-containing compound of the present invention are substituted with deuterium and / or fluorine can be obtained.

The condensation reaction by hydrolysis for obtaining the 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. The hydrolysis / condensation reaction of the bifunctional silane compound is a reaction in which an alkoxy group or a halogen group is hydrolyzed by water to form a silanol group (Si-OH group), and the resulting silanol group, a silanol group and an alkoxy group, The halogen group proceeds by condensation. In order to accelerate the hydrolysis reaction, an appropriate amount of water is preferably added, and a catalyst may be added. In addition, the condensation reaction proceeds also by moisture in the air, or a trace amount of water contained in a solvent other than water. A solvent may be used for this reaction. The solvent is not particularly limited, but specific examples thereof include water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone, dioxane, tetra And hydrophilic organic solvents such as hydrofluoric acid, hydrofluoric acid, and hydrofuran. These may be used alone or in combination of two or more.

As the catalyst, an acid or base can be used. 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; Inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia; Amine compounds (organic bases) such as trimethylamine, triethylamine, monoethanolamine and diethanolamine; Titanium compounds such as tetraisopropyl titanate and tetrabutyl titanate; Tin compounds such as dibutyl tin laurate and octyl tartaric acid; Boron compounds such as trifluoroborane; Aluminum compounds such as aluminum trisacetylacetate; Chlorides of metals such as iron, cobalt, manganese and zinc, and metal carboxylates such as naphthenate and octylate of these metals, and these may be used singly or in combination of two or more. When the hydrolysis / condensation reaction is carried out from two or more bifunctional silane compounds, the hydrolysis / condensation reaction may be carried out by separately performing hydrolysis to some extent and then by mixing them both, Condensation reaction may be carried out.

As described above, the acyclic polysiloxane compound (a1) having an unsaturated bond as a precursor has, after the above hydrolysis and condensation reaction, a monofunctional monosilane compound when p is 1 and a trifunctional Reacting the monosilane compound with a tetrafunctional monosilane compound when p is 4 and then reacting it with a monofunctional silane compound having an unsaturated group. When p is 2, a monofunctional silane compound having an unsaturated group . ≪ / RTI >

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

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

The silicon-containing compound (B2) can be obtained, for example, by reacting a cyclic polysiloxane compound (b2) having an unsaturated bond with the acyclic polysiloxane compound (b1) as a precursor. The cyclic polysiloxane compound (b1) can be obtained by condensation reaction of one kind or two or more kinds of bifunctional silane compounds by hydrolysis, then, when p is 1, it is a monofunctional monosilane compound and when p is 3, Reacting the functional monosilane compound with a tetrafunctional monosilane compound when p is 4, and further reacting with a Si-H group introducing compound. The cyclic polysiloxane compound (b1) and the cyclic polysiloxane compound (b2) having an unsaturated bond are bonded by the reaction between the Si-H group of the (b1) and the unsaturated group of the (b2). Typical functional groups of the bifunctional silane compound are an alkoxy group, a halogen group or a hydroxyl group.

Examples of the bifunctional silane compound used for producing the above-mentioned cyclic polysiloxane compound (b1) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dibutyldimethoxysilane, Dialkoxymonosilane compounds such as dibutyldiethoxysilane, dioctyldimethoxysilane and dioctyldiethoxysilane; A monosilane compound in which one or two alkoxy groups of these dialkoxymonosilane compounds are substituted with a halogen atom or a hydroxyl group selected from the group consisting of fluorine, chlorine, bromine and iodine; And a disiloxane compound and an oligosiloxane compound 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 , Monoalkoxysilane compounds such as trioctylethoxysilane, triphenylethoxysilane, triphenylmethoxysilane, methyldiphenylethoxysilane, and dimethylphenylethoxysilane; And monosilane compounds in which the alkoxy groups of these monoalkoxysilane compounds are substituted with a halogen atom or a hydroxyl group selected from the group consisting of fluorine, chlorine, bromine and iodine.

Examples of the trifunctional monosilane compound include trisethoxymethylsilane, trismethoxymethylsilane, trisethoxyethylsilane, trismethoxyethylsilane, trisethoxybutylsilane, trismethoxybutylsilane, trisethoxy Trisalkoxysilane compounds such as octylsilane, trismethoxyoctylsilane, trisethoxyphenylsilane, and trismethoxyphenylsilane; And monosilane compounds in which one to three alkoxy groups of these trisalkoxysilane compounds are substituted with a halogen atom or a hydroxyl group selected from the group consisting of fluorine, chlorine, bromine and iodine.

Examples of the tetrafunctional monosilane compound include tetrakisalkoxysilane compounds such as tetrakisethoxysilane and tetrakismethoxysilane; And monosilane compounds in which one to four alkoxy groups of these tetrakisalkoxysilane compounds are substituted with a halogen atom or a hydroxyl group selected from the group consisting of fluorine, chlorine, bromine and iodine.

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-triphenyl-1,3,5-trivinylcyclotrisiloxane, 1,3,5,7-tetraphenyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5 , 7,9-pentaphenyl-1,3,5,7,9-pentavinyl cyclopentasiloxane, and the like.

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

On the other hand, as the cyclic polysiloxane compound (b2) having a bifunctional silane compound, a monofunctional monosilane compound, a trifunctional monosilane compound, a tetrafunctional monosilane compound, a Si-H group introducing compound or an unsaturated bond, A compound in which some or all of the hydrogen atoms of the silicon-containing compound of the present invention, which will be described later, are substituted with deuterium and / or fluorine can be obtained by using a compound in which some or all of the hydrogen atoms are substituted with deuterium and / have.

The condensation reaction by hydrolysis to obtain an acyclic polysiloxane compound (b1) which is a precursor of the silicon-containing compound (B2) can be carried out by a so-called sol-gel reaction, ) ≪ / RTI >

The reaction between the noncyclic polysiloxane compound (b1) which is a precursor and the cyclic polysiloxane compound (b2) having an unsaturated bond may be carried out by a hydrosilylation reaction method. For example, a silicon-containing compound (B2) is obtained by mixing an acyclic polysiloxane compound (b1) with a cyclic polysiloxane compound (b2) having an unsaturated bond, adding a certain amount of a platinum catalyst and then heating.

The silicon-containing compound of the present invention can be used not only as a main component of the curable composition as described later, but also as a resin, a plastic modifier, etc. mixed with another polymer compound or a polymer composition.

On the other hand, in the non-cyclic siloxane chain of the general formula (1) or (2), although not in the range of the silicon-containing compound of the present invention, boron, magnesium, aluminum, phosphorus, titanium, zirconium, hafnium, , Niobium, tantalum, tin, tellurium, and the like. As the method, there can be mentioned, for example, a method in which hydrolysis / condensation reaction is carried out by using these ternary feeder derivatives in combination, and elements other than silicon are combined in the siloxane chain. Also, some of the hydrogen atoms of the above silicon-containing compounds may be substituted with deuterium and / or fluorine.

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

The curable composition of the present invention comprises a silicon-containing compound (A1) wherein Z in the general formula (1) is a hydrogen atom, a silicon-containing compound A compound (B1), and a hydrosilylation reaction catalyst (C) as essential components. In the curable composition of the present invention, the Z group of the silicon-containing compound (A1) and the Z group of the silicon-containing compound (B1) are reacted by the action of heat and the hydrosilylation reaction catalyst (C) to cure. Preferred examples 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).

The curable composition of the present invention preferably contains 5 to 5000 parts by mass of the silicon-containing compound (B1) per 100 parts by mass of the silicon-containing compound (A1), more preferably 10 to 1000 parts by mass. The content of the hydrosilylation reaction catalyst (C) in the curable composition of the present invention is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass, from the viewpoints of curability and storage stability. 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 at least one metal selected from the group consisting of platinum, palladium and rhodium which promotes the hydrosilylation reaction. 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, for example, a compound containing palladium or rhodium as the platinum-based metal in place of platinum in the platinum-based catalyst. These may be used alone or in combination of two or more. In particular, from the viewpoint of curability, platinum is preferably contained, and specifically platinum-carbonylvinylmethyl complex is preferable. Also included in the hydrosilylation reaction catalyst (C) is a so-called Wilkinson catalyst containing the platinum group metal such as chlorotris (triphenylphosphine) rhodium (I).

The curable composition of the present invention may optionally contain a compound (D) capable of reacting with the silicon-containing compound (A1) or the silicon-containing compound (B1).

The compound (D) can be used, for example, for the purpose of improving adhesion. The compound (D) is a compound which reacts with a Si-H group in the silicon-containing compound (A1) or a compound which reacts with an alkenyl group or an alkynyl group in the silicon-containing compound (B1) Or more. The compound species is not particularly limited, but a polysiloxane compound is preferable from the viewpoint of the heat resistance of the cured product. Examples of the polysiloxane compound include silicon having groups such as a vinyl group, an acetylene group and a Si-H group at both terminals of a linear or branched polydimethylsiloxane; Silicon having vinyl groups, acetylene groups, Si-H groups and the like at both ends of random and / or block bodies of dimethylsiloxane and diphenylsiloxane having linear or branched chains; Silicon in which a part of the methyl groups of the linear or branched polydimethylsiloxane is substituted with a group selected from a vinyl group, an acetylene group and a Si-H group; A silicone in which a methyl group or a part of phenyl groups in a random and / or block form of dimethylsiloxane and diphenylsiloxane having a straight chain or branch is substituted with a group selected from a vinyl group, an acetylene group and a Si-H group; A vinyl group, an acetylene group, and a resin 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) If it is more than 50% by mass, the flexibility and light resistance of the resulting cured product may deteriorate.

In the curable composition of the present invention, an optional component such as an inorganic filler and weatherability-imparting agent may be further blended.

Examples of the inorganic filler include inorganic materials such as so-called fillers and minerals, and those modified by organic modification treatment or the like. Specific examples thereof include silicon dioxide such as colloidal silica, silica filler and silica gel; Metal oxides such as aluminum oxide, zinc oxide and titanium oxide; Mica, montmorillonite, silica, diatomaceous earth, sericite, kaolinite, flint, feldspar, vermiculite, attapulgite, talc, minnesotite, pyrophyllite minerals such as pyrophyllite; And those modified by an organic modification treatment or the like.

The particle diameter of the inorganic filler is preferably 100 占 퐉 or less, more preferably 50 占 퐉 or less in view of heat resistance. When the use of the cured product emphasizes transparency, it is preferable to use fine particles having a size of 1 탆 or less which are small in the amount used. The content of the inorganic filler in the curable composition of the present invention is preferably from 0 to 10% by mass, more preferably from 0 to 10% by mass, more preferably from 0 to 10% by mass, When it is used for imparting, it is preferably 10 to 90 mass%.

As the weathering-imparting agent, there may be used generally known ones such as a light stabilizer, an ultraviolet absorber, a phenol-based antioxidant, a sulfur-based antioxidant and a phosphorus-based antioxidant. Examples of the light stabilizer include hindered amines. Examples of ultraviolet absorbers include 2-hydroxybenzophenones, 2- (2-hydroxyphenyl) benzotriazoles, 2- (2-hydroxyphenyl) Triaryl-1,3,5-triazines, benzoates and cyanoacrylates. Examples of the phenol antioxidant include triethylene glycol-bis [3- (3-t-butyl- (BHT), 2,6-di-t-butyl-paracresol (DBPC), and the like. As the sulfur-based antioxidant, Dialkyl thiodipropionates,? -Alkyl mercaptopropionic acid esters, and phosphorus-based antioxidants include organic phosphites.

When the weathering-imparting agent is used, the content thereof is preferably from 0.0001 to 50 mass%, more preferably from 0.001 to 10 mass%, and more preferably from 0.001 to 10 mass%, of the curable composition of the present invention from the viewpoints of heat resistance, electrical properties, curability, mechanical properties, storage stability, Is more preferable.

In the curable composition of the present invention, various other known resins, additives, fillers and the like may be blended to the extent that the intended performance of the present invention is not impaired. Examples of various resins that can be optionally compounded include polyimide resins, polyether resins such as polyethylene glycol and polypropylene glycol, polyurethane resins, epoxy resins, phenol resins, polyester resins, melamine resins, polyamide resins, Feed resin, and the like, and examples of additives that can be arbitrarily combined include an antistatic agent and the like.

The amount of the optional components other than the silicon-containing compound (A1), the silicon-containing compound (B1) and the hydrosilylation reaction catalyst (C) is such that the silicon-containing compound (A1) Containing compound (B1) is preferably 10 parts by mass or less based on 100 parts by mass of the total amount of the compound (B1).

The curable composition of the present invention has good fluidity at room temperature (25 캜) and excellent handling properties. Regarding the fluidity, the viscosity measured by an E-type viscometer at room temperature (25 ° C) is preferably 50 Pa · S or less, more preferably 10 Pa · S or less, in the absence of an inorganic filler.

The cured product of the curable composition of the present invention is excellent in heat resistance, crack resistance, transparency, light resistance and the like. Specifically, a cured product having a temperature of 300 ° C or higher, more preferably 400 ° C or higher, which causes a mass reduction of 5% by mass of the cured product, is preferably obtained from the curable composition of the present invention. In addition, a cured product having less occurrence of cracks is preferably obtained.

The cured product of the present invention is obtained by curing the curable composition of the present invention. The heating temperature at the time of curing is preferably 0 to 300 占 폚, more preferably 100 to 200 占 폚. 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 excellent 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 and is particularly excellent in transparency, heat resistance, crack resistance, light resistance, solvent resistance, alkali resistance, weather resistance, stain resistance, flame retardancy, moisture resistance, gas barrier property, flexibility, It is a material excellent in mechanical properties such as insulating property and low dielectric constant, optical characteristics, electric characteristics 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 the cured product has various properties such as crack resistance, heat resistance, solvent resistance, alkali resistance, weather resistance, Excellent in physical properties. The curable composition of the present invention is useful as a display material, a light material, a recording material, an encapsulating material for semiconductors, a high voltage insulating material, a potting / sealing material for insulation, dustproofing, sealing materials, test models for plastic parts, coating materials, interlayer insulating films, insulating packing, heat shrinkable rubber tubes, O-rings, sealing materials for display devices, protective materials, optical waveguides, optical fiber protection materials, optical lenses, It can be applied to adhesives, high heat-resistant adhesives, high heat-radiating materials, high heat-resistant sealing materials, members for solar cells and fuel cells, solid electrolytes for batteries, insulating coverings, photosensitive drums for radiators, In addition, it can be applied to concrete protecting materials, lining, soil removers, sealing agents, cold cooling materials, and glass coatings in the field of civil engineering and building materials. Also, in the field of medical materials, tubes, sealing materials, coating materials, sterilization A sealing material for a device, a contact lens, an oxygen-enriched film, and the like.

<Examples>

Hereinafter, the present invention will be further described by examples and the like, but the present invention is not limited to these examples and the like. On the other hand, "parts" and "%" in the examples are based on mass standards.

[Synthesis Example 1]

100 parts of dichlorodimethylsilane was added dropwise to a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of a 48% aqueous solution of sodium hydroxide, followed by polymerization at 105 ° C for 5 hours. The resultant reaction solution was washed with 500 parts of ion-exchanged water, dehydrated and 20 parts of pyridine were added. 20 parts of dimethylvinylchlorosilane was further added thereto, and the mixture was stirred at 70 ° C for 30 minutes. Thereafter, after washing with 100 parts of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 ° C. Subsequently, the mixture was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 DEG 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 noncyclic polysiloxane compound (a1-1) was Mw = 20,000. On the other hand, all subsequent GPCs were performed under these conditions.

(Measurement conditions of GPC)

Column: TSK-GEL MULTIPORE HXL M, manufactured by TOSOH CORPORATION, 7.8 mm x 300 mm,

Developing solvent: tetrahydrofuran

[Example 1]

100 parts of the noncyclic polysiloxane compound (a1-1) obtained in Synthesis Example 1 was dissolved in 200 parts of toluene, 0.003 part of a platinum catalyst and 10 parts of 1,3,5,7-tetramethylcyclotetrasiloxane as a cyclic polysiloxane compound were added to prepare 105 Lt; 0 &gt; C for 2 hours. The solvent was distilled off under reduced pressure at 70 占 폚 and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 캜 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 added dropwise to a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of a 48% aqueous solution of sodium hydroxide, followed by polymerization at 105 ° C for 5 hours. The resultant reaction solution was washed with 500 parts of ion-exchanged water, and 20 parts of pyridine was dehydrated in the toluene solution. 20 parts of dimethylchlorosilane was further added, followed by stirring at 70 DEG C for 30 minutes. Thereafter, after washing with 100 parts of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 ° C. Subsequently, the solution was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 DEG C to obtain an acyclic polysiloxane compound (b1-1). As a result of GPC analysis, the molecular weight of the noncyclic polysiloxane compound (b1-1) was Mw = 20,000.

[Example 2]

100 parts of the noncyclic polysiloxane compound (b1-1) obtained in Synthesis Example 2 was dissolved in 200 parts of toluene, and 0.003 part of a platinum catalyst and 0.1 part of a cyclic polysiloxane compound having an unsaturated bond, 1,3,5,7-tetramethyl-1,3 , And 10 parts of 5,7-tetravinylcyclotetrasiloxane were added and reacted at 105 ° C for 2 hours. The solvent was distilled off under reduced pressure at 70 占 폚 and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 캜 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 added dropwise to a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of a 48% aqueous solution of sodium hydroxide, followed by polymerization at 105 ° C for 5 hours. The resulting reaction solution was washed with 500 parts of ion-exchanged water, and then the toluene solution was dehydrated. 20 parts of pyridine was added, and 0.5 part of methyltrichlorosilane was further added. After stirring at room temperature for 30 minutes and at 70 占 폚 for 30 minutes, the solution was divided in half.

2.5 parts of dimethylvinylchlorosilane as a monofunctional silane compound having an unsaturated bond was added to one side and the mixture was stirred at room temperature for 30 minutes and at 70 ° C for 30 minutes and then washed with ion-exchanged water to remove pyridine hydrochloride, To obtain a cyclic polysiloxane compound (a1-2).

To the other side, 2.5 parts of dimethylchlorosilane as a Si-H group introducing compound was added. The mixture was stirred at room temperature for 30 minutes and at 70 占 폚 for 30 minutes, and then washed with ion-exchanged water to remove pyridine hydrochloride to obtain an acyclic polysiloxane compound ).

[Example 3]

100 parts of the unsaturated bond-containing non-cyclic polysiloxane compound (a1-2) obtained in Synthesis Example 3 was dissolved in 200 parts of toluene, to which 0.003 part of a platinum catalyst and 1.3 parts of a cyclic polysiloxane compound 1,3,5,7-tetramethylcyclotetrasiloxane 10 And the mixture was reacted at 105 ° C for 2 hours. The solvent was distilled off under reduced pressure at 70 占 폚 and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 캜 to obtain a silicon-containing compound (A-2). As a result of the analysis by GPC, the molecular weight of the silicon-containing compound (A-2) was Mw = 42,000.

[Example 4]

100 parts of the noncyclic polysiloxane compound (b1-2) obtained in Synthesis Example 3 was dissolved in 200 parts of toluene, 0.003 part of a platinum catalyst, and 1 part of a cyclic polysiloxane compound having an unsaturated bond, 1,3,5,7-tetramethyl-1,3 , And 10 parts of 5,7-tetravinylcyclotetrasiloxane were added and reacted at 105 ° C for 2 hours. The solvent was distilled off under reduced pressure at 70 占 폚 and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 캜 to obtain a silicon-containing compound (B-2). As a result of GPC analysis, the molecular weight of the silicon-containing compound (B-2) was 42,000.

[Synthesis Example 4]

100 parts of dichlorodimethylsilane was added dropwise to a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of a 48% aqueous solution of sodium hydroxide, and the mixture was reacted at 105 DEG C for 5 hours. The resulting reaction solution was washed with 500 parts of ion-exchanged water, and then the toluene solution was dehydrated. 20 parts of pyridine was added, and 0.5 part of tetrachlorosilane was further added. After stirring at room temperature for 30 minutes and at 70 占 폚 for 30 minutes, the solution was divided in half.

2.5 parts of dimethylvinylchlorosilane as a monofunctional silane compound having an unsaturated bond was added to one side and the mixture was stirred at room temperature for 30 minutes and at 70 ° C for 30 minutes and then washed with ion exchange water to remove pyridine hydrochloride, To obtain an amorphous polysiloxane compound (a1-3).

To the other side, 2.5 parts of dimethylchlorosilane as a Si-H group introducing compound was added. The mixture was stirred at room temperature for 30 minutes and at 70 ° C for 30 minutes, and then washed with ion-exchanged water to remove pyridine hydrochloride to obtain an acyclic polysiloxane compound 3).

[Example 5]

100 parts of the unsaturated bond-containing non-cyclic polysiloxane compound (a1-3) obtained in Synthesis Example 4 was dissolved in 200 parts of toluene, and 0.003 part of a platinum catalyst and 0.1 part of a cyclic polysiloxane compound having an unsaturated bond, 1,3,5,7-tetramethyl 10 parts of cyclotetrasiloxane were added and reacted at 105 ° C for 2 hours. The solvent was distilled off under reduced pressure at 70 占 폚 and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 캜 to obtain a silicon-containing compound (A-3). As a result of the analysis by GPC, the molecular weight of the silicon-containing compound (A-3) was Mw = 52,000.

[Example 6]

100 parts of the noncyclic polysiloxane compound (b1-3) obtained in Synthetic Example 4 was dissolved in 200 parts of toluene, 0.003 part of a platinum catalyst, and 0.1 part of a cyclic polysiloxane compound having an unsaturated bond, 1,3,5,7-tetramethyl-1,3 , And 10 parts of 5,7-vinylcyclotetrasiloxane were added and reacted at 105 ° C for 2 hours. The solvent was distilled off under reduced pressure at 70 占 폚 and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 캜 to obtain a silicon-containing compound (B-3). As a result of the analysis by GPC, the molecular weight of the silicon-containing compound (B-3) was Mw = 52,000.

[Example 7]

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 were mixed to prepare a platinum-carbonylvinylmethyl And 0.005 part of a complex were mixed to obtain a curable composition No. 1.

[Example 8]

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 were mixed to prepare a platinum-carbonylvinylmethyl And 0.005 part of a complex were mixed to obtain a curable composition No. 2.

[Example 9]

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 were mixed to prepare a platinum-carbonylvinylmethyl And 0.005 part of a complex were mixed to obtain a curing composition No. 3.

[Comparative Example 1]

50 parts of an unsaturated bond-containing non-cyclic polysiloxane (a1-1) obtained in Synthesis Example 1 and 50 parts of the non-cyclic polysiloxane compound (b1-1) obtained in Synthesis Example 2 were blended, and a platinum-carbonylvinyl And 0.005 part of a methyl complex were mixed to obtain a comparative curable composition (non-1).

[Comparative Example 2]

50 parts of polysiloxane (Mw: 30,000, vinyl group amount: 3.5 mmol / g) randomly condensed with dimethyldimethoxysilane and vinylmethyldimethoxysilane as monomers, and 50 parts of dimethyldimethoxysilane and methyldimethoxysilane as monomers, 50 parts of condensed polysiloxane (Mw: 30,000, Si-H group content: 3.5 mmol / g) were mixed and 0.005 part of a platinum-carbonylvinylmethyl complex as a curing catalyst was mixed to obtain a comparative curable composition .

[Comparative Example 3]

A polysiloxane resin (Mw: 30,000, vinyl group amount: 3.5 mmol / g), which was randomly condensed at a ratio of 1: 4: 5 in terms of molar ratio using vinyltrimethoxysilane, methyltrimethoxysilane and dimethyldimethoxysilane as monomers, (Mw: 30,000, amount of Si-H group: 50 parts), and random condensation of trimethoxysilane, methyltrimethoxysilane and dimethyldimethoxysilane as monomers at a ratio of 1: 4: 3.5 mmol / g), and 0.005 part of platinum-carbonylvinylmethyl complex as a curing catalyst were mixed to obtain a comparative curable composition (non-3).

[Comparative Example 4]

50 parts of the silicon-containing compound (A-1) obtained in Example 1 and 50 parts of polydimethylsiloxane polydimethylsiloxane (Mw: 20,000) at both ends were mixed and 0.005 part of platinum-carbonylvinylmethyl complex as a curing catalyst was mixed, A comparative curable composition (non-4) was obtained.

[Comparative Example 5]

50 parts of the silicon-containing compound (B-1) obtained in Example 2 and 50 parts of polydimethylsiloxane (Mw: 20,000) of Si-H groups at both ends were mixed and mixed with 0.005 part of platinum-carbonylvinylmethyl complex as a curing catalyst To obtain a comparative curable composition (non-5).

[Comparative Example 6]

90 parts of dichlorodimethylsilane and 9 parts of dichlorodiphenylsilane were mixed and added dropwise to a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of a 48% aqueous solution of sodium hydroxide, followed by polymerization at 105 ° C for 5 hours. The resultant reaction solution was washed with 500 parts of ion-exchanged water, and 20 parts of pyridine was dehydrated by adding 20 parts of dimethylvinylchlorosilane. The mixture was stirred at 70 캜 for 30 minutes. Thereafter, after washing with 100 parts of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 ° C. Subsequently, the mixture was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 DEG C to obtain an acyclic polysiloxane compound (non-a1-1) having an unsaturated bond.

100 parts of the obtained non-cyclic polysiloxane compound (non-a1-1) having unsaturated bonds was dissolved in 200 parts of toluene, 0.003 part of a platinum catalyst and 10 parts of 1,3,5,7-tetramethylcyclotetrasiloxane as a cyclic polysiloxane compound were added The reaction was carried out at 105 ° C for 2 hours. The solvent was distilled off under reduced pressure at 70 占 폚 and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 캜 to obtain a silicon-containing compound (A-1). As a result of GPC analysis, the molecular weight of the silicon-containing compound (A-1) was Mw = 22,000.

On the other hand, 90 parts of dichlorodimethylsilane and 10 parts of dichlorodiphenylsilane were mixed and 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, followed by polymerization at 105 ° C for 5 hours. The resultant reaction solution was washed with 500 parts of ion-exchanged water, and 20 parts of pyridine was dehydrated in the toluene solution. 20 parts of dimethylchlorosilane was further added, followed by stirring at 70 DEG C for 30 minutes. Thereafter, after washing with 100 parts of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 ° C. Subsequently, the solution was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 DEG C to obtain an acyclic polysiloxane compound (b1-1).

100 parts of the obtained non-cyclic polysiloxane compound (ratio b1-1) was dissolved in 200 parts of toluene, and 0.003 part of a platinum catalyst and 0.1 part of a cyclic polysiloxane compound having an unsaturated bond, 1,3,5,7-tetramethyl- 10 parts of 7-tetravinylcyclotetrasiloxane were added and reacted at 105 ° C for 2 hours. The solvent was distilled off under reduced pressure at 70 占 폚 and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 캜 to obtain a silicon-containing compound (non-B-1). As a result of GPC analysis, the molecular weight of the silicon-containing compound (non-B-1) was Mw = 22,000.

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

[Comparative Example 7]

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 a 48% aqueous solution of sodium hydroxide, followed by polymerization at 105 ° C for 5 hours. The resultant reaction solution was washed with 500 parts of ion-exchanged water, and 20 parts of pyridine was dehydrated by adding 20 parts of dimethylvinylchlorosilane. The mixture was stirred at 70 캜 for 30 minutes. Thereafter, after washing with 100 parts of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 ° C. Subsequently, the solution was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 DEG C to obtain an acyclic polysiloxane compound (non-a1-2) having an unsaturated bond.

100 parts of the obtained noncyclic polysiloxane compound (non-a1-2) having an unsaturated bond was dissolved in 200 parts of toluene, 0.003 part of a platinum catalyst and 10 parts of 1,3,5,7-tetramethylcyclotetrasiloxane as a cyclic polysiloxane compound were added , And the reaction was carried out at 105 ° C for 2 hours. The solvent was distilled off under reduced pressure at 70 占 폚 and then washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 캜 to obtain a silicon-containing compound (non-A-2). As a result of GPC analysis, the molecular weight of the silicon-containing compound (non-A-2) was Mw = 22,000.

On the other hand, 75 parts of dichlorodimethylsilane and 24 parts of dichlorodiphenylsilane were mixed and added dropwise into a mixture of 100 parts of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide solution, and polymerization was carried out at 105 ° C for 5 hours. The resultant reaction solution was washed with 500 parts of ion-exchanged water, and 20 parts of pyridine was dehydrated in the toluene solution. 20 parts of dimethylchlorosilane was further added, followed by stirring at 70 DEG C for 30 minutes. Thereafter, after washing with 100 parts of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 ° C. Subsequently, the mixture was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 캜 to obtain an acyclic polysiloxane compound (b1-2).

100 parts of the obtained non-cyclic polysiloxane compound (ratio b1-2) was dissolved in 200 parts of toluene, and 0.003 part of a platinum catalyst and 0.1 part of a cyclic polysiloxane compound having 1,3,5,7-tetramethyl- 10 parts of 7-tetravinylcyclotetrasiloxane were added and reacted at 105 ° C for 2 hours. The solvent was distilled off under reduced pressure at 70 占 폚 and washed with 100 parts of acetonitrile. Thereafter, the solvent was distilled off under reduced pressure at 70 캜 to obtain a silicon-containing compound (non-B-2). As a result of analysis by GPC, the molecular weight of the silicon-containing compound (non-B-2) was Mw = 22,000.

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

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

Each of the comparative curable compositions (non-1) to (non-5) obtained in the above-mentioned Examples 7 to 9 and Comparative Examples 1 to 5 and Comparative Examples 1 to 5 was coated on an aluminum plate to a thickness of about 1 mm And heated at 150 DEG C for 30 minutes and cured to obtain Cured Products No. 1 to 3 and Cured Products 1 to 5. On the other hand, the numbers of the curable compositions used correspond to the numbers of the obtained cured products. For these cured products, evaluation of the cured state and 180-degree bending test were carried out as follows.

As for the cured state, it is judged whether or not the cured film after the predetermined curing time is tacky. The state of fluidity is X, the case of having no tackiness is indicated by? Respectively.

In the 180-degree bend test, the state of the film was observed when the cured film obtained by film-forming at a film thickness of about 1 mm was bent 180 degrees on an aluminum plate. A sample which did not crack or peel off when bent at 180 ° was rated ◯, a sample which cracked at 180 ° but no crack or peeling at 90 ° was rated △, and a sample which cracked at 90 ° was evaluated as × .

The results are shown in Table 1.

Cured goods Hardened state 180 degree bending test Example 10 No.1 ◎ ○ Example 11 No.2 ◎ ○ Example 12 No.3 ◎ ○ Comparative Example 8 Rain 1 × Unevaluated Comparative Example 9 Rain 2 ◎ × Comparative Example 10 Rain 3 ◎ △ Comparative Example 11 Rain 4 ○ △ Comparative Example 12 Rain 5 ○ △

As is apparent from Table 1, the cured products Nos. 1 to 3 of Examples 10 to 12 were equivalent to or improved in cured state as compared with the cured ratios 2 to 5 of Comparative Examples 9 to 12, All improved. Further, a sufficient solid cured product was not obtained from the curable composition (non-1). From this, it was confirmed that the cured state and flexibility were improved by taking the constitution of the present invention.

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

The curable compositions Nos. 1 to 3 obtained in Examples 7 to 9 and the curable compositions (non-6) and (non-7) obtained in Comparative Examples 6 and 7 were each molded into a frame of 20 mm x 20 mm x 3 mm And heated at 150 占 폚 for 1 hour to obtain cured products No. 4 to 6 and a ratio of 6 and 7 having a thickness of 3 mm. These cured products were subjected to light deterioration test using a high-pressure mercury lamp at an output of 9.96 W / cm at 365 nm for 2 hours of irradiation. Table 2 shows the transmittance at 400 nm before and after the photo-thermal test.

Curable composition Cured goods Transmittance before irradiation (%) Transmittance after irradiation (%) Example 13 No.1 No.4 92 92 Example 14 No.2 No.5 92 92 Example 15 No.3 No.6 92 92 Comparative Example 11 -6 Rain 6 91 86 Comparative Example 12 Non-7 Rain 7 90 80

As is clear from Table 2, the hardeners Nos. 4 to 6 of Examples 13 to 15 all exhibited improved light resistance compared to the hardness ratios 6 and 7 of Comparative Examples 11 and 12. [ From these results, it was confirmed that the cured product obtained by curing the curable composition in which R ^a to R ^e consisted only of aliphatic groups had good light resistance.

According to the present invention, it is possible to provide a curable composition having excellent handling and curability, a cured product having excellent heat resistance, transparency and flexibility, and a silicon-containing compound for imparting them.

Claims (9)

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

In general formula (1) (In the general formula (1), R ^a to R ^d are each independently a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R ^e is a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or an unsubstituted or saturated aliphatic hydrocarbon group If an aromatic hydrocarbon group of 6 to 12 carbon atoms substituted with a hydrocarbon group, R ^e is a plurality of each independently. Y is an alkylene group of 2 to 4 carbon atoms, Z is an alkenyl of 2 to 4 carbon atoms or a hydrogen atom M is a weight average molecular weight (Mw) of the silicon-containing compound represented by the general formula (1), and M is a number-average molecular weight Is a number from 3000 to 10000.) A silicon-containing compound represented by the following general formula (2).

In general formula (2) (In the general formula (2), R ^a to R ^d each independently represent a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, R ^e is a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, If an aromatic hydrocarbon group of 6 to 12 carbon atoms substituted with a hydrocarbon group, R ^e is a plurality of each independently. Y is an alkylene group of 2 to 4 carbon atoms, Z is an alkenyl of 2 to 4 carbon atoms or a hydrogen atom K is a number of from 2 to 7, and p is a number of from 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) 3,000 to 1,000,000. ) 3. The method according to claim 1 or 2, And R ^e is a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms. 3. The method according to claim 1 or 2, And R &lt; ^a &gt; to R &lt; ^e & gt ^; are all methyl groups. (B1) a silicon-containing compound represented by the following general formula (1) wherein Z is an alkenyl group or an alkynyl group having 2 to 4 carbon atoms, and (C) a silicon-containing compound wherein Z is a hydrogen atom, ) Hydrosilylation reaction catalyst. &Lt; RTI ID = 0.0 &gt; 21. &lt; / RTI &gt;

In general formula (1) (In the general formula (1), R ^a to R ^d each independently represent a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, and R ^e is a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or an unsubstituted or saturated aliphatic hydrocarbon group If an aromatic hydrocarbon group of 6 to 12 carbon atoms substituted with a hydrocarbon group, R ^e is a plurality of each independently. Y is an alkylene group of 2 to 4 carbon atoms, Z is an alkenyl of 2 to 4 carbon atoms or a hydrogen atom M is a weight average molecular weight (Mw) of the silicon-containing compound represented by the general formula (1), and M is a number-average molecular weight Is a number from 3000 to 10000.) (B2) a silicon-containing compound wherein Z is an alkenyl group or an alkynyl group having 2 to 4 carbon atoms in the general formula (2), and (C) a silicon-containing compound in which Z is a hydrogen atom in the general formula (2) ) Hydrosilylation reaction catalyst. &Lt; RTI ID = 0.0 &gt; 21. &lt; / RTI &gt;

In general formula (2) (Wherein R ^a to R ^d each independently represent a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms and R ^e is a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or an unsubstituted or saturated aliphatic hydrocarbon group If an aromatic hydrocarbon group of 6 to 12 carbon atoms substituted with a hydrocarbon group, R ^e is a plurality of each independently. Y is an alkylene group of 2 to 4 carbon atoms, Z is an alkenyl of 2 to 4 carbon atoms or a hydrogen atom K is a number of from 2 to 7, and p is a number of from 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) 3,000 to 1,000,000. ) 6. The method of claim 5, Wherein the silicon-containing compound of the component (A1) and the silicon-containing compound of the component (B1) are all methyl groups in R ^a to R ^e in the general formula (1). The method according to claim 6, Both the silicon-containing compound in the silicon-containing compound and the component (B2) in the component (A2) is a curable composition, characterized in that R is ^a ~R ^e in the formula (2) of all methyl group. A cured product obtained by curing the curable composition according to any one of claims 5 to 8.