TW200911886A - Silicon-containing compound, curable composition and cured product - Google Patents

Abstract

Disclosed is a silicon-containing compound represented by the general formula (0) below. Also disclosed is a curable composition containing 0.01-20 parts by mass of an epoxy curable compound per 100 parts by mass of the silicon-containing compound. This curable composition enables to obtain a cured product having excellent heat resistance and flexibility. (In the general formula (0), R<a>-R<g> each represents a C1-12 saturated aliphatic hydrocarbon group or a C1-12 aromatic hydrocarbon group; Y represents a C2-4 alkylene group; Z represents a group represented by one of the formulae (2)-(6) shown above; K represents a number of 2-7; T represents a number of 1-7; P represents a number of 0-3; and M and N represent numbers satisfying the following relation: N:M = 1:1-1:100, with the total of all M's and all N's being not less than 15, which make the mass average molecular weight of the compound to be 3,000-1,000,000. In the formulae (2)-(6), X<a>-X<c> each represents a C1-8 alkanediyl group, a -COO- group or a single bond; R<h>-R<j> each represents a hydrogen atom or a methyl group; and r represents 0 or 1.)

Description

200911886 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a new compound containing a specific structure, a compound containing Shi Xi, a curable composition containing the compound, and the curability And a hardened material which is not hardened. The compound containing ruthenium has a polymer compound having a ring-forming structure of an epoxy group, and can be formed by curing and curing the epoxy curable compound. It can be used as a hardened material for sealing materials, high-voltage insulation materials, etc. Γ\ [Prior Art] For composite materials that combine organic raw materials and inorganic raw materials, various researches on 'in the health industry' are also used to make inorganic a method of filling a U-machine with a molecular compound, or a method of coating a metal surface with a second modification of an organic polymer, etc. For the organic/inorganic composite materials, the raw materials constituting the composite material have a micron or higher ^, 'so _ can be - part of the physical properties increased above the expected value, but other f-number or physical properties only show that according to organic raw materials and inorganic raw materials The value expected by the addition rule of energy or physical properties. In recent years, 'the study of organic/inorganic composite materials for τ', ''', and the raw material categories of organic raw materials and inorganic raw materials are nanometers. An organic/inorganic composite that is formed at a molecular level and at a molecular level. The industry expects that such materials and materials - the characteristics of each raw material section, and both of the original body ~", and thus have the new functionality that is unpredictable by the addition rules and the raw materials themselves. I308〇6.d〇 c 200911886 In this organic/inorganic composite material, there is a chemical bond type in which the raw material of the other side and the other raw material are bonded at a molecular level via a covalent bond, and the raw material of the second=two raw materials serves as a substrate and the raw materials of the other side are fine. a mixed type in the ground and composited. As for the method of synthesizing the organic raw materials used in the organic/suspicious two, the use of the solvent "the so-called sol-gel method" means the precursor molecule

Hydrolysis = a polycondensation reaction carried out thereafter, and a cross-linking = machine = compound reaction is obtained at a low temperature. The inorganic raw material obtained by the sol-gel method has a problem of poor storage stability such as gelation in a short period of time. Profitable literature! In the following method, the test method is used to improve the stability of storage. The condensation rate caused by the length of the base of the burnt base of the burnt base of the three bases is:: Poor! After polycondensation of methyltrimethoxy sulphate, a polycondensation, a long-chain alkyltrialkoxide of hydrazine is added to block the sterol group in the polyoxyalkylene; The catalyst is subjected to a polycondensation reaction of methyltrimethoxy-zetanic sintering. 'Acetone acetone is added when a specific molecular weight is reached, and a ligand exchange is carried out in the reaction 2. However, these methods have a problem of flexibility in the preservation of the stability of the inorganic material obtained by the sol-gel method. On the other hand, as the chemical bonding type organic/inorganic composite material, a curable composition containing a specific polymer containing 7 is proposed. For example, Patent Document 1 discloses a curable composition containing cerium: a cerium-containing polymer (A) having an octa-linked structure and having an alkenyl group and an alkynyl group, having a parent-linked structure and having a fluorenyl group. The ruthenium-containing polymer (B) and the platinum-based catalyst (D)' are excellent in workability and hardenability, and the obtained cured product is also excellent in heat resistance 130806.doc 200911886. However, the curable composition containing bismuth has a problem that the hardening property is not necessarily sufficient, and a cured product having sufficient performance cannot be obtained at a low temperature in a short time. Further, Patent Document 2 discloses an epoxy polyoxyxene resin composition into which an epoxy group is introduced, which is obtained by an addition reaction of a polyorganohydrogen hydride and an epoxy group containing an alkenyl group, and a mechanical Strength, moisture resistance, heat recovery, and workability are good. However, those disclosed herein do not provide a cured product having sufficient heat and flexibility.

[Non-Patent Document 丨] Japanese Journal of Chemical Society, N〇9, 57 ι (η%) [Patent Document U Japanese Patent Laid-Open Publication No. 2005-325174 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei No. Hei. DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION The object of the present invention is to provide a curable composition which is excellent in heat resistance and scratch resistance which can be obtained by (4) s ★ π #斤. [Means for Solving the Problems] The inventors of the present invention have found that the above-mentioned problems can be solved by the above-mentioned problems in order to solve the above-mentioned problems in the structure of the above-mentioned ring-cut oxygen-fired structure, that is, the compound of the present invention can be solved. The present invention provides a compound: ^ is represented by the formula (0) containing hydrazine [Chemical 1] 130806.doc 200911886

J is a saturated aliphatic nicotine having a reverse atomic number of 1 to 12, 戋 can be 饴 4 &amp; ^ a saturated aliphatic nicotine substituted with 6 carbon atoms of an aromatic hydrocarbon group; Y is a carbon atom number 2~ (4) base, z is a group represented by any one of the following formulas (2) to (6), κ is a number of 2 to 7] is a number of 1 to 7, and a polymerization portion of T is a repeating number The polymerization portion with κ_τ as a repeating number may be either block-shaped or random; ρ is the number of 〇~3; μ&amp;Ν (wherein Ra~Rg may be the same or

N: M = 1: 丨 ~ 丨: 100, and the total value of all Μ and all ν is 15 or more, and the mass average molecular weight of the compound containing ruthenium represented by the general formula (〇) is 3000~ In addition, the polymer portion of the repeating number is /, and the polymerized portion having the repeat number of Ν is either a block shape or a random shape. [Chemical 2]

CH-}^-X—CH“CH-CH2 (2)—CHfCHf^ ^—d_'CH2 (3)

(6) (wherein Xa to X represent an alkylene group having 1 to 8 carbon atoms substituted by an oxygen atom and/or an ester bond, -COO- or a single bond; and Rh to Rj represent a hydrogen atom or a group Base; r means 〇 or 1). Further, the present invention provides a curable composition containing 0.01 to 20 parts by mass of the ring I30806.doc 200911886 oxygen-curable compound with respect to the above-mentioned compound containing hydrazine in 100 parts of summer. Further, the present invention provides a curable composition comprising, in an amount of from 1 to 3 parts by mass, based on 1 part by mass of the epoxy-containing compound, and from 1 to 50 parts by mass, per 1 part by mass of the compound containing ruthenium. Oxygen compound. Further, the present invention provides a cured product obtained by curing the curable composition. [Effects of the Invention] According to the present invention, it is possible to provide a novel cerium-containing compound which, when used together with an epoxy-curable compound, is a curable composition excellent in curability and can be formed into a heat-resistant composition. A cured product excellent in properties and flexibility. [Embodiment] First, the compound containing ruthenium of the present invention represented by the above formula (0) will be described. σ I (0), as a saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms represented by Ra to Rg, can be rebelled. J. Methyl, ethyl, propyl, isopropyl, butyl Base, second butyl, second _, ^ butyl, isobutyl 'pentyl, isopentyl, second pentyl, hexyl 3 « • hexyl, 3-hexyl, cyclohexyl, 1-methyl Cyclohexyl, heptyl, 2-heptyl, 0-good Α% heptyl, isoheptyl, third heptyl, n-octyl, isooctyl, decyl-octyl, 2-ethylhexyl, anthracene Base, isodecyl, decyl, dodecyl and the like. Λ In addition, the Ra to Rg table - number 6 to 12 of the material / the money and the fat (iv) the ketone-substituted carbon atom group of the whole carbon source: the base 'also includes the substituent, that is, saturated aliphatic hydrocarbon, 6 to 12 people. As the substituent, i.e., saturated aliphatic 130806.doc-10-200911886, for example, the above-exemplified saturated aliphatic group can satisfy the above-mentioned number of carbon atoms. Therefore, examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms which may be substituted by a saturated aliphatic hydrocarbon group, which are represented by the ruler 3 to phenyl group, a naphthyl group, a 2-phenylphenyl group, and a 3-methylbenzene group are mentioned. Base, methyl phenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-butylphenyl, 4-tert-butylphenyl, 4-hexyl Phenyl, 4·cyclohexylphenyl, 2”3-monomethyl, 2,4·dimethylphenyl, 2,5-dimethylphenyl, 2,6-r=yl’, 3, 4-two? Phenylphenyl, 3,5-di-n-phenyl, cyclohexyl, biphenyl, 2,4,5-trimethylphenyl, and the like.

Further, the alkylene group having 2 to 4 carbon atoms represented by Y may, for example, be -CH2CH2-^-CH2CH2CH2-&gt; -CH ΓΗ PH or -CH2CH(CH3). 2CH2CH, 2_, .CH(CH3)CH2_, two-pass: (z) is a group having a group represented by any one of the above formulas (7) to (6). The m-methylene group in the above formulas (2), (4), and (5) may be a carbon atom or a single bond which may be substituted by an oxygen atom and/or a vinegar bond. As the basis of the second aspect, the p column can be exemplified by -CH2-, -ch2ch2-. -ch2ch2ch2-, -CH2CH2CH, CH, CH, ^H2CH2-, -CH(CH3)CH2--2(ch3)_, as Asian? The group consists of an oxygen source, a _substituent, a methylene group, and an oxygen group. The compound is represented by the following [Chemical Formula 3]. Substitutes, for example, can be listed as [化3] Γ-丨 ro-rr〇 r. ―rr. ~ ~r°~rr η tti

T0 (3⁄4 f - 〇 - C - c - 〇 - L1 Η: H 130806.doc 200911886, the preferred form of the ruthenium-containing compound of the present invention represented by the ι formula (ο) is a compound represented by the following formula (1) The compound containing the compound represented by the following general formula (1), which is represented by the above formula (8), is T=K in the compound containing the compound of the earth. The compound obtained by the usual synthesis method has the following formula. (1) A compound containing a cut compound or a compound of the above formula (3) having a compound of the formula (1), which is a compound containing ♦ represented by the following formula (1) as a main component. Even if the user has used the compound represented by (R SlH0)K as the compound introduced into the cyclodoxime ring, the compound of the formula "KT of the above formula (〇) is greater than] The reason for this is that the formation of a compound in which a non-cyclic polysulfide is bonded to two or more of the cyclodoxy oxime via Y is extremely disadvantageous in terms of energy.

(wherein 'the heart can be the same or not @, is a saturated aliphatic hydrocarbon group having a carbon number, or an aromatic hydrocarbon group having 6 to 12 carbon atoms which can be substituted by a saturated aliphatic hydrocarbon group, and Y is a carbon atom number of 2 The alkyl group '4' is the same group as the above formula (0), k is the number of 2 to 7 'p is the number of b. The claw and ^ are η: (4): !~i : (10) and ^ The number of the compounds containing ruthenium represented by the general formula (1) is 130 806. doc -12 to 2009 11 886, and the number of repeats is m. The portion and the polymerized portion having a repeating number of η may be either block-shaped or random. As the oxime in the above formula (0) or formula (1), the following structure is preferred because of the workability in the production of a compound containing ruthenium, the compound containing ruthenium, and the sclerosing composition described later. The storage stability and the heat, electrical properties, hardenability and mechanical properties of the cured product are good. [Chemical 5]

-CHrCH;

-CHrCHrCHr〇—CH2-CH-CH2 In the compound containing ruthenium of the present invention, when Ra to Rg is increased, the ratio of the saturated fat and the base of smoke is increased, and the obtainability of the cured product is improved. The ratio of the hydrocarbon group is increased, and the hardenability and hardness of the obtained cured product are improved. The ratio of the saturated aliphatic hydrocarbon group to the aromatic tobacco group can be arbitrarily set in accordance with the wide physical properties of the cured product. In the compound containing the compound of the present invention, the compound containing the compound of the aryl group having a carbon number of M2 substituted by a saturated aliphatic hydrocarbon group can easily control the ratio of the saturated fatty smoky group to the aromatic smoky group. Therefore, (four). In the group represented by Ra to Rg, the compound of the carbon source and the aliphatic nicotine group and the aromatic atomic group having a counter atomic number of 6 to 12 which may be substituted by a saturated aliphatic hydrocarbon group are as follows: The preferred ratio (number) of the latter and the working base is that the former is 1 〇〇: 卜 1:2, and more preferably 2 〇: is a saturated atomic number of 1 to 12 carbon atoms. Further, the reason is that the U ^ smoky group is preferably a methyl group, and the number of atoms is a sulphur group of 12, preferably a phenyl group, for the carbon substituted by a saturated aliphatic hydrocarbon group, which is preferably 130806. .doc -13· 200911886 Good heat resistance. In the above formula (1), k is from 2 to 7 and the obtained cured product is not easily obtained, and the k is 3. . If it is more than 7, the number of functional groups is excessively flexible. If the k is 2 to 5, the industrial energy base is appropriate, so it is preferable, and the best &gt; the present invention has a f-average molecular weight of the side ~ (10) j. If the mass average molecular weight is less than 3, the heat resistance of the obtained cured product is insufficient, and if the mass average molecular weight is more than 1,000,000, the viscosity becomes large and the operation is hindered. The mass average molecular weight is preferably from 5 to 500,000, more preferably from 10,000 to 100,000. The ruthenium-containing compound of the present invention is not particularly limited as long as it is produced by a known reaction. The following production method is described by using the compound represented by the above formula (1) in the compound containing 11 of the present invention. The compound containing ruthenium can be obtained, for example, by using a cyclic polyoxy siloxane compound (al) having an unsaturated bond as a precursor, and reacting it with a cyclic polyoxo-oxygen compound (a2) to obtain a polylithic eve. The oxane-interstitial (a3) is obtained by reacting a % oxygen compound (a4) introduced into the z group with the polyoxyalkylene intermediate (a3); or an epoxy compound (a4) introduced into the Z group and a ring The polyoxy siloxane compound (a2) is reacted to obtain an epoxy group-containing cyclic polyoxy siloxane compound (a5), and the acyclic polyoxy siloxane compound having an unsaturated bond and the methoxy group have a % oxy group. It is obtained by reacting a cyclic polysulfide compound (a5). In view of the workability in the production of k, it is preferred that the former is via the polyoxane intermediate (a3). 130806.doc 14 200911886 The above-mentioned acyclic polyoxy siloxane compound (al) having an unsaturated bond can be obtained by subjecting one or two or more difunctional decane compounds to hydrolysis reaction by hydrolysis. When P is 1, it reacts with a monofunctional monodecane compound, reacts with a trifunctional monodecane compound when p is 3, and reacts with tetraglycan monodecane compound when 卩 is 4, and further with a single palace having an unsaturated group. Obtained by reacting a decane compound. When p is 2, it can be obtained by reacting with a monofunctional decane compound having an unsaturated group after the condensation reaction. The functional group of the decane compound is typically an alkoxy group, a halogen group or a hydroxyl group. f % octa-unsaturated bond of acyclic polyoxy siloxane compound (a 丨) and cyclic poly siloxane compound (a2) by (al) unsaturated bonding carbon and (& 2) The Si H group reacts and bonds. Examples of the above-mentioned difunctional Shixia compound used in the preparation of the above-mentioned acyclic polysiloxane compound having an unsaturated bond include dimethyldimethoxydecane and dimercaptodiethoxylate. a dialkoxy monodecane compound such as decane, diphenyldimethoxydecane, diphenyldiethoxydecane, methylphenyldimethoxydecane or Q methylphenyl ethoxy decane; Substituting one or two alkoxy groups of the monoalkoxymonodecane compounds with a monodecane compound selected from a group consisting of a ruthenium, a gas, a bromine and an iodine, or a hydroxyl group; A dioxo-oxygen compound and an oligomeric siloxane compound obtained by condensing the monolithic compound. Examples of the monofunctional monodecane compound include tridecylethoxy zephyr, trimethylmethoxy zeshi, triphenylethoxy zephyr, triphenylmethoxy zexi, and methyl. Diphenylethoxy alcohol, dimethyl phenyl ethoxy shixiyuan and other single-burning oxygen stone compound compound; these single-burning oxygen stone Xiyuan compound 130806.doc -15- 200911886 / odor and hard composition The alkoxy group of the substance in the group is substituted with a monodecane compound selected from fluorine, chlorine, a halogen atom or a hydroxyl group. The above-mentioned mono-p-monodecane compound may, for example, be a tri-alkoxy group such as triethyl group: tribasic acid, trimethoxymethyl ishixiyuan, triethoxyphenyl phosphatase, or tris; oxyphenyl decane. a decane compound; i to 3 alkoxy groups of the trialkoxy decane compound are substituted with a monodecane compound selected from the group consisting of a dentate atom or a hydroxyl group in a group consisting of gas, gas, and jin.

ϋ As the above-mentioned tetra-g-enable monodecane compound, for example, four kinds of alkoxy compound such as tetraethoxy sulphate, tetramethoxy ketone, etc. The oxy group is substituted with a mono-decane compound selected from a group consisting of fluorine, chlorine, =, and iodine. Examples of the monofunctional decane compound having an unsaturated group include dimethyl vinyl garnet, methoxymethyl methoxy sylvestre, dimethylethylene ethoxy ketone, and diphenyl. Vinyl gas (tetra), diphenyl ethoxide, oxyphenol, diphenylvinyl methoxy (tetra), methyl phenyl ethane decane, methyl phenyl ethoxy decane, methyl phenyl oxime Base decane and the like. Examples of the above-mentioned cyclic polyoxo-oxygen compound (5)) include U3,5-trimethylcyclotrifluoride, 1,3,5,7·tetramethylcyclotetracalyx, and ^5. Indole ring pentaoxane, 5,7,9,11·hexamethylcyclohexaoxane, 1,3,5,7,9,U,134 f base ring seven-stone oxy-oxygen, A Base octadecane, H5-triethylcyclotrioxane, tetrahexylcyclotetraoxane, ^, pentaethylcyclopentaoxane, 1,3,5,7,9,U _ hexaethylcyclohexaoxane, triphenyl sulfonium trioxane, 1,3,5,7-tetraphenyl ring four stone oxime, ... 仏 pentaphenyl ring five stone eve 130806. Doc •16· 200911886 Oxytomane, l,3,5,7,9,ll-hexaphenylcyclohexaoxane, etc. Examples of the epoxy compound (a4) to which the z group is introduced include, for example, a polyoxyalkylene intermeric oxime 3) or a cyclic polyoxyalkylene (a2) Specific examples of the epoxy compound of the Si—H group-based unsaturated bond group in the middle of the compound include the compounds shown below. [Chemical 6]

CflpCH-^^—CH-CH2 CHfCH—^ CHfCH-CHr〇-fi-^° CH.^CHr〇_.c

CHfCH-CH-CH2 CHpCH-CHrO-CH^CHV CHPCH-C-〇-CH-Ah2 CHPC-?-〇--cHrCH-NCH (7 K7 CHpCH-C-〇-CH;

CHpCH-^y CHfCH-CHj-O-C-^J^y' CHpCH-C-O-CHj

CHpC—C-O-CH; 〇 CH, CHfC-CH “〇1~&lt;^7 0

a condensation reaction by hydrolysis to obtain a precursor of a compound containing ruthenium, that is, a non-cyclic polymethicone (al) having an unsaturated bond, which can be obtained by a so-called sol-gel reaction get on. The difunctionalization: the hydrolysis/condensation reaction of the substance can be carried out by: activating the oxy group or the functional group by water to form a sterol group (Si_〇H group), and the resulting sterol group The condensation of each other, the base and the base, or the base with the i group. In order to allow the hydrolysis reaction to proceed rapidly, it is preferred to add an appropriate amount of water, and a catalyst may be added. Further, the condensation reaction is also carried out by the moisture of the air or the trace amount of water contained in the solvent other than water. In the reaction, it is also possible to use 130806.doc 17-200911886. The preparation of the preparation is not particularly limited, and the steroids, methanol, ethanol, and steroids are 5', for example, water, or A Hydrophilic solvents such as acetaminophen, isopropanol, n-butanol, isobutanol, c, T, 6, ketone, di- π arylene, ~ alkane, tetrahydrofuran can be used! Two or more types are used in combination or in combination. Organic cold cutting, the special catalyst above, can use acid or test, specifically, for example, inorganic acids such as phosphoric acid, sulfuric acid, etc.; organic acids such as diisopropyl vinegar; sodium hydroxide, hydrogen and oxygen = wind-specific inorganic Tests; amine compounds such as trimethylamine, triethylamine, monoethanolamine, bis-amine (organic test H 酉日 special compound • 曰 ^ ^ _, tin laurin, dibutyl tin, octyl stannic acid and other tin compounds; Boron such as boron fluoride; boron compounds, aluminum compounds such as aluminum triacetate, metal chlorides such as iron, primary, pot, zinc, etc., and metal carboxylates such as salts and octanoates For the above-mentioned catalysts, one type or two or more types may be used in combination. When the y-body is hydrolyzed by two or more kinds of difunctional decane compounds, the condensation reaction may be carried out separately after a certain degree of hydrolysis. Further, the hydrolysis and condensation reaction may be further carried out by mixing and mixing all of the difunctional decane compounds together. The above-mentioned hydrazine-driven substance, that is, an acyclic polysiloxane compound having an unsaturated bond (1) may be used. Obtained by: After the above hydrolysis and condensation reaction, when P is 1, it is further reacted with a monofunctional monodecane compound, and when p is 3, it is further reacted with a trifunctional monodecane compound, and when 1) is 4, it is further reacted with a tetrafunctional monodecane compound. It is then obtained by reacting with a monobromo bromide compound having an unsaturated group; when p is 2, it can be obtained by reacting with a monofunctional terpene compound having an unsaturated group. 130806.doc •18- 200911886 /In the reaction of a non-cyclic polyoxyl compound (8) having an unsaturated bond with a cyclic polyoxo compound (a2), a method of using a gasification method can be used. . The example &amp; 'polyoxyalkylene intermediate (10) can be obtained by mixing a non-cyclic poly 7 oxy-fired compound (al) with a cyclic polyoxo oxo compound (8)) 'adding any amount of hydrazine hydrogenation reaction The medium is heated. Further, the reaction of the z-group epoxy compound (a4) with the S-buzone group in the cyclic polyoxy-oxygen structure can also be carried out by using a hydrogenation reaction. The above-mentioned catalyst for the hydrogenation reaction of the invention is, for example, a known catalyst containing one or more metals selected from the group consisting of platinum, ruthenium and iridium. For example, as a starting catalyst, an initial thioglycidylmethyl fluorenyl vinyl tetradecyldioxane complex, a platinum-cyclovinyl fluorene complex, and an initial octyl group may be mentioned. Complex compound, etc. (4) Catalyst. Examples of the catalyst and the money-based catalyst include, for example, a compound of the genus or the genus of the genus Platinum. These hydrogenated reaction catalysts may be used in combination of two or more types. In particular, from the viewpoint of hardenability, the light cup is contaminated with ruthenium 3 having a platinum, and specifically, a platinum-carboxyvinylmethyl complex is preferred. Further, - (a base phosphine) emulsified ruthenium (I), etc. 3 has the above-mentioned tumbling metal of the household jin Gutian. The month's Wilkinson catalyst is also included in the above-mentioned Shixi hydrogenation catalyst. The calculation θ = the amount of the total amount of the ruthenium reactant used in the fly 矽虱 矽虱 reaction catalyst is 5 mass % w · β set /. In the following, it is more preferably 0.0001 to 1.0% by mass. 0 ' In addition to the main component of the curable composition, the sigma-containing product of the present invention can be used as a main component of the curable composition as described below. Molecular compounds or polymer compositions are used in applications such as resins and indium plastic modifiers. 130806.doc •19- 200911886 Furthermore, although in the scope of the present invention, s, s, and scorpion compounds, in the above formula (9) or (1), non-renzhen, Shao, scale, titanium, In the wrong, the nipple key can be introduced into elements other than butterflies, carriers, zinc, 铌' buttons, tin, hooves, and the like. As a method thereof, for example, the following methods can be cited: a derivative of these other elements. Into the hydrolysis-condensation reaction, an element other than ruthenium is incorporated in the oxalate chain. Further, some or all of the hydrolyzed milk atoms of the above-mentioned compound may be substituted with hydrazine and/or fluorine. Next, the curable composition of the present invention will be described. The curable composition 俜 ^ 糸 3 of the present invention is formed by the above-mentioned compound containing ruthenium and a cyclogenic compound. When the curable composition of the present invention contains only the above-mentioned compound; the compound of the cerebral ceramide is used as a component containing a methoxy group in the milk, the content of the oxime-curable compound is preferably (10) by mass. The compound containing Shi Xi is 0.01 to 20 parts by mass. In addition, when the compound containing the compound and the epoxy compound described later is contained as the epoxy group-containing component, the content of the epoxy curable compound is better than the θ weight of the pregnancy, and is 100 parts by mass based on the total mass of the two. 0.01 to 20 parts by mass. If the content of the epoxy-curable compound is less than 0.01%, the film may not be sufficiently cured. If the amount of the epoxy-curable compound is more than 20 parts by mass, the heat resistance of the obtained cured product may be affected. The epoxy curable compound may be a conventionally known epoxy hardener, and those which cure the epoxy resin by the action of a heat 'energy line or the like can be preferably used. As the epoxy curable compound, a viscous curing agent, an amine curing agent, a guanamine curing agent, a quinone imide curing agent, a simazole complex curing agent, an acid needle curing agent, and an organic cerium salt can be used. A hardener or a metallocene system 130806.doc -20- 200911886 A hardener, an aromatic iron-based hardener, or the like, or a commercially available epoxy hardener or a cationic polymerization initiator. Among these, an amine-based curing agent and an organic rust (tetra) curing agent are preferred because of good compatibility with the above-mentioned compound containing cerium. Examples of the above-mentioned amine-based curing agent include di-extension ethyltriamine, tri-extension ethyltetramine, tetra-extended ethylpentamine, diethylaminopropylamine, and N-amine: ethyl brigade, and Phenylenediamine, poly(oxypropylene)diamine, p,p,-diaminodiphenylfane, P,P--aminodiphenyl sulfone, ρ,ρι-diaminodiphenyl ether, Aniline _ BF3, p-toluidine BF3, o-toluidine _BF3, dimethyl aniline, N methyl aniline - BF3, N-ethyl aniline Β Β ρ 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 N,N'-:ethylaniline·called, ethylamine _ called, n-butylamine _bf guangpei-bf3, diphenylamine. BF3, o-dimethylaminomethylbenzene-monomethylamine Methyl) phenol, triethanolamine-borate, and the like. Examples of the organic onium salt-based curing agent include a diazonium salt, a scale salt, and a ruthenium I, etc., which may be cured by cationic polymerization by heat or by energy rays such as (4) light. In general, the former uses an aliphatic sulfonium salt and the latter uses an aromatic sulfonium salt. Organic bismuth salt type hardening = This is good hardening by the use amount of 乂 乂 ν, so it is mainly useful when hardening by energy line ^, as a user of the present invention, a good 疋 aromatic 鐄 鐄 salt, aroma The reason for the salt-disintegration is that the compatibility with the compound containing Shi Xi is better. —The above-mentioned aromatic onium salt may, for example, be 4·isopropoxymethylenemethylbis(indenyltetrakis(phenyl)phenyl)borate, 4—isopropoxymethyldiphenylphosphonium/fluorene fluorene Acid salt, 4_isopropoxy _4'-methyldiphenyl hexafluoroantimonate, I30806.doc 200911886 (nonylphenyl cumyl) sulfonium hexafluorophosphate, (tolyl cumene) Hexafluoroantimonate, (p-phenylpyridyl)phosphonium tetrakis(pentafluorophenyl)borate, bis(t-butylphenyl)phosphonium hexafluorophosphate, bis(t-butyl Phenyl) indole hexafluoroantimonate, bis(t-butylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, and the like. Examples of the above aromatic onium salt include 4,4'-bis[bis(4-heptyloxyphenyl)nonylphenyl]thioether bishexafluoroantimonate, and 4,4'-bis[di(4). -heptyloxyphenyl)nonylphenyl]thioether bishexafluorophosphate, 4-(4-phenylmercapto-phenylthio)phenyl-di-(4-fluorophenyl)phosphonium hexafluorophosphate Salt, 4,4'-bis[bis((β-hydroxyethoxy)phenyl)nickenyl]phenyl sulfide dihexafluorophosphate, 4,4'-bis[bis((β-hydroxyethoxy) Phenyl) indenyl] phenyl sulfide dihexafluoroantimonate, 4,4'-bis[bis(fluorophenyl)indenyl] phenyl sulfide dihexafluorophosphate, 4,4'-double [double (fluorophenyl) fluorenyl] phenyl sulfide dihexafluoroantimonate, 4,4'-bis(diphenylfluorenyl) phenyl sulfide dihexafluorophosphate, 4,4'-bis(diphenyl Thiophene) phenyl sulfide dihexafluoroantimonate, 4-(4-benzylidenephenylthio)phenyl-di-(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluorophosphate , 4-(4-phenylmercaptophenylthio)phenyl-bis-(4-(β-hydroxyethoxy)phenyl)phosphonium hexafluoroantimonate, 4-(4-phenylmercaptobenzene Thio)phenyl-bis-(4-fluorophenyl)phosphonium hexafluorophosphate, 4-(4-benzylidenephenylthio)benzene -bis-(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(4-benzylidenephenylthio)phenyl-diphenylphosphonium hexafluorophosphate, 4-(4-benzoquinone Phenylthio)phenyl-diphenylphosphonium hexafluoroantimonate, 4-(phenylthio)phenyl-di-(4-(β-hydroxyethoxy)phenyl)nickel hexafluorophosphate, 4-(phenylthio)phenyl-bis-(4-(β-yl)ethoxy)phenyl) hexafluoroate, 4-(phenylthio)phenyl•di-(4- Fluorophenyl)phosphonium hexafluorophosphate, 4-(phenylthio)phenyl-di-(4-fluorophenyl)phosphonium hexafluoroantimonate, 4-(phenylthio)phenyl-diphenylanthracene Hexafluorophosphate, 4-(phenylthio)phenyl-diphenylphosphonium hexafluoroantimonate 130806.doc -22- 200911886 Salt, 4-(2-chloro-4-benzomethylphenylthio)benzene Bis(4-fluorophenyl)phosphonium hexafluorophosphate, 4-(2-chloro-4-benzomethylphenylthio)phenyl bis(4-fluorophenyl) hexafluoroantimonate, 4 -(2-Ga-4-phenylmercaptophenylthio)phenyldiphenyl hexafluorophosphate, 4-(2- gas-4-phenylmercaptophenylthio)phenyldiphenylanthracene Hexafluoroantimonate, 4-(2- gas-4-benzylidenephenylthio)phenylbis(4.hydroxyphenyl)phosphonium hexafluorophosphate, 4-(2- Chloro-4-phenylmercaptophenylthio)phenylbis(4-diphenyl)phosphonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenyl hexafluoroantimonate, 4 - ethoxylated phenyl diindenyl hexafluorophosphate, 4 - ethoxylated benzyl monomethyl hexafluoroate, 4-methoxy methoxy phenyl dimethyl hexafluoro Phosphate, 4-decyloxycarboxyloxyphenyldifluorenyl hexafluoroantimonate, 4-ethoxycarboxyoxyphenyldimethylphosphonium hexafluorophosphate, ethoxylated ethoxyoxybenzene Base bisinyl nickel hexafluoroantimonate. Further, examples of the guanamine-based curing agent include a polyamine resin, a dipropyl acrylamide complex, and a dicyandiamide. Examples of the acid needle-based curing agent include phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid needle, maleic acid needle, hexahydrophthalic acid, and methyl acid-resistant acid. Liver, glutaric acid liver, pyromellitic anhydride, base-bis(3·butane_I,2-dicarboxylic acid) anhydride, tetrabromo-o-phenyl diacid anhydride, and the like. An epoxy compound to be blended as an optional component in the curable composition of the present invention will be described. In the curable composition of the present invention, if an epoxy compound is used, the mechanical strength of the cured product obtained by curing the curable composition can be improved. When used for: the purpose of the description, the content of the epoxy compound is better than that of the compound having a ruthenium. The ruthenium is negatively damaged. The better use amount is 5 to 25 130806.doc -23- 200911886 Further, it is more preferably 10 to 20 parts by mass. Further, the epoxidation day is used, and the content of the epoxy-curable compound is preferably 0.01 to 30 parts by mass based on 100 parts by mass of the above-mentioned compound having 3 oxime. The epoxy compound is a compound having one or two or more epoxy groups in the molecule, and is a monomeric or dimeric oligomeric or polymeric compound. X 'the ring of these epoxy compounds The oxy group may be present as a terminal group or may be present as a side group. Examples of the epoxy compound include 2,2-bis(3,4-epoxycyclohexyl)propane@, 3,4-ring I. Cyclohexylmethyl (^-epoxy) cyclohexanyl acid vinegar, 2·(3,4_epoxy)cyclohexyl_5 mountain snail (10) soil·epoxy)cyclohexyl-intermediate chewing, double[( 3,4_epoxycyclohexyl)methyl]adipate, 6-(3,4-epoxycyclohexaoxy)hexanoic acid (3,4-epoxycyclohexyl) methyl vinegar Ring epoxy compound Double hopes: shrinking water (four), double F-glycidyl ether, double s bis glycerol hydrazine bis double epoxy resin; benzene hope (four) varnish epoxy resin, age (four) varnish epoxy Shuyue, succinyl benzoic acid (four) varnish epoxy resin (4) varnish-type epoxy resin; tetraphenyl-based phenyl carbaryl glycidin, tetra-based benzophenone _ glycidol, epoxidized polyethylene An aromatic epoxy resin such as a polyfunctional epoxy resin; a polyglycidyl ether of an aliphatic polyol; a polyglycidol of an epoxy polyether of an aliphatic polyol; an aliphatic polyol and a fat a polyglycidyl ether of a polyvalent carboxylic acid of a polyvalent carboxylic acid; a polyglycidyl vinegar of an aliphatic polycarboxylic acid; a polyglycidol of an aromatic polyhydric alcohol and an aromatic polycarboxylic acid; Dimers, oligomers, polymers obtained by vinyl polymerization of glycidol or methyl propylene glycol vinegar; glycidol acrylate or glycidyl methacrylate and other 130806.doc -24- 200911886 Ethylene monomer polymerization of vinyl monomers Acquired vegetable oil, epoxidized vegetable oil from the object, % oxygen, etc. 乂Vapor, % emulsified polybutadiene: the above-mentioned epoxy compound 'molecular weight is ι〇〇~ι〇〇〇 significantly improved The mechanical strength of the hardened material to be obtained is Μ, and the epoxy equivalent is preferred, and the metal oxide fine powder is prepared as an optional component in the jg &amp; 5 of the present invention. The metal oxide fine powder can be used, for example, to improve the amount of each material after hardening: raw or used as a filler. When the content of the fine powder of the genus is used, the content of the fine powder relative to _ parts by mass is It is better that ~ ~ 〇〇〇 mass parts. A better amount, and more preferably 10 to 100 parts by mass. In the case of the above-mentioned metal oxide micropowder, I*TM m can be exemplified by an inorganic material such as a mineral, such as a colloidal silica dioxide or a dioxane (tetra) fossil gel. Shixi class; oxidation, oxygen, a milk oxide; mica, montmorillonite, #钦, and other metals / stone stone 溱 溱 soil, 绢啦卉 ancient stone, seam stone, feldspar powder, warp stone 'Eupupo II Minerals such as stone-ridge stone, etc., can also be changed to "stones and leaves (4). The towel of the material (4) is a dioxane type. For the viewpoint of heat resistance, the above metal is good. 〇〇 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Doc •25· 200911886 A well-known general user such as a fixative, a UV absorber, an I-based antioxidant, a sulfur-based antioxidant, and a filled antioxidant. For example, a light stabilizer may be a hindered amine, and a UV absorber may be mentioned. 2_Phenyldibenzoguanidine, 2-(2-pyridylphenyl)benzo Terpenoids, 2_(2_p-phenylphenyldiaryl-1'3'5.diazines, benzoates, cyanoacrylates, phenolic antioxidants, triethylene glycol·double [M3 ·Third butyl·5·methyl collar phenyl)propionic acid vinegar], dibutyl permethyl toluene (ΒΗΤ), 26-di-t-butyl group, p-methyl (10) PC, etc., sulfur-based antioxidants Examples of the second-grade thiodipropionic acid vinegar and the β-homo-based thioglycolic acid vinegar, and the scaly antioxidants include organic (tetra) acid esters. When the weather resistance imparting agent is used, heat resistance and electrical properties are obtained. The content of the curable composition of the present invention is preferably from 1 to 5 % by mass, more preferably from 0.001 to 10, from the viewpoints of hardenability, mechanical properties, storage stability, and workability. In the curable composition of the present invention, various well-known various resins, fillers, additives, and the like can be blended in the range which does not impair the target performance of the present invention. Examples of various resins which can be arbitrarily formulated include Poly-resin, polyethylene glycol or polypropylene glycol, etc., poly-resin, polyurethane resin, epoxy tree An antistatic agent, a photosensitizer, an acid proliferator, etc. may be mentioned as an example of an additive which can be arbitrarily formulated, such as a resin, a polyester resin, a melamine resin, a polyamide resin, or a polyphenylene sulfide. The target performance of the present invention is such that the compounding amount of the optional components (excluding the epoxy compound and the metal oxide fine powder described above) is preferably 10 in terms of (10) parts by mass of the compound containing the compound of the stone. The mass fraction is 130806.doc -26 - 200911886. The curable composition of the present invention has excellent fluidity at room temperature (25 ° C) and is excellent in handleability. In the state of the micropowder at room temperature (25. The viscosity measured by the E-type viscometer under (:) is preferably 50 Pa·s or less, more preferably 10 Pa·s or less. By selecting the above epoxy curable compound, the hardening type of the curable composition 4 of the present invention can be selected from the group consisting of heat curing, light curing, and curing using both light and heat. The hardening temperature at the time of heat hardening is preferably 6 〇 2 (8). Hey, more () Good is 80~15〇C. The hardening time is preferably 0.1 to H) hours, more preferably 1 to 6 hours. When performing photohardening, the active energy lines that can be used include ultraviolet rays, electron rays, X-rays, radiation, high-frequency waves, etc., and ultraviolet rays are the best in the economy. Ultraviolet light sources include ultraviolet lasers, mercury lamps, high-pressure mercury lamps, xenon lamps, sodium lamps, and metal lamps. The ultraviolet source used herein is preferably a high pressure mercury lamp. The optimum conditions for the irradiation energy vary depending on the film thickness to be applied, and are usually in the range of 100 to 10,000 mJ/cm2. Further, i) When the glass is thermally cured after photohardening, it is usually heated in the range of 60 to 15 Torr. The cured product obtained by curing the curable composition of the present invention under the conditions described above is transparent, crack resistant, heat resistant, solvent-soluble, alkali-based, and weather-resistant. , flame retardancy, moisture resistance, gas barrier properties, flexible 14 #长率 or strength, electrical insulation, low dielectric constant and other mechanical properties: properties, optical properties, electrical properties and other excellent materials. (3) The curable composition formed by the compound containing ruthenium of the present invention is excellent in stability, stability, and the like, and further has the crack resistance of the cured product, and the heat resistance is 130806.doc •27-200911886 Solvent, testability, and weather resistance are excellent in physical properties. The display material of the hardening composition material of the present invention, such as the characteristics of the hardening of the material, the electric property, etc.; the electrical/electronic material, (4) the sealing material of the material/semiconductor, the electric material, the insulation material/ ^Note/sealing;. Aowei Wanshui/moisture-proof irrigation/producing master molds for sealing materials, plastic parts, coating materials, interlayer insulation film, insulation package, heat collection, sealant/protective material m its ^0 clothing 'display device is not dense... fiber protection material, optical lens,

^Replacement Adhesive, High Heat Resistant Adhesive, High Heat Dissipating Material, High ,,,, Sealing Material, Solar Cell/Fuel Φ ^ @b Ding Battery Component, Battery Solid: Desolvation: Insulation Coating Photosensitive drums and gas separation membranes for materials and photocopiers can also be applied to concrete protection materials in civil engineering/building materials, masonry, soil injection, sealant, cold storage and heat storage materials, glass coating enamel, and further in the field of medical materials. It can also be applied to test tubes, sealing materials, coating materials, sealing materials for sterilization treatment devices, contact lenses, oxygen-rich enamel, and the like. [Examples] The present invention will be further described by the following examples, but the present invention is not limited by the examples, and the "parts" or "%" in the examples are by mass unless otherwise specified. As the benchmark. [Synthesis Example 1] 100 parts of dioxane dimethyl decane was added dropwise to a mixture of i part of ion-exchanged water, 50 parts of toluene and 450 parts of 48% aqueous sodium hydroxide solution, and allowed to make 1 〇 5. (: Polymerization for 5 hours. The obtained reaction solution was washed with 500 parts of ion-exchanged water, and then the deuterated solution was dehydrated and added to 2〇130806.doc -28-200911886 parts of pyridine, and further added thereto 10 The dimethyl hydrazine was stirred at 70 C for 30 minutes. Then, after washing with 1 part of ion-exchanged water, the solvent was distilled off under reduced pressure at 150 ° C. Then 100 parts of acetonitrile was added. After washing, the solvent was distilled off under reduced pressure at 70 ° C to obtain an acyclic polyoxane compound having an unsaturated bond. The result of GPC analysis under the following conditions was acyclic. The molecular weight of the polyglycolic compound (&amp; dim) is Mw = 20,000. Further, the following GPC is carried out under these conditions. (Measurement conditions of GPC)

TSU GEL MULTIp〇RE HXL® manufactured by TOSOH Co., Ltd., 7.8 mm×300 mm Development solvent: tetrahydrofuran [Synthesis Example 2] 100 parts of the non-cyclic polysulfide (4) obtained in Synthesis Example 1 〇) was dissolved in 200 parts of toluene, and 3 parts of platinum catalyst and 1 part of tetramethylcyclotetraoxane as a cyclic polyoxyalkylene compound were added to make 105. . The reaction was carried out for 2 hours. After distilling off the solvent under reduced pressure under thieves, it was washed with 1 part acetonitrile. Thereafter, the solvent was decompressed under a thief to obtain an intermediate (4) of polysulfide gas. The analysis result of Gpc is that the molecular weight of the polysulfide-oxygen intermediate (a3-0) is Mw=22, 〇〇(). [Example 1] Production of a compound containing ruthenium (A_〇) The poly-stone-oxygenated intermediate (4)_〇 obtained in Synthesis Example 2 of 100 wounds was dissolved in 200 wounds, and added 19 The 3-ethylamino-7-oxabicyclo[M, oxime] was burned as an epoxy compound of z. The mixture was stirred at 105 ° C for 2 hours. After the solvent was distilled off under reduced pressure, the solvent was purified by (10) portions of acetonitrile. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; As a result of GPC analysis, the molecular weight of the compound containing ruthenium (A_〇) was Mw=30,000, and the epoxy equivalent (molecular weight per unit number of epoxy groups) determined by potentiometric titration according to JIS specification K7236 was 3 〇〇〇g/mmol. Further, the following epoxy equivalents were measured by this method. [Synthesis Example 3] 90 parts of dichlorodioxanane and 9 parts of dichlorodiphenyl decane were mixed and added dropwise to 100 parts of ion-exchanged water, 5 parts of toluene, and 45 parts of 48% of oxidized hydroxide. In a mixture of aqueous sodium solutions, the mixture was polymerized at 丨〇5 〇c for 5 hours. The obtained reaction solution was washed with water in an amount of 500 parts of ion-exchanged water, and then the toluene solution was dehydrated, and 2 parts of pyridine was added thereto, and 10 parts of dimethylvinyl gas decane was further added thereto at 7 Torr. Stir under the arm for 3 minutes. Then, after washing with 1 part of ion-exchanged water, the solvent was distilled off under reduced pressure at 15 (rc), followed by washing with 100 parts of acetonitrile, and then the solvent was evaporated under reduced pressure at 7 Torr to obtain An acyclic polyoxyalkylene compound (al-Ι) having an unsaturated bond. The molecular weight of the acyclic polyoxo (i_i) is mw=2〇, 〇〇〇. [Synthesis Example 4] 100 parts The acyclic polyfluorene oxide obtained in Synthesis Example 3 was dissolved in 200 parts of toluene, and 3 parts of platinum catalyst and ι were used as the cyclic polyoxyalkylene. The compound was calcined with 1,3,5,7-tetramethylcyclotetrazepine, and allowed to react at 1 〇 5 ° C for 2 hours at 70 ° (after distillation of the solvent under reduced pressure for 1 part) The acetonitrile is washed, and then the solvent is distilled off under reduced pressure at 70 ° C to obtain a polyoxane intercalation (a3·!). The analysis result of GPC is the molecular weight of the polyoxyalkylene intermediate (a3-l). Mw = 22,000. 130806.doc -30- 200911886 [Example 2] Production of a compound containing ruthenium (A-!) 1 〇 0 part of the polyoxy siloxane intermediate obtained in Synthesis Example 4 ^^^ Compatible in 200 parts of toluene, add 19 parts 3-vinyl-7-oxabicyclo[4,^]heptane which was introduced as an epoxy compound of z, and stirred under a pressure of 1 Torr for 2 hours. The solvent was distilled off under reduced pressure at 70 ° C. After washing with acetonitrile, the solvent was distilled off under reduced pressure at 70 ° C to obtain a compound (A-1) containing ruthenium. The result of analysis by GPC was that the molecular weight of the compound containing ruthenium (octa-ruthenium) was Mw. = 30,000, epoxy equivalent (molecular weight per unit number of epoxy groups) is 3000 g / mmol 〇 [Example 3] Production of Compound (a-2) containing Shi Xi will be obtained in 100 parts of Synthesis Example 4. The polyoxyalkylene intermediate (^-" was dissolved in 200 parts of toluene, and 19 parts of allyl glycidyl ether as an epoxy compound introduced into z was added, and the mixture was stirred at 105 t for 2 hours. After distilling off the solvent under reduced pressure, the solvent was washed with 100 parts of acetonitrile, and then the solvent was evaporated under reduced pressure to give a compound (A2) containing hydrazine. The analysis result of Gpc was a compound containing hydrazine (A- 2) The molecular weight is Mw == 30,000, and the epoxy equivalent (molecular weight per unit number of epoxy groups) is 3 〇〇〇g/mm 〇 1. [Synthesis Example 5] Mixing 90 parts of dimethyl dimethyl decane with 9 parts of dichlorodiphenyl decane, and adding it to a mixture of 100 parts of ion-exchanged water, 5 parts of benzene and 45 parts of sodium oxyhydroxide使5. The polymerization was carried out for 5 hours. The obtained reaction solution was washed with 500 parts of ion-exchanged water, and then the toluene solution was dehydrated, and 2 parts of pyridine and 5 parts of ruthenium were added. Phenyl trioxane was stirred at room temperature for 3 minutes and then stirred at 7 Torr for 3 minutes. 130806.doc • 31 - 200911886 15 parts of dimethylvinyl gas decane was added thereto, and stirred at room temperature for 3 minutes' followed by stirring at 70 ° C for 30 minutes. Then, after washing with 1 part of ion-exchanged water, the solvent was distilled off under reduced pressure at 15 °C. Then, it was washed with 100 parts of acetonitrile. Then, the solvent was distilled off under reduced pressure at 7 rc to obtain an acyclic polysiloxane compound (al_2) having an unsaturated bond. The analysis result of GPC was acyclic polyfluorene. The molecular weight of the oxane (a^2) is Mw = 33, 〇〇〇. [Synthesis Example 6]

100 parts of the acyclic polyoxy siloxane compound (al-2) obtained as a precursor in Synthesis Example 5 was dissolved in 200 parts of toluene, and 3 parts of platinum catalyst and 10 parts of ruthenium were added. 1,3,5,7-tetramethylcyclotetraoxane, which is made at 1〇5. The reaction was carried out for 2 hours. After the solvent was distilled off under reduced pressure at rc (yield: EtOAc), EtOAc (EtOAc) The molecular weight of the dream oxygenated intermediate "3_2" was Mw = 36,000. [Example 4] Production of a compound containing ruthenium (A-3) 100 parts of the polysulfide intermediate (5)_2) obtained in Synthesis Example 6 was dissolved. In the U towel, add 19 parts of the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The analysis result of the compound containing Shi Xi is called GPC, and the compound containing Shi Xi is the second =, ''Ethylene equivalent (the molecular weight per unit number of epoxy groups) is 2000 g/mrn〇i. Synthesis Example 7] 130806.doc •32- 200911886

90 parts of dioxedonyl decane and 0.2 parts of dichlorodiphenyl decane were mixed and added dropwise to 1 part of ion-exchanged water, 5 parts of toluene and 45 parts of 48 parts. /〇 Hydrogen Oxidation of a mixture of aqueous sodium solutions to 1 〇5. The underarm was polymerized for 5 hours. The obtained reaction solution was washed with 5 parts of ion-exchanged water, and then the ?-Hexyl toluene solution was dehydrated, 2 parts of pyridine and 5 parts of tetrachloromethane were added, and the mixture was stirred at room temperature for 30 minutes. Then stir for 3 minutes at a few seven. 15 parts of dimethylvinyl decane was added thereto, stirred at room temperature for 3 Torr, and then stirred at 70 C for 30 minutes. Then, after washing with water of ion exchange water, the solvent was distilled off under reduced pressure at 150t:T. Then, it was washed with 1 part of acetonitrile, and then the solvent was distilled off under reduced pressure at 7 (rc) to obtain an acyclic polyoxane compound (al_3) having an unsaturated bond. The analysis result of Gpc was acyclic polyphosphate. The molecular weight of the oxygen-fired (al _3) is Mw = 4 〇, _ [Synthesis Example 8] 100 parts of the acyclic polyoxosiloxane compound (al-3) obtained as a precursor in Synthesis Example 7 Dissolved in 200 parts of toluene, adding 3 parts of the starting catalyst and IGA of 1,3,5,7-tetramethylcyclotetraoxane, and making it at 1〇5. After distilling off the solvent under reduced pressure at 70 C, the mixture was washed with acetonitrile, and then decompressed (4) solvent at 7 Gt to obtain a poly(tetra)-isomer (a3 3) GPC. The molecular weight of the burned intermediate (4)_3) was Mw = 44,000. [Example 5] Manufacture of a compound containing shixi (eight _4) (10) parts of the polyoxanthine intermediate (aw) obtained in Synthesis Example 8 was dissolved in toluene, and 19 parts were added. The lower the propyl glycidol, the lower (four) 2 hours. After 7 (r s under _ desolvation), the residue was washed with acetonitrile of 130806.doc -33 - 200911886, and the solvent was distilled off under reduced pressure at 70 ° C to obtain a compound (A-4) containing ruthenium. Analysis of GPC As a result, the molecular weight of the compound (A-4) containing ruthenium was Mw = 44,000, and the epoxy equivalent (molecular weight per unit number of epoxy groups) was 1000 g/mmol. [Example 6] Sturability composition No. 1 99.9 parts of the ruthenium-containing compound (A-0) obtained in the above Example 1 and 0.1 part of 4,4'-bis[bis(4-heptyloxyphenyl)nonylphenyl] were produced. The thioether bishexafluoroantimonate was mixed to obtain a curable composition No. 1. [Example 7] Production of the curable composition No. 2 90 parts of the compound containing ruthenium obtained in the above Example 1 was obtained. (A- 0) and 10 parts of JEFFAMIN D-2000 (manufactured by HUNTSMAN, a diamine-based curing agent) were mixed to obtain a curable composition No. 2. [Example 8] Curing composition No. 3 99.9 parts of the ruthenium-containing compound (A-1) obtained in the above Example 2, and 0.1 part of 4,4'-bis[bis(4-heptyloxyphenyl)nonylphenyl]sulfate were produced. Ether double The hexafluoroantimonate was mixed to obtain a curable composition No. 3. [Example 9] Production of the curable composition No. 4 99.9 parts of the compound containing ruthenium obtained in the above Example 2 (A- 1), and 0.1 part of 4-isopropoxy-4'-methyldiphenylphosphonium tetrakis(pentafluorophenyl)borate are mixed to obtain a curable composition N 〇. 4. [Example 10] Production of Curable Composition No. 5 99.9 parts of the ruthenium-containing compound (A-3) obtained in the above Example 4, and 0.1 part of 4,4-bis[bis(4-heptyloxyphenyl) The mercaptophenyl]thioether bishexafluoroantimonate was mixed to obtain a curable composition No. 5. 130806.doc -34- 200911886 [Example 11] The curable composition No. 6 was manufactured in a ratio of 99.9 parts. The ruthenium-containing compound (A-4) obtained in the above Example 3, and 0.1 part of 4,4'-bis[bis(4-heptyloxyphenyl)nonylphenyl] sulfide dihexafluorocarbon The acid salt was mixed to obtain a curable composition No. 6. [Example 12] Production of the curable composition No. 7 99.9 parts of the compound containing ruthenium (A-1) obtained in the above Example 2 was obtained. , 0.1 parts of 4, 4'-double [two (4- The oxyphenyl)nonylphenyl]thioether bishexafluoroantimonate and 5 parts of a cerium oxide filler (FB-7SDC; manufactured by Electric Chemical Industry Co., Ltd.) were mixed to obtain a curable composition No. 5. [Example 13] Production of curable composition No. 8 84 parts of the compound (A-1) containing ruthenium obtained in the above Example 2, and 0.1 part of 4,4'-bis[di(4-) Heptyloxyphenyl)nonylphenyl]thioether bishexafluoroantimonate and 15 parts of 2,2-bis(3,4-epoxycyclohexyl)propane are mixed to obtain a hardenable composition N 〇 . 8. [Example 14] Production of curable composition No. 9 90 parts of the compound (A-1) containing ruthenium obtained in the above Example 2, and 10 parts of JEFFAMIN D-2000 (manufactured by HUNTSMAN Co., Ltd.) The amine hardener) was mixed to obtain a curable composition No. 9. [Example 15] Production of curable composition No. 10 85 parts of the compound (A-1) containing ruthenium obtained in the above Example 2, and 10 parts of JEFFAMIN D-2000 (manufactured by HUNTSMAN, diamine) A hardening agent) and 5 parts of a cerium oxide filler (FB-7SDC; manufactured by Electric Chemical Industry Co., Ltd.) were mixed to obtain a curable composition No. 10. [Example 16] Production of Curable Composition No. 11 130806.doc -35- 200911886 90 parts of the ruthenium-containing compound (A-1) obtained in the above Example 2, and 10 parts of ADEKA Hardener EH -220 (manufactured by ADEKA, mixed epoxy curing agent) was mixed to obtain a curable composition No. 11. [Comparative Example 1] Comparison of curable composition 1 manufactured by using 99.9 parts of KF-102C Shin-Etsu Chemical, 3,4-epoxycyclohexyl polymethyloxirane bonded in a pendant type ; an epoxy equivalent of 3600 g/mmol), and 0.1 part of 4,4'-bis[bis(4-heptyloxyphenyl)nonylphenyl] thioether hexafluoroantimonate mixed to obtain hardening The composition was compared with 1. [Comparative Example 2] The curable composition was compared with the production of 2, 99.9 parts of X-22-169B (manufactured by Shin-Etsu Chemical Co., Ltd., 3,4-epoxycyclohexane-terminated polydioxanoxane; epoxy Equivalent to 1700 g/mmol) and 0.1 part of 4,4'-bis[bis(4-heptyloxyphenyl)nonylphenyl] thioether hexafluoroantimonate are mixed to obtain a curable composition Compare with 2. [Comparative Example 3] Comparison of the curable composition with the production of 3, 90 parts of KF-101 (manufactured by Shin-Etsu Chemical Co., Ltd., a polyglycol-based oxygenated group having a glycidyl group bonded to the lateral position; 350 g/mmol) and 10 parts of ADEKA Hardener EH-220 (manufactured by Adeka, mixed epoxy curing agent) were mixed to obtain a comparative composition 3 for a curable composition. [Comparative Example 4] Comparison of the curable composition with the production of 4, 99.0 parts of 1,3,5,7-tetradecyl-1,3,5,7-tetrakis(3,4-epoxycyclohexylethyl) a cyclotetraoxane and 1 part of 4,4'-bis[bis(4-heptyloxyphenyl)nonylphenyl] thioether hexafluoroantimonate are mixed to obtain a sclerosing composition. Use 4. [Examples 17 to 27, Comparative Examples 5 to 8] 130806.doc -36- 200911886 The curable compositions Nos. 1 to 11 and Comparative Examples 丨 to 4 obtained in the above Examples 6 to 16 were placed on the nameplate. The obtained curable composition was prepared by using a film having a film thickness of about 丨mm from 1 to 4, and hardening under the conditions of Table 2 and 2 to obtain a cured product 1 to 丨丨, and a cured product 丨 4 . Further, the hardening conditions in Table i indicate that the heat treatment was carried out under the conditions of the lower stage after the photohardening was carried out under the conditions of the upper stage using a high pressure mercury lamp. The cured product was evaluated for the hardened state, the heat resistance test, and the 180 degree bending test in the following manner. The hardening state is judged based on whether or not the cured film has a feeling of adhesion after a specific curing time, and the state of fluidity is evaluated as χ, and there is no fluidity but the degree of adhesion is evaluated as Δ~Q 'no adhesion feeling (4) It is ◎. In the heat resistance test, the temperature was measured by measuring 5% by mass of TG/DTA in an air atmosphere. In the 180-degree bending test, the state of the film when the film was bent at 18 degrees was observed on a cured film obtained by forming a film having a film thickness of about 丨 on an aluminum plate. The sample with no crack and peeling when the film was bent at 180 ° was evaluated as 〇, and the sample which was cracked at the time of bending and bent at 90 degrees was evaluated as △, and the bending was 90. The sample with cracks at the time was evaluated as χ. The results are shown in Table 2. Further, in Table w, an organic sulfonium-based curing agent is used as a cured product of a curable composition of an epoxy curable compound, and in Table 2, an amine-based curing agent or a mixed curing agent is used as a ring-curing property. A cured product of a curable composition of a compound. 130806.doc -37- 200911886

[II 180 degree f-curve test 〇〇〇〇〇〇〇〇 1 X 5 mass% reduction temperature (°C) 〇 inch Ο inch Ο m ΓΛ 1 &lt; Ν m hardened state ◎ ◎ ◎ ◎ ◎ ◎ ◎ &lt; X ◎ Hardening conditions 365 nm j 1000 mJ 150 ° C, 30 minutes 365 nm » 1000 mJ 150 ° C, 30 minutes i 365 nm, 1000 mJ 150 ° C, 30 minutes 365 nm, 1000 mJ 150 ° C, 30 minutes 365 nm , 1000 mJ 150 ° C, 30 minutes 365 nm, 1000 mJ 150 ° C, 30 minutes 365 nm, 1000 mJ 150 ° C, 30 minutes 365 nm, 1000 mJ 150 ° C, 30 minutes 365 nm, 1000 mJ 150 ° C , 30 minutes 365 nm, 1000 mJ 150 ° C, 30 minutes Remarks 1 1 1 1 1 Use metal oxide fine powder (&lt;ό) Use epoxy compound (,7) 1 1 1 Epoxy hardening compound strontium salt ( M) Salt-salt salt (*5) Salt, salt, salt, salt and salt! Salt-salt salt compound containing bismuth (A-0) (Al) (Al) 1 (A-3) (A-4) (Α-1) (A-1) Comparative Compound 1 (M) 丨Comparative Compound 2 (·2) Comparative Compound 3 (#3) Curable Composition No. 1 (Example 6) No. 3 (Example 8 ) inch No. 5 (Example 10) No. 6 (Example 11) No. 7 (Example 12) No. 8 ( Example 13) ί Comparison 1 (Comparative Example 1) Comparison 2 (Comparative Example 2) Comparison 4 (Comparative Example 4) I hardened material CN m inch iri Comparison 1 Comparison 2 Comparison 3 Example 17 Example ^ _1 Example 19 Example 20 Example 21 Example 22 Example 23 Comparative Example 5 Comparative Example 6 Comparative Example 7 Domain ¢(^103⁄43⁄4 ti4t)^-(NCNF 遨 遨 c cfi41H) s 硪枓 M Butterfly B-4-砩赫肊呼寸 (f (Isl wants to 侩ww^^txul^^iK^ISIrw-lc^fMf^^^^^f^^-toMl^-^H^ ^^^0蛘(硪〇硪Rofi^fi-inch ds-r'v^-ffr-sz.ve two (Γ (^^^f®-M^w^tofi®ifi-gas e_wx-&lt;鹖**紫#&gt;) CQ69l -CNlfN-x (ζ* 130806.doc •38- 200911886 tCN&lt;] § 〇〇〇〇X 士, φΐ surface ί m § 〇mg ΓΛ 硬化 Hardened state ◎ ◎ ◎ ◎ ◎ Hardening condition 150 ° C, 3 hours 150 ° C, 3 hours 150 ° C, 3 hours 150 ° C, 3 hours 150 ° C, 3 hours remarks t 1 use metal oxide powder 1 1 epoxy hardening compound amine hardener amine hardener amine hardening Agent mixed hardener mixed hardener containing antimony compound (A-0) (A-1) (A-1) (A-1) Comparative compound 1 Sturability Compound CN Jun 4 ^ No. 9 (Example 14) 1 No. 10 | (Example 15) No. 11 (Example 16) Comparative 3 (Comparative Example 3): Hardened material 00 〇 Comparison 4 1 Example 24 Example 25 Example 26 Example 27 Comparative Example 8 j 1 ^-^^-^^♦^wy^^^sRl-^-i^ti^^^r^^V^Hav-s-HHSSPJBHV^Hav -* 130806.doc -39 200911886 It can be confirmed from Table 1 that the curable composition No. 1 and No. 3 to 8 which are curable compositions of the present invention are displayed in comparison with the curable composition by 1, 2 Good hardening state. In addition, the cured products 1 to 7 which are obtained as the cured product of the present invention obtained by curing the curable composition No. 1, No. 3 to 8 which are the curable composition of the present invention, are compared with the cured product. It has better specific heat resistance and is also more flexible than the cured product. From this, it is understood that the ruthenium-containing compound of the present invention is characterized in that a ring is introduced into the cyclodecane ring.

The oxy group can be cured by the hardenability of the curable composition, and the heat and flexibility of the cured product. Further, from the comparison between the cured product 1 and the cured product 2, it was confirmed that the heat resistance of the obtained cured product was further improved by introducing an aromatic group into R and R of the chemical substance containing ruthenium. Further, by comparing the cured product 2 with the cured product 6, it is possible to further impart heat resistance by making the base metal oxide fine powder. From Table 2, it was confirmed that the cured product 8 to Η obtained by curing only the curable electric human body of the present invention by thermal curing is superior to the cured product 4 in terms of (four) properties and flexibility. From this, it is understood that the compound containing ruthenium according to the present invention is characterized in that it has an increase in the heat resistance of the epoxy group and the hardened material in the case of the ring-like compound and the pullability of the compound: the cured product 8 and the cured product 9 It can be confirmed that the heat resistance of the cured product obtained by the combination of the Re and Rf^^ of the compound containing the compound of Shishi is improved by the comparison between the cured product 19 and the hardened material iq. 2. By using metal oxide fine powder, it can be further imparted with heat resistance 130806.doc

Claims (1)

200911886 X. Patent application scope: 1 · A compound containing ruthenium, which is represented by the following general formula (0) [Chemical 1] ^ a saturated aliphatic hydrocarbon group or an aromatic smoky group having 6 to 12 carbon atoms which may be substituted with a saturated aliphatic hydrocarbon group; γ is a condensing group having a carbon number of 2 to 4, and Z is represented by the following formula (2)~ (6) The beauty expressed by any of them. [Chemical 2] ? 〇〇~fCHrCH-)rXi-CHrCH-CH2 (2) —CHfCHr^-cil-CH, (3) (wherein, Xa to Xe represents an alkylene group having 1 to 8 carbon atoms which may be substituted by an oxygen atom and/or an ester bond, -COO- or a single bond; and Rh~" means a nitrogen atom or a fluorenyl group; r represents 0 or 1); K is a number of 2 to 7 'T is a number from 1 to 7, and the polymerized portion having a repeating number of T and the polymerized portion having a repeating number of KT may be either block-shaped or random. P; P is 0~3; Μ and N are N: M=1: 1~1: 1〇〇, and the total value of all Μ and all N is 15 or more, and is expressed by the formula The mass average molecular weight of the compound containing ruthenium is 3000 to 1 million; in addition, the polymerization portion with Μ as the repeat number and the Ν 重复 repeat number of 130806.doc 200911886 may be blocky or It may be random.) 2. A compound containing ruthenium which is represented by the following formula (1). [Chemical 3] _"nH. -Si+R*) 4-p (wherein, Ra~ Rg may be the same or different, and is a saturated aliphatic hydrocarbon group having a carbon number of 1 to I? or an aromatic hydrocarbon group having 6 to 2 carbon atoms which may be substituted with a saturated aliphatic hydrocarbon group; Y is a carbon number 2 to 4 = alkyl Ζ is the same group as the above formula (0),] &lt; is a number of 〜P 1 ～4 3. 4. of 2 to 7; m and η are n: m=l : η : 1〇〇, and The number of m+n^i5 is such that the mass average VIII of the compound containing hydrazine represented by the general formula (1) is from 3 to 1,000,000; The merging portion of the repeating number may be either block-shaped or random:), n The compound containing the hydrazine of claim 1 or 2, wherein ... and "and", and the aliphatic hydrocarbon group are substituted by a carbon atom 6 to 12 of the aromatic furnace ^ U saturating - the kind of hardening composition - which is 0.01 to 2 tantalum with respect to 1 part by mass of the compound containing yttrium according to any one of 3, Ming Yong item 1 3 Jinci, epoxy hardening compound. Only 5⁄4 of 5. A sclerosing composition, which is related to 1 〇〇 之 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士 士a compound, an epoxy compound containing ο.ομοΛ 1 epoxy hardening compound and 1 to 50 ΙΑ e 贝 贝 贝 贝 。 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 如 如 如 如 如 如 如 如A metal oxide fine powder containing 1 to 1000 masses of 130806.doc 200911886 parts. 7. A cured product obtained by hardening the curable composition according to any one of claims 4 to 6. f \ 130806 .doc 200911886 VII. Designation of Representative Representatives (1) The representative representative of the case is: (none) (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: —(2) A CHj-CHf -CH-CHj —CHfCH-xM^y -α° (6) 130806.doc