KR101526862B1 - 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 (0). The curable composition of the present invention contains 0.01 to 20 parts by mass of an epoxy-curable compound per 100 parts by mass of the silicon-containing compound, and the resulting cured product is excellent in heat resistance and flexibility.

(Wherein R ^a to R ^g are a C _1-12 saturated aliphatic hydrocarbon group or a C _1-12 aromatic hydrocarbon group, Y is a C _2-4 alkylene group, and Z is a group represented by the formulas (2) to 6), K is a number of 2 to 7, T is a number of 1 to 7, and P is a number of 0 to 3. M and N are N: M = 1: 1 to 1 : 100, and the sum of all M and all N is 15 or more, and the mass average molecular weight of the compound is 3,000 to 1,000,000. In the formulas (2) to (6), X ^{a to} X ^c are C _1-8 Al represents alkanediyl group, -COO- or a single bond, r ^h ~ r ^j represents a hydrogen atom or a methyl group, r represents 0 or 1.)

Silicon-containing compounds, epoxy-curable compounds, heat-resistant, flexible

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 curing the curable composition. The silicon-containing compound is a macromolecular compound having a cyclosiloxane structure into which an epoxy group is introduced. By curing the epoxy-curable compound, a cured product useful as a sealing material, a high-voltage insulating material, or the like can be formed.

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 studied. Such a material is expected to be a material having new functionalities completely different from each material itself, which not only combines the characteristics of each material but also combines the advantages of each material and can not be predicted by the provisional rule.

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 Adding a silanol group in the polysiloxane, and further polycondensation reaction of methyltrimethoxysilane using an aluminum catalyst, adding acetylacetone at a point of time when a predetermined molecular weight is reached, and performing ligand exchange in the reaction system It is attempting to improve the storage stability. 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- Discloses a silicon-containing curable composition which is excellent in handleability and curability and is excellent in heat resistance of the obtained cured product. However, this silicon-containing curable composition has a problem that the curing property is not necessarily sufficient and a cured product having sufficient performance at a low temperature and in a short time can not be obtained.

Patent Document 2 discloses an epoxy silicone resin composition which is obtained by an addition reaction of a polyorganohydrogensiloxane and an epoxy compound containing an alkenyl group and is excellent in mechanical strength, moisture resistance, heat resistance and workability, However, what is disclosed here does not give a cured product having sufficient heat resistance and flexibility.

[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

[Patent Document 2] Japanese Patent Application Laid-Open No. 5-287077

An object of the present invention is to provide a curable composition having excellent heat resistance and flexibility.

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted studies to solve the above problems and found that a silicon-containing compound having an epoxy group introduced into a cyclosiloxane structure solves the above problems, and has completed the present invention.

That is, the present invention provides a silicon-containing compound represented by the following general formula (0).

(식 중, R^a∼R^g는 같아도 달라도 좋고, 탄소원자수 1∼12의 포화지방족 탄화수소기, 또는 포화지방족 탄화수소기로 치환되어 있어도 좋은 탄소원자수 6∼12의 방향족 탄화수소기이고, Y는 탄소원자수 2∼4의 알킬렌기이고, Z는 하기 식 (2)∼ (6) 중 어느 하나로 표현되는 기이고, K는 2∼7의 수이고, T는 1∼7의 수이며, T를 반복수로 하는 중합 부분과, K-T를 반복수로 하는 중합 부분은 블록 형상이어도 랜덤 형상이어도 된다. P는 0∼3의 수이다. M 및 N은 N:M=1:1∼1:100이면서 모든 M과 모든 N의 합계가 15 이상이 되는 수이고, 또한 일반식(0)으로 표현되는 규소 함유 화합물의 질량평균 분자량을 3000∼100만으로 하는 수이다. 또한, M을 반복수로 하는 중합 부분과, N을 반복수로 하는 중합 부분은 블록 형상이어도 랜덤 형상이어도 된다.)

(Wherein R ^a to R ^g may be the same or different and each represents a saturated aliphatic hydrocarbon group of 1 to 12 carbon atoms or an aromatic hydrocarbon group of 6 to 12 carbon atoms which may be substituted with a saturated aliphatic hydrocarbon group and Y represents a carbon atom number of 2 And Z is a group represented by any one of the following formulas (2) to (6), K is a number of 2 to 7, T is a number of 1 to 7, and T is a repetition number The polymerized portion and the polymerized portion in which KT is a repetition number may be in a block form or in a random form and P is a number of 0 to 3. M and N are N: M = 1: 1 to 1: N is a number of 15 or more and a mass average molecular weight of the silicon-containing compound represented by the general formula (0) is 3,000 to 1,000,000. Further, a polymerized portion having M as a repetition number and N The polymerized portion to be a repeating number may be a block or a random.

delete

Wherein X ^{a to} X ^c represent an alkanediyl group having 1 to 8 carbon atoms which may be substituted with an oxygen atom and / or an ester bond, -COO- or a single bond, and R ^h to R ^{j each} represent a hydrogen An atom or a methyl group, and r represents 0 or 1.)

The present invention also provides a curable composition containing 0.01 to 20 parts by mass of an epoxy-curable compound per 100 parts by mass of the silicon-containing compound.

Further, the present invention provides a curable composition containing 0.01 to 30 parts by mass of an epoxy-curable compound and 1 to 50 parts by mass of an epoxy compound, based on 100 parts by mass of the silicon-containing compound.

The present invention also provides a 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 (0) will be described.

Examples of the saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms represented by R ^a to R ^g in the general formula (0) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert- Heptyl, heptyl, isoheptyl, heptyl, n-octyl, heptyl, n-octyl, , Isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isonyl, 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 ^a to R ^g has 6 to 12 carbon atoms in total in the saturated aliphatic hydrocarbon group as a substituent. As the saturated aliphatic hydrocarbon group which is a substituent, for example, among saturated aliphatic hydrocarbon groups exemplified above, those capable of satisfying the carbon atom number can be employed. Thus, R ^a ~R ^g are substituted with a saturated aliphatic hydrocarbon group represented by even as the aromatic hydrocarbon group of 6 to 12 carbon atoms good, phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3-isopropyl Phenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4- tertiary butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 2,3-dimethylphenyl, , 2,5-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.

Z in the general formula (0) is an epoxy-containing group represented by any one of the formulas (2) to (6). X ^a to X ^c in the formulas (2), (4) and (5) are an alkanediyl group having 1 to 8 carbon atoms which may be substituted with an oxygen atom and / or an ester bond, It is a combination. Examples of the alkanediyl group include -CH ₂ -, -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 ) -, methylene is substituted with an oxygen atom, methylene is substituted with an ester bond, and methylene is replaced with an oxygen or an ester bond. 3].

A preferred form of the silicon-containing compound of the present invention represented by the above general formula (0) is a silicon-containing compound represented by the following general formula (1). The silicon-containing compound represented by the following general formula (1) is T = K among the silicon-containing compounds represented by the above general formula (0). What is obtained by a common synthetic method is a silicon-containing compound represented by the following general formula (1), or a mixture of plural kinds of silicon-containing compounds represented by the general formula (0) and represented by the following general formula (1) Containing compound as a main component. For example, a compound having a KT of greater than 1 in the general formula (0) can be produced even when using ^a cyclopolysiloxane represented by ^a polyfunctional (R ^a SiHO) _K as a compound introducing ^a cyclopolysiloxane ring do. This is because the production of a compound in which two or more Si-H noncylic polysiloxanes of a cyclopolysiloxane are bonded through Y is energetically disadvantageous.

(Wherein R ^a to R ^g may be the same or different and each represents a saturated aliphatic hydrocarbon group of 1 to 12 carbon atoms or an aromatic hydrocarbon group of 6 to 12 carbon atoms which may be substituted with a saturated aliphatic hydrocarbon group and Y represents a carbon atom number of 2 M is an integer of 1 to 4, and Z is a group the same as that of the general formula (0), k is a number of 2 to 7, 1: 100 and m + n? 15, and the mass average molecular weight of the silicon-containing compound represented by the general formula (1) is 3,000 to 1,000,000. , n may be a block shape or a random shape.

Examples of Z in the general formula (0) or the general formula (1) include: operability in producing a silicon-containing compound; storage stability of a silicon-containing compound and a curable composition described below; The following structure is most preferable.

In the silicon-containing compound of the present invention, when the ratio of the saturated aliphatic hydrocarbon group in R ^a to R ^g is increased, the flexibility of the resulting cured product is improved. When the proportion of the aromatic hydrocarbon group is increased, the heat resistance and hardness ). The ratio of the saturated aliphatic hydrocarbon group to the aromatic hydrocarbon group can be arbitrarily set depending on the physical properties required for the cured product. Among the silicon-containing compounds of the present invention, the silicon-containing compound, which is an aromatic hydrocarbon group having 6 to 12 carbon atoms, in which R ^e and R ^f may be substituted with a saturated aliphatic hydrocarbon group, can easily control the ratio of the saturated aliphatic hydrocarbon group and the aromatic hydrocarbon group It is preferable.

In the group represented by R ^a to R ^g in the silicon-containing compound of the present invention, a preferable ratio of a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms and an aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted with a saturated aliphatic hydrocarbon group Number of electrons: electron: the latter is 100: 1 to 1: 2, more preferably 20: 1 to 1: 1. The saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms is preferably a methyl group because the heat resistance is good and the aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted with a saturated aliphatic hydrocarbon group is preferably a phenyl group because heat resistance is good.

K in the general formula (1) 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 because 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 process will be described as a representative of the silicon-containing compound of the present invention represented by the above general formula (1).

The silicon-containing compound can be produced, for example, by reacting the polysiloxane intermediate (a3) obtained by reacting the cyclic polysiloxane compound (a2) with a cyclic polysiloxane compound (a1) having an unsaturated bond as a precursor and an epoxy compound (a4) (A4) in which the Z group is introduced into the cyclic polysiloxane compound (a2) are reacted, and the resulting cyclic polysiloxane compound (a5) is reacted with the unsaturated polysiloxane compound (a1) having an unsaturated bond . In view of workability in manufacturing, the method of passing through the former polysiloxane intermediate (a3) is preferable.

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 in the production of the unsaturated bond-having cyclic polysiloxane compound (a1) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, Dialkoxymonosilane compounds such as methoxysilane, methylphenyldiethoxysilane and the like; 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 monoalkoxysilanes such as trimethylethoxysilane, trimethylmethoxysilane, triphenylethoxysilane, triphenylmethoxysilane, methyldiphenylethoxysilane and dimethylphenylethoxysilane, compound; 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 trisalkoxysilane compounds such as trisethoxymethylsilane, trismethoxymethylsilane, 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, methylphenylvinyl Chlorosilane, 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.

Examples of the epoxy compound (a4) introducing the Z group include an epoxy compound having an unsaturated bonding group reacting with the Si-H group in the cyclic polysiloxane structure in the polysiloxane intermediate (a3) or the cyclic polysiloxane (a2) Specific examples thereof include the following compounds.

The condensation reaction by hydrolysis to obtain an acyclic polysiloxane compound (a1) having an unsaturated bond which is a precursor of the silicon-containing compound 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, metal carboxylates such as naphthenate and octylate of these metals, and the like, and they 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 uncyclized polysiloxane compound (a1) having an unsaturated bond as a precursor can be obtained by reacting a monofunctional monosilane compound when p is 1 and a trifunctional monosilane compound when p is 3, Reacting the silane compound with a monofunctional siloxane compound having an unsaturated group when p is 4 and reacting it with a monofunctional silane compound having an unsaturated group when p is 4 and reacting with a monofunctional silane compound having an unsaturated group when p is 2 .

For the reaction of the cyclic polysiloxane compound (a2) having the unsaturated bond-containing acyclic polysiloxane compound (a1) as a precursor, a hydrosilylation reaction method may be used. For example, the polysiloxane intermediate (a3) can be obtained by mixing the cyclic polysiloxane compound (a1) and the cyclic polysiloxane compound (a2), heating the resulting mixture after adding a certain amount of the hydroxysilylation reaction catalyst. Also, the hydroxy silylation reaction may be similarly used for the reaction of the epoxy compound (a4) introducing the Z group and the Si-H group in the cyclic polysiloxane structure.

Examples of the hydroxysilylation catalyst include known catalysts containing at least one metal selected from the group consisting of platinum, palladium and rhodium. Examples of the platinum-based catalysts include platinum-based catalysts such as platinum-carbonylvinylmethyl complexes, platinum-divinyltetramethyldisiloxane complexes, platinum-cyclovinylmethylsiloxane complexes, and platinum-octylaldehyde complexes. As the palladium-based catalyst and the rhodium-based catalyst, for example, in the platinum-based catalyst, a compound containing palladium or rhodium, which is a platinum-group metal, can be used instead of platinum. These may be used alone or in combination of two or more. Particularly, it is preferable that platinum is contained in view of curability, and specifically platinum-carbonylvinylmethyl complex is preferable. Further, a so-called Wilkinson catalyst containing the platinum group metal such as chlorotris (triphenylphosphine) rhodium (I) is also included in the hydroxysilylation reaction catalyst. The amount of these is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass, based on the total amount of the reactants.

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 (0) or (1), although not within the scope 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 the silicon-containing compound and the epoxy-curable compound. In the curable composition of the present invention, the content of the epoxy curing compound is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the silicon-containing compound when only the silicon-containing compound is contained as the epoxy group-containing component. The content of the silicon-containing compound and the epoxy compound described below as an epoxy group-containing component is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the total mass of both. If it is less than 0.01 part by mass, it may not be sufficiently cured, and if it exceeds 20 parts by mass, the heat resistance of the resulting cured product may be affected.

The above-mentioned epoxy curing compound may be an ordinary epoxy curing agent, but it is preferable to cure the epoxy resin by action of heat, energy rays or the like. As the epoxy curing compound, an epoxy curing agent, an amine curing agent, an amide curing agent, an imide curing agent, an imidazole curing system curing agent, an acid anhydride curing agent, an organic onium salt curing agent, a metallocene curing agent, A commercially available epoxy curing agent or cation polymerization initiator may be used.

Among these, an amine-based curing agent and an organic onium salt-based curing agent are preferable because they have good compatibility with the silicon-containing compound.

Examples of the amine curing agent include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-phenylenediamine, poly (oxypropylene) diamine, p, p '- diamino diphenyl methane, p, p'--diaminodiphenyl sulfone, p, p'--diaminodiphenyl ether, aniline · BF _3, BF ₃ · p- toluidine, o- toluidine · BF _3, dimethyl Aniline BF ₃ , N-methyl aniline BF ₃ , N-ethyl aniline BF ₃ , N, N'-dimethylaniline BF ₃ , N, N'- diethylaniline BF ₃ , ethylamine BF ₃ , there may be mentioned n-butylamine · BF ₃ , piperidine · BF ₃ , diphenylamine · BF ₃ , o-dimethylaminomethylphenol, 2,4,6-tris (dimethylaminomethyl) phenol, triethanolamine · borate, .

Examples of the organic onium salt curing agent include a diazonium salt, an iodonium salt and a sulfonium salt. They may be those which give curing by thermal cationic polymerization, Or the like. Generally, an aliphatic onium salt is used as the former and an aromatic onium salt is used as the latter. Organic onium salt based curing agents are useful when curing by irradiation with energy rays is mainly used because good curing can be obtained with a small amount of use. Examples of the aromatic iodonium salts and aromatic sulfonium salts used in the present invention include It is preferable because it is good.

Examples of the aromatic iodonium salt include 4-isopropoxy-4'-methyldiphenyliodonium tetrakispentafluorophenylborate, 4-isopropoxy-4'-methyldiphenyliodonium hexafluorophosphate, 4-isopropoxy-4'-methyldiphenyliodonium hexafluoroantimonate, (tolylcumyl) iodonium hexafluorophosphate, (tolylcumyl) iodonium hexafluoroantimonate, (tolyl Bis (tertiary butylphenyl) iodonium hexafluorophosphate, bis (tertiary butylphenyl) iodonium hexafluoroantimonate, bis (tertiarybutylphenyl) iodonium hexafluorophosphate, bis Phenyl) iodonium tetrakis pentafluorophenyl borate and the like.

Examples of the aromatic sulfonium salts include 4,4'-bis [di (4-heptoxyphenyl) sulfophenyl phenyl] sulfide bishexafluoroantimonate, 4,4'-bis [di ) Sulfonium hexafluorophosphate, 4- (4-benzoylphenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate, 4,4'-bis [bis ((? -hydroxyethoxy) phenyl) sulfonio] phenylsulfide bishexafluorophosphate, 4,4'-bis [bis ((? -hydroxyethoxy) Bis [bis (fluorophenyl) sulfonio] phenylsulfide bishexafluorophosphate, 4,4'-bis [bis (fluorophenyl) sulfonium ] Phenylsulfide bishexafluoroantimonate, 4,4'-bis (diphenylsulfonio) phenylsulfide bishexafluorophosphate, 4,4'-bis (diphenylsulfonio) phenylsulfide Bishexafluoroantimo 4- (4-benzoylphenylthio) phenyl-di- (4- (beta -hydroxyethoxy) phenyl) sulfonium hexafluorophosphate, 4- 4- (4-benzoylphenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate, 4- ( (4-benzoylphenylthio) phenyl-diphenylsulfonium hexafluorophosphate, 4- (4-benzoylphenylthio) phenyl-diphenylsulfonium hexafluorophosphate, 4- Phenylthio) phenyl-diphenylsulfonium hexafluoroantimonate, 4- (phenylthio) phenyl-di- (4- (? - hydroxyethoxy) phenyl) sulfonium hexafluorophosphate, 4- (Phenylthio) phenyl-di- (4- (? - hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate, 4- Fluorophosphate, 4- (phenylthio) phenyl-di- (4-fluoro Phenyl) sulfonium hexafluoroantimonate, 4- (phenylthio) phenyl-diphenylsulfonium hexafluorophosphate, 4- (phenylthio) phenyl-diphenylsulfonium hexafluoroantimonate, 4- 4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4- Hexafluoroantimonate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4- (2-chloro-4- benzoylphenylthio) phenyldiphenylsulfonium hexafluoro (2-chloro-4-benzoylphenylthio) phenylbis (4-hydroxyphenyl) sulfonium hexafluorophosphate, 4- (4-hydroxyphenyl) sulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimone 4-acetoxyphenyldimethylsulfonium hexafluorophosphate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, 4-methoxyphenyldimethylsulfonium hexafluorophosphate, Carbonyloxyphenyldimethylsulfonium hexafluoroantimonate, 4-ethoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, 4-ethoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate, and the like. .

Examples of the amide-based curing agent include a polyamide resin, a diacetone acrylamide complex, and dicyandiamide. Examples of the acid anhydride-based curing agent include phthalic anhydride, trimellitic anhydride, benzophenonetetracarboxylic acid anhydride, maleic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, anhydroglutaric acid, pyromellitic anhydride, (3-butane-1,2-dicarboxylic acid) anhydride, and tetrabromophthalic anhydride.

Next, an epoxy compound to be blended as an optional ingredient in the curable composition of the present invention will be described.

In the curable composition of the present invention, the use of an epoxy compound can improve the mechanical strength of the cured product obtained by curing the curable composition. The content of the epoxy compound is preferably 1 to 50 parts by mass based on 100 parts by mass of the silicon-containing compound when used for the above purpose. More preferably, the amount is 5 to 25 parts by mass, more preferably 10 to 20 parts by mass. When an epoxy compound is used, the content of the epoxy curing compound is preferably 0.01 to 30 parts by mass based on 100 parts by mass of the silicon-containing compound.

The epoxy compound is a compound having one or two or more epoxy groups in the molecule, and is a monomeric, dimeric, oligomeric or polymeric compound. The epoxy group of these epoxy compounds may be present as a terminal group or as a pendant group. Examples of the epoxy compound include 2,2-bis (3,4-epoxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, 2- (3,4- (3,4-epoxy) cyclohexylm-dioxane, bis [(3,4-epoxycyclohexyl) methyl] adipate, 6- (3,4-epoxycyclohexanecarboxylic acid) (Cyclo-alicyclic) epoxy compounds such as benzyloxy) hexanoic acid (3,4-epoxycyclohexyl) methyl ester; Bisphenol-type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F and diglycidyl ether of bisphenol S; Novolak type epoxy resins such as phenol novolac epoxy resin, cresol novolac epoxy resin, and hydroxybenzaldehyde phenol novolac epoxy resin; Aromatic epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and polyfunctional epoxy resin such as epoxidized polyvinyl phenol; Polyglycidyl ethers of aliphatic polyhydric alcohols; Polyglycidyl ethers of alkylene oxide adducts of aliphatic polyhydric alcohols; Polyglycidyl ethers of polyester polyols of aliphatic polyhydric alcohols and aliphatic polyvalent carboxylic acids; Polyglycidyl esters of aliphatic polycarboxylic acids; Polyglycidyl esters of polyester polycarboxylic acids of aliphatic polyhydric alcohols and aliphatic polyvalent carboxylic acids; Dimers, oligomers and polymers obtained by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate; Oligomers, polymers obtained by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate with other vinyl monomers; Epoxidized vegetable oil; Ester exchangers of epoxidized vegetable oils; Epoxylated polybutadiene, and the like.

The epoxy compound preferably has a molecular weight of 100 to 1000 because the improvement in mechanical strength of the obtained cured product becomes remarkable, and the epoxy equivalent is preferably 100 to 2000 g / mol.

Next, the metal oxide fine powder blended as an optional ingredient in the curable composition of the present invention will be described.

The metal oxide fine powder may be used, for example, in order to improve various physical properties after curing, or in an amount required as a filler. When the metal oxide fine powder is used for these purposes, the content of the metal oxide fine powder is preferably 1 to 1000 parts by mass based on 100 parts by mass of the silicon-containing compound. More preferably, the amount is 5 to 500 parts by mass, more preferably 10 to 100 parts by mass.

Examples of the metal oxide fine powder include inorganic materials such as minerals. Specifically, silicon dioxide such as colloidal silica, silica filler and silica gel; metal oxides such as aluminum oxide, zinc oxide and titanium oxide; Mica, montmorillonite, silicate, diatomaceous earth, sericite, kaolinite, flint, feldspar, vermiculite, attapulgite, talc, minnesotite, (pyrophyllite), and the like, and they may be modified by organic modification treatment or the like. Of these, silicon dioxide is preferred.

The particle diameter of the metal oxide fine particles is preferably 100 占 퐉 or less, more preferably 50 占 퐉 or less in view of heat resistance.

The silicon-containing curable composition of the present invention may also optionally contain a weather-imparting agent as an optional component. As the weathering-imparting agent, there may be used those generally used which are generally known, 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- Di-t-butyl-para-cresol (DBPC), and the sulfur-based antioxidant may be di Alkyl thiodipropionates and? -Alkyl mercaptopropionic acid esters, and examples of the phosphorus antioxidant 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 known resins, fillers, additives, 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 arbitrarily combined include polyimide resins, polyether resins such as polyethylene glycol and polypropylene glycol, polyurethane resins, epoxy resins, phenol resins, polyester resins, melamine resins, polyamide resins, Phenol resin, phenol resin, phenol resin, phenol resin, phenol resin, phenol resin and phenol resin.

The amount of these optional components (excluding the epoxy compound and the metal oxide fine powder) is preferably 10 parts by mass or less per 100 parts by mass of the silicon-containing compound in order to avoid impairing the object of the present invention Or less.

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 a state not containing the metal oxide fine powder.

By selecting the above-mentioned epoxy-curable compound, the curable composition of the present invention can be selected as a type of curing by thermal curing, photo-curing, or curing by both light and heat. The curing temperature in the case of thermosetting is preferably 60 to 200 占 폚, more preferably 80 to 150 占 폚. The curing time is preferably 0.1 to 10 hours, more preferably 1 to 6 hours. In the case of photocuring, ultraviolet rays, electron beams, X-rays, radiation, high-frequency waves and the like are available as the active energy rays to be used, and ultraviolet rays are most economically preferable. Examples of ultraviolet light sources include an ultraviolet laser, a mercury lamp, a high-pressure mercury lamp, a xenon lamp, a sodium lamp, and an alkali metal lamp. As the ultraviolet source used here, a high-pressure mercury lamp is preferable. The irradiation energy varies depending on the applied film thickness, but is usually in the range of 100 to 10000 mJ / cm 2. When the thermosetting is performed after the photo-curing, it is usually necessary to heat in a range of 60 to 150 占 폚.

The cured product obtained by curing the curable composition of the present invention under the above-described conditions is excellent in transparency, crack resistance, heat resistance, solvent resistance, alkali resistance, weather resistance, stain resistance, flame retardancy, The material is excellent in mechanical properties such as strength, elongation, strength, electrical insulation, low dielectric constant, optical properties, and electric characteristics.

The curable composition containing the silicon-containing compound of the present invention is excellent in stability, curability and the like, and the cured product is excellent in various properties such as crack resistance, heat resistance, solvent resistance, alkali resistance, weather resistance, . 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 injecting agent, sealing agent, cold cooling material and glass coating in the field of civil engineering and construction materials. Also, in the field of medical materials, A sealing material for a processing apparatus, a contact lens, an oxygen-enriched film, and the like.

<Examples>

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. On the other hand, unless otherwise stated, "parts" and "%" in the examples are based on mass.

[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. After washing the obtained reaction solution with 500 parts of ion-exchanged water, the toluene solution was dehydrated and 20 parts of pyridine was added. 10 parts of dimethylvinylchlorosilane was further added 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 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 (a1-0) having an unsaturated bond. Analysis by GPC under the following conditions revealed that the molecular weight of the noncyclic polysiloxane compound (a1-0) 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

[Synthesis Example 2]

100 parts of the noncyclic polysiloxane (a1-0) 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, which is a cyclic polysiloxane compound, 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 占 폚 to obtain a polysiloxane intermediate (a3-0). As a result of analysis by GPC, the molecular weight of the polysiloxane intermediate (a3-0) was Mw = 22,000.

[Example 1] Production of silicon-containing compound (A-0)

100 parts of the polysiloxane intermediate (a3-0) obtained in Synthesis Example 2 was dissolved in 200 parts of toluene, and 19 parts of 3-vinyl-7-oxabicyclo [4,1,0] heptane, which is an epoxy compound for introducing Z, Lt; / RTI &gt; for 2 hours. After the solvent was distilled off under reduced pressure at 70 ° C, the residue was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C to obtain a silicon-containing compound (A-0). As a result of the analysis by GPC, the molecular weight of the silicon-containing compound (A-0) was Mw = 30,000 and the epoxy equivalent (molecular weight per unit of epoxy group) determined by the potentiometric titration method based on JIS K7236 was 3000 g / mmol. On the other hand, all subsequent measurements of epoxy equivalent are based on this method.

[Synthesis Example 3]

90 parts of dichlorodimethylsilane and 9 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 resulting reaction solution was washed with 500 parts of ion-exchanged water, dehydrated with toluene, and 20 parts of pyridine was added. 10 parts of dimethylvinylchlorosilane was further added thereto, 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 ° C to obtain an acyclic polysiloxane compound (a1-1) having an unsaturated bond. The molecular weight of the noncyclic polysiloxane (a1-1) was Mw = 20,000.

[Synthesis Example 4]

100 parts of the noncyclic polysiloxane (a1-1) obtained in Synthesis Example 3 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, 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 polysiloxane intermediate (a3-1). As a result of analysis by GPC, the molecular weight of the polysiloxane intermediate (a3-1) was Mw = 22,000.

[Example 2] Production of silicon-containing compound (A-1)

100 parts of the polysiloxane intermediate (a3-1) obtained in Synthesis Example 4 was dissolved in 200 parts of toluene, and 19 parts of 3-vinyl-7-oxabicyclo [4,1,0] heptane, which is an epoxy compound introducing Z, Lt; / RTI &gt; for 2 hours. After the solvent was distilled off under reduced pressure at 70 ° C, the residue was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C to obtain a silicon-containing compound (A-1). As a result of the analysis by GPC, the molecular weight of the silicon-containing compound (A-1) was Mw = 30,000 and the epoxy equivalent (molecular weight of the epoxy group) was 3000 g / mmol.

[Example 3] Production of silicon-containing compound (A-2)

100 parts of the polysiloxane intermediate (a3-1) obtained in Synthesis Example 4 was dissolved in 200 parts of toluene, and 19 parts of allyl glycidyl ether, which is an epoxy compound introducing Z, was added thereto, followed by stirring at 105 DEG C for 2 hours. After the solvent was distilled off under reduced pressure at 70 캜, the solvent was washed with 100 parts of acetonitrile, and then 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 = 30,000 and the epoxy equivalent (molecular weight of the epoxy group) was 3000 g / mmol.

[Synthesis Example 5]

90 parts of dichlorodimethylsilane and 9 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 obtained reaction solution was washed with 500 parts of ion-exchanged water, dehydrated, and 20 parts of pyridine and 0.5 part of phenyltrichlorosilane were added. The mixture was stirred at room temperature for 30 minutes and then at 70 DEG C for 30 minutes. 15 parts of dimethylvinylchlorosilane was added thereto, followed by stirring at room temperature for 30 minutes and then 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 DEG C to obtain an acyclic polysiloxane compound (a1-2) having an unsaturated bond. As a result of GPC analysis, the molecular weight of the noncyclic polysiloxane (a1-2) was Mw = 33,000.

[Synthesis Example 6]

100 parts of the uncylated polysiloxane compound (a1-2) obtained in Synthesis Example 5 was dissolved in 200 parts of toluene, 0.003 part of a platinum catalyst and 10 parts of 1,3,5,7-tetramethylcyclotetrasiloxane were added, Lt; / RTI &gt; After the solvent was distilled off under reduced pressure at 70 占 폚, the residue was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 占 폚 to obtain a polysiloxane intermediate (a3-2). As a result of analysis by GPC, the molecular weight of the polysiloxane intermediate (a3-2) was Mw = 36,000.

[Example 4] Production of silicon-containing compound (A-3)

100 parts of the polysiloxane intermediate (a3-2) obtained in Synthesis Example 6 was dissolved in 200 parts of toluene, 19 parts of allyl glycidyl ether was added, and the mixture was stirred at 105 DEG C for 2 hours. After the solvent was distilled off under reduced pressure at 70 ° C, the residue was washed with 100 parts of acetonitrile, and the solvent was distilled off under reduced pressure at 70 ° C 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 = 36,000 and the epoxy equivalent (molecular weight of the epoxy group) was 2000 g / mmol.

[Synthesis Example 7]

90 parts of dichlorodimethylsilane and 9 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, dehydrated, and 20 parts of pyridine and 0.5 part of tetrachlorosilane were added. The mixture was stirred at room temperature for 30 minutes and then at 70 DEG C for 30 minutes. 15 parts of dimethylvinylchlorosilane was added thereto, followed by stirring at room temperature for 30 minutes and then 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 (a1-3) having an unsaturated bond. As a result of GPC analysis, the molecular weight of the noncyclic polysiloxane (a1-3) was Mw = 40,000.

[Synthesis Example 8]

100 parts of the uncylated polysiloxane compound (a1-3) obtained in Synthesis Example 7 was dissolved in 200 parts of toluene, 0.003 part of a platinum catalyst and 10 parts of 1,3,5,7-tetramethylcyclotetrasiloxane were added, Lt; / RTI &gt; After the solvent was distilled off under reduced pressure at 70 ° C, the residue was washed with 100 parts of acetonitrile, and then the solvent was distilled off under reduced pressure at 70 ° C to obtain a polysiloxane intermediate (a3-3). As a result of analysis by GPC, the molecular weight of the polysiloxane intermediate (a3-3) was Mw = 44,000.

[Example 5] Production of silicon-containing compound (A-4)

100 parts of the polysiloxane intermediate (a3-3) obtained in Synthesis Example 8 was dissolved in 200 parts of toluene, 19 parts of allyl glycidyl ether was added, and the mixture was stirred at 105 DEG C for 2 hours. After the solvent was distilled off under reduced pressure at 70 캜, the mixture was washed with 100 parts of acetonitrile, and the solvent was distilled off under reduced pressure at 70 캜 to obtain a silicon-containing compound (A-4). As a result of the analysis by GPC, the molecular weight of the silicon-containing compound (A-4) was Mw = 44,000 and the epoxy equivalent (molecular weight of the epoxy group) was 1000 g / mmol.

[Example 6] Production of curing composition No. 1

99.9 parts of the silicon-containing compound (A-0) obtained in Example 1 and 0.1 part of 4,4'-bis [di (4-heptoxyphenyl) sulfonio phenyl] sulfide bishexafluoroantimonate were mixed To obtain a curable composition No. 1.

[Example 7] Production of curable composition No. 2

90 parts of the silicon-containing compound (A-0) obtained in Example 1, and 10 parts of JEFFAMIN D-2000 (manufactured by Hansa Inc., diamine-based curing agent) were mixed to obtain Curable Composition No. 2.

[Example 8] Production of curing composition No. 3

99.9 parts of the silicon-containing compound (A-1) obtained in Example 2 and 0.1 part of 4,4'-bis [di (4-heptoxyphenyl) sulfophenyl phenyl] sulfide bishexafluoroantimonate were mixed To obtain a curable composition No. 3.

[Example 9] Production of curable composition No. 4

99.9 parts of the silicon-containing compound (A-1) obtained in Example 2, and 0.1 part of 4-isopropoxy-4'-methyldiphenyliodonium tetrakis pentafluorophenylborate were mixed to obtain Curable Composition No. 4 .

[Example 10] Production of curable composition No. 5

99.9 parts of the silicon-containing compound (A-3) obtained in Example 4, and 0.1 part of 4,4'-bis [di (4-heptoxyphenyl) sulfonio phenyl] sulfide bishexafluoroantimonate To obtain a curable composition No. 5.

[Example 11] Production of curable composition No. 6

99.9 parts of the silicon-containing compound (A-4) obtained in Example 3 and 0.1 part of 4,4'-bis [di (4-heptoxyphenyl) sulfophenyl phenyl] sulfide bishexafluoroantimonate were mixed To obtain a curable composition No. 6.

[Example 12] Production of curable composition No. 7

, 99.9 parts of the silicon-containing compound (A-1) obtained in Example 2, 0.1 part of 4,4'-bis [di (4-heptoxyphenyl) sulfonium phenyl] sulfide bishexafluoroantimonate, And 5 parts of a silica filler (FB-7SDC; manufactured by Denki Kagaku Kogyo) were mixed to obtain a curable composition No. 5.

[Example 13] Preparation of curable composition No. 8

84 parts of the silicon-containing compound (A-1) obtained in Example 2, 0.1 part of 4,4'-bis [di (4-heptoxyphenyl) sulfonio phenyl] sulfide bishexafluoroantimonate, And 15 parts of 2,2-bis (3,4-epoxycyclohexyl) propane were mixed to obtain a curable composition No. 8.

[Example 14] Production of curable composition No. 9

90 parts of the silicon-containing compound (A-1) obtained in Example 2, and 10 parts of JEFFAMIN D-2000 (manufactured by Hansusu Co., Ltd., diamine-based curing agent) were mixed to obtain Curable Composition No. 9.

[Example 15] Production of curing composition No. 10

85 parts of the silicon-containing compound (A-1) obtained in Example 2, 10 parts of JEFFAMIN D-2000 (manufactured by Hantsu Corporation, diamine curing agent) and 5 parts of silica filler (FB-7SDC; manufactured by Denki Kagaku Kogyo) To obtain a curable composition No. 10.

[Example 16] Production of curable composition No. 11

90 parts of the silicon-containing compound (A-1) obtained in Example 2 and 10 parts of Adeka Hardener EH-220 (Adeka, mixed system epoxy curing agent) were mixed to obtain Curable Composition No. 11.

[Comparative Example 1] Production of Comparative Curing Composition 1

99.9 parts of KF-102 (polymethylsiloxane having 3,4-epoxycyclohexane group bonded thereto as a pendant type, manufactured by Shinetsu Kagaku Co., Ltd., epoxy equivalent: 3600 g / mmol), and 4,4'-bis [di Phenyl) sulfoniophenyl] sulfide bishexafluoroantimonate were mixed to obtain a curable composition comparative 1.

[Comparative Example 2] Production of Comparative Curing Composition 2

99.9 parts of X-22-169B (polydimethylsiloxane of 3,4-epoxycyclohexane, epoxy equivalent 1700 g / mmol, manufactured by Shinetsu Kagaku), and 4,4'-bis [di (4-heptoxyphenyl) Sulfonephenyl] sulfide bishexafluoroantimonate (0.1 part) were mixed to obtain a curable composition comparative 2.

[Comparative Example 3] Preparation of Comparative Curing Composition 3

90 parts of KF-101 (polydimethylsiloxane bonded with a glycidyl group in the pendant form, manufactured by Shinetsu Kagaku Co., Ltd., epoxy equivalent: 350 g / mmol) and 90 parts of ADEKA HARDNER EH-220 Were mixed to obtain Comparative Curing Composition No. 3.

[Comparative Example 4] Preparation of Comparative Curing Composition 4

99.0 parts of 1,3,5,7-tetramethyl-1,3,5,7-tetrakis (3,4-epoxycyclohexylethyl) cyclotetrasiloxane, and 4,4'-bis [di Sulfoxyphenyl) sulfophenylphenyl] sulfide bishexafluoroantimonate 1 part were mixed to obtain a curable composition comparative 4.

[Examples 17 to 27, Comparative Examples 5 to 8]

The curable compositions Nos. 1 to 11 obtained in Examples 6 to 16 and the comparative curable compositions 1 to 4 obtained in Comparative Examples 1 to 4 were each filmed on an aluminum plate to a film thickness of about 1 mm, To obtain cured products 1 to 11 and cured products 1 to 4. On the other hand, the curing conditions in Table 1 show that the curing conditions were subjected to heat treatment under the condition of the bottom after the light curing was performed using the high pressure mercury lamp at the upper condition.

These cured products were subjected to the evaluation of the cured state, the heat resistance test, and the 180 degree bend test as follows.

As for the cured state, it is judged whether or not the cured film has a tackiness after a predetermined curing time. The state of fluidity is X, the case where there is no fluidity and the case where tackiness is present is indicated by? Respectively.

In the heat resistance test, a 5 mass% reduction temperature by TG / DTA in an air atmosphere was measured.

In the 180-degree bending 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. Samples with no cracks or delaminations at the time of bending at 180 deg. Are rated as?, Samples with cracks at 180 deg. But not cracking or peeling at 90 deg., Samples with cracking at 90 deg. Respectively.

The results are shown in Tables 1 and 2. On the other hand, in Table 1, a cured product of a curable composition using an organic onium salt-based curing agent as an epoxy curable compound is described, and a cured product of a curable composition using an amine curable agent or a mixed curing agent as an epoxy curable compound is described in Table 2 .

From Table 1, it was confirmed that the curable compositions No. 1 and No. 3 to 8, which are the curable compositions of the present invention, exhibit a better cured state than the comparative curable compositions 1 and 2. Further, the cured products 1 to 7 of the present invention obtained by curing the curable compositions No. 1 and No. 3 to 8, which are the curable compositions of the present invention, have better heat resistance than the comparative cured products 3, And it was confirmed that sincerity is good. From this, it can be seen that the curing property of the curable composition and the heat resistance and flexibility of the cured product are improved by introducing the cyclosiloxane ring epoxy group, which is a characteristic of the silicon-containing compound of the present invention.

Further, by comparing the cured product 1 with the cured product 2, it was confirmed that the heat resistance of the obtained cured product is further improved by introducing an aromatic group into the R ^e and R ^f of the silicon containing compound. Further, by comparing the cured product 2 with the cured product 6, it was confirmed that even by using the metal oxide fine powder, better heat resistance can be imparted.

From Table 2, it was confirmed that the cured products 8 to 11 obtained by curing the curable composition of the present invention by thermal curing only had better heat resistance and flexibility than the comparative cured product 4. From this, it can be seen that heat resistance and flexibility of the cured product are improved by introducing a cyclosiloxane ring epoxy group, which is a feature of the silicon-containing compound of the present invention.

Further, by comparing the cured product 8 with the cured product 9, it was confirmed that the heat resistance of the resulting cured product was further improved by introducing an aromatic group into the R ^e and R ^f of the silicon containing compound, , It was confirmed that even by using the metal oxide fine powder, better heat resistance can be imparted.

According to the present invention, a novel silicon-containing compound can be provided, and when used in combination with an epoxy-curing compound, the silicon-containing compound can form a curable composition having excellent curability and can form a cured product having excellent heat resistance and flexibility.

Claims (9)

A silicon-containing compound represented by the following general formula (0).

(Wherein R ^a to R ^d and R ^g each independently represent a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms substituted with an unsubstituted or saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms R ^e and R ^f are each independently an unsubstituted or aromatic hydrocarbon group having 6 to 12 carbon atoms substituted with a saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms and Y is an alkylene group having 2 to 4 carbon atoms , Z is a group represented by any one of the following formulas (2) to (6), K is a number of 2 to 7, T is a number of 1 to 7, P is a number from 0 to 3. The M and N are N: M = 1: 1 to 1: 100, and the sum of all M and all N is 15 or more, and the mass average molecular weight of the silicon-containing compound represented by the general formula (0) is from 3,000 to 1,000,000 Furthermore, the overlapping portion in which M is a repetition number and the overlapping portion in which N is a repetition number may be a block shape or a random shape.)

(Wherein X ^{a to} X ^c represent an alkanediyl group having 1 to 8 carbon atoms substituted with an unsubstituted or an oxygen atom and / or an ester bond, -COO- or a single bond, and R ^h to R ^j are A hydrogen atom or a methyl group, and r represents 0 or 1.) A silicon-containing compound represented by the following general formula (1).

(Wherein R ^a to R ^d and R ^g each independently represent a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms substituted with an unsubstituted or saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms R ^e and R ^f are each independently an unsubstituted or aromatic hydrocarbon group having 6 to 12 carbon atoms substituted with a saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms and Y is an alkylene group having 2 to 4 carbon atoms And Z is a group represented by any one of the following formulas (2) to (6), k is a number of 2 to 7, and p is a number of 1 to 4. m and n satisfy n: m = 1: 1 to 100 and m + n = 15, and the mass average molecular weight of the silicon-containing compound represented by the general formula (1) is from 3,000 to 1,000,000. And the overlapping portion in which n is a repetition number may be a block shape or a random shape.)

(Wherein X ^{a to} X ^c represent an alkanediyl group having 1 to 8 carbon atoms substituted with an unsubstituted or an oxygen atom and / or an ester bond, -COO- or a single bond, and R ^h to R ^j are A hydrogen atom or a methyl group, and r represents 0 or 1.) 3. The method according to claim 1 or 2, The number of saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms and the number of aromatic hydrocarbon groups having 6 to 12 carbon atoms substituted with unsubstituted or saturated aliphatic hydrocarbons having 1 to 6 carbon atoms in the group represented by R ^a to R ^g Electron: the latter) is 100: 1 to 1: 2. A curable composition characterized by containing 0.01 to 20 parts by mass of an epoxy-curable compound per 100 parts by mass of the silicon-containing compound according to any one of claims 1 to 5. A curable composition characterized by comprising 0.01 to 30 parts by mass of an epoxy curing compound and 1 to 50 parts by mass of an epoxy compound, based on 100 parts by mass of the silicon-containing compound of any one of claims 1 to 6. 5. The method of claim 4, And 1 to 1000 parts by mass of a fine metal oxide powder. A cured product obtained by curing the curable composition according to claim 4. 6. The method of claim 5, And 1 to 1000 parts by mass of a fine metal oxide powder. A cured product obtained by curing the curable composition according to claim 5.