TW201237103A - Curable composition, cured article, and method for using curable composition - Google Patents

Abstract

The present invention is a curable composition containing: (A) a specific silane compound random copolymer and (B) a silane coupling agent having a reactive cyclic ether structure, the mass ratio of (A) and (B) being (A):(B) = 95:5 to 80:20. The present invention is also a cured article formed when the composition is cured, and a method for using the composition as an adhesive or the like for a material with which an optical element is fixed. The present invention provides a curable composition from which a cured article having superior heat resistance and transparency and having high adhesive strength is obtained, a cured article formed when the composition is cured, and a method for using the composition as an adhesive or the like for a material with which an optical element is fixed.

Description

201237103 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. In this case, when there is a chemical formula, please reveal the chemical formula that best describes the characteristics.

R1 VI. Description of the Invention: [Technical Field to Which the Invention Is Applicable] The present invention relates to a hardenable composition which is excellent in transparency and heat resistance and which has a hardened material; it is obtained by hardening the composition, and using the same The composition is used as an adhesive for an optical element fixing material or a secondary encapsulating agent for a fixing material. [Prior Art] Up to now, the curable composition has been improved in various ways according to the use. 2 201237103 It is widely used as a raw material, an adhesive, and a coating agent for optical parts and molded bodies. For example, the hardenability of the cured product excellent in transparency can be formed, and the product can be favorably used as a raw material and a coating agent for optical parts, and a hardenable composition of a cured product having a high adhesion can be formed. It can be used well as an adhesive and a coating agent. In the recent years, the curable composition is also used as a composition for an optical element fixing material such as an adhesive for an optical element fixing material and a sealing agent for an optical element fixing material when the optical element package is manufactured. The optical element includes various types of lasers such as semiconductor lasers (LDs) and light-emitting elements such as light-emitting diodes (LEDs), light-receiving elements, composite optical elements, and optical integrated circuits. In recent years, optical elements of blue light and white light having shorter wavelengths than the peak wavelength of light have been developed and widely used. The high luminance of the light-emitting element having a short peak wavelength of such light emission is progressing rapidly, and the heat generation amount of the optical element tends to become larger. However, with the increase in the brightness of the optical element in recent years, the cured product of the composition for the optical element fixing material is exposed to higher-energy light and higher-temperature heat emitted from the optical element for a long time, and deterioration occurs. Problems such as cracks or peeling. In order to solve this problem, there is a proposal for a composition for an optical element fixing material containing a polyfluorene sesquioxide compound as a main component. However, even in the cured product of the composition for an optical element fixing material which is a main component of the polyfluorene sesquioxide compound described in Patent Documents 1 to 3, it is difficult to maintain a sufficient adhesive force to obtain heat resistance and transparency. The situation. Further, as a composition for optical element packaging, Patent Document 3 201237103 m 4 has an epoxy resin composition using a Moon-ring epoxy resin, and Patent Document 5 has an epoxy resin composition containing a polythiol compound. Proposal. However, even in the case of using such a composition, there is a case where it is impossible to satisfy the sufficient deterioration of the light-resistance with the change with time, or the contact force is lowered. Because of the urgent development of the company, it is possible to obtain a hardenable composition of a cured product which is excellent in heat and transparency and has a strong adhesion. [Patent Document 1] [Patent Document 1] JP-A-2004-359933 [Patent Document 2] JP-A-2002-359869 [Problems to be Solved by the Invention] The present invention has been completed in view of the facts of the prior art. [Patent Document 5] JP-A-2009-001 752 (Patent Document 5) A problem is to provide a cured composition of a cured product which is excellent in heat resistance and transparency and has a high adhesion, a cured product obtained by curing the composition, and a composition for use as an optical element fixing material. A method of encapsulating agent for a subsequent agent or an optical element fixing material. [Means for Solving the Problem] The inventors of the present invention have found that a specific ratio includes: (A) a random copolymer of a specific decane compound; and 4 201237103 (B) a special ratio of a cetane couple. The composition of the mixture can maintain excellent transparent heat resistance for a long time! · The raw material, and the hardened material which can also have a high adhesion force at both temperatures, achieves the completion of the present invention. According to a first aspect of the present invention, there is provided a curable composition of the following [1] to [8] [1] a curable composition which is a (A) decane compound random copolymer which is attached to a molecule, and is described below. Among the recurring units shown in formula (i), (ii) and (iii), there are (i) and (ii), (i) and (iii), (ii) and (iii), or (i), The reciprocal units of ii) and (iii), the weight average molecular weight is i,000~30, 〇〇〇; and (β) the decane coupling agent having a reactive cyclic ether structure, with (Α) and (Β) and mass ratio To (Α):(Β) = 95:5~8〇: The ratio of 2〇 contains

In the formula, R represents a hydrogen atom or a carbon group having 1 to 6 carbon atoms, and D is a single bond or a carbon number of 20 which may have a substituent. R2 represents an alkyl group having 1 to 20 carbon atoms or a phenyl group which may have a substituent. [2] The curable composition according to [1], wherein the above-mentioned (Α) 夕 烧 5 5 201237103 compound random copolymer is represented by a group represented by the formula Ri-CiKCiO-D - ([R '-CHCCfO-D]), a random copolymer of decane compound having a molar amount of R2 ([R2]) and a molar ratio of [t-CHCCfO-D]: [R2]=5:95 to 50:50. [3] A hardening composition which is a random copolymer of (A') Shixi-sinter compound, which is represented by the formula (i): ri_ch(cn)-D-SiCORS^x1)3" Burning at least one of the compound (1); and a mixture of at least one of the oxalate compounds of the fragment compound (2) represented by the gas (2).RSi(〇R)q(X)3-q , a weight average molecular weight of 1, 〇〇〇 30, 〇〇〇; and (B) a decane coupling agent having a reactive cyclic ether structure, with (A,) and (b) to mass ratio, (eight) :^) = 95:5~80:20 ratio of inclusion: where R1 represents a hydrogen atom or an alkyl group of carbon number, D is a single bond or a carbon number which may have a substituent. a group, R3 represents an alkyl group having 1 to 6 carbon atoms, X1 represents a dentate atom, and p represents an integer of 〇~3; wherein R2 represents an alkyl group of carbon number 20 or a stupid group which may have a substituent 'R4 is a carbon number 四(tetra) group, X2 is a _ atom, and ^ is an integer of 0 to 3. ^ [4] The sclerosing composition as described in [3], wherein the above (a,) a random copolymer of a compound, a compound (1) and a residual compound (/ The molar ratio of the oxime compound is 随机 化合物 化合物 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 5.9 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物The curable composition, wherein 201237103, the above (B), is a sulphur coupling agent having a cyclohexene oxide group. [6] The hardening according to any one of [1] to [5] The composition further contains (C) a metal complex in which the metal atom is aluminum, ruthenium or titanium, and the content of the component (c) is (A) component or (a,) component 丨 00 mass part, including 〇 mass part The hardening composition according to any one of [1] to [5] further comprising (D) an alicyclic acid anhydride having a carboxyl group, and a content of the component (d) The (a) component or the (A') component 1 〇〇 mass portion includes a 〇 mass portion or more, and a 〇 mass portion or less. [8] The curable composition according to any one of [1] to [7] According to the second aspect of the present invention, the cured product of the following [9] and [1〇] can be provided. [9] A cured product which is hard. [10] A hardened composition according to any one of [n] to [7], wherein the hardening composition according to any one of [n] to [7] is cured. According to the third aspect of the present invention, there is provided a method of using the curable composition of the present invention as follows [11;], [12] [11] A method of any of [丨~I; 7] One of the curable compositions described above is used as an adhesive for fixing an optical element. [12] The curable composition according to any one of [7] to [7], which is used as an encapsulant for an optical element fixing material. [Effect of the Invention] According to the curable composition of the present invention, even when irradiated with high-energy light 7 201237103 or a high temperature state, coloring is not caused for a long period of time, and transparency is lowered.

And an encapsulant for optical component fixing materials. In particular, the following is a description of the method of using the curable composition, 2) the cured product, and 3) the curable composition, which will be described in detail below. 1) Curable composition The curable composition of the present invention is characterized in that (A) a random copolymer of a decane compound, which is attached to the molecule, is represented by the following formulas (i), (i), and (iii) Among the recurring units, there are repetitive units of (i) and (ii), (i) & (iii), (ii) and (iii), or (i), (ii) and (iii), weight average molecular weight. Between 1,000 and 30, 000; and (B) a decane coupling agent having a reactive cyclic ether structure, with (8) and (6) and mass ratio, (8): (8) = 95:5-80 The ratio of :20 is included: 201237103

CH-CN

(i) (8) (iii) In the formula, R1 represents an argon atom or an alkyl group having 1 to 6 carbon atoms, and D is a single bond or a divalent organic group having 1 to 20 carbon atoms which may have a substituent. R2 represents an alkyl group having 1 to 20 carbon atoms or a stupid group which may have a substituent. (A) Cycloal Compound Random Copolymer The curable composition of the present invention, as the component (A), is contained in the reversing unit described in the above formulas (i), (ii) and (iii), and has (i) and (h), (Ο) and (iii), (ii) and (iii), or (i)' and (iii) of the recurring unit, a weight average molecular weight of 丨, 000~30, 000 decane compound random copolymer ( Hereinafter, there is a case called "the decane compound random copolymer (A)".) The decane compound random copolymer (A) may have a reversal unit represented by (丨), (ii) (iii), respectively. In the formulae (1) to (1 1 1), R1 represents a hydrogen atom or an alkyl group having a carbon number of 6, and preferably a hydrogen atom. The alkane of the carbon number i to 6 represented by Ri The base may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a t-butyl group, an isobutyl group, a second butyl group, a positive 201237103 pentyl group or a n-hexyl group. Or a divalent organic group having a carbon number of 1 to 2 carbon which may have a substituent. The divalent organic group ' may be a calcined group having a carbon number of 1 to 2 Å having a substituent, and a carbon which may have a substituent 2 to 20 alkenylene group, alkynylene group having 2 to 20 carbon atoms which may have a substituent, an arylene group having 6 to 20 carbon atoms which may have a substituent, and an alkylene group which may have a substituent a combination of an alkenyl group or an alkynylene group and a arylene group which may have a substituent, and a divalent organic group having 7 to 20 carbon atoms which may have a substituent, etc. a methyl group, an ethylene group, a propylene group, a triadenylene group, a tetrakisinyl group, a pentamethylene group, a hexamethylene group, etc. The alkenylene group of the above alkenylene group may be a vinylidene group or a propylene group. a butenylene group, a pentenylene group, etc. The alkynylene group of the above alkynylene group may, for example, be an ethynylene group or a propylene group. The arylene group of the above arylene group may be an adjacent sub-phenyl group or m-phenylene group. a p-phenylene '2,6-yarnylene group, etc. The substituent of the above-mentioned alkylene group, a sub-base group and an alkynylene group may be a functional atom of a fluorine atom or a gas atom; An alkoxy group such as an oxy group; an alkylthio group such as a methylthio group or an ethylthio group; an alkoxy group such as a methoxycarbonyl group or an ethoxy group; or the like. Substituent a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; an alkyl group such as a methyl group or an ethyl group; an alkoxy group such as a methoxy group or an ethoxy group; a methylthio group; An alkylthio group such as a thio group, etc. These substituents may be bonded to an alkylene group, an alkenylene group, an alkynylene group, and a group of the group 10 201237103 'aryl group, etc., may be the same Or a plurality of different bonds. It may be composed of a combination of an (alkylene, alkenylene or alkynylene group) having a substituent and an arylene group which may have a substituent, and may have a carbon number of 2 The organic group may have at least one of the above substituents (alkylene, alkenylene or alkynylene) and at least one linear bond to the above-mentioned arylene group having a substituent. Specifically, it can be represented by the following formula

Ch2 (CH2)2 CH, CH II CH Among these, D is a hardened material having a high adhesion, an alkylene group having 1 to 10 carbon atoms, and an alkylene group having a carbon number of 6 More, the alkylene group of the number 3 is particularly preferred. In the formula (i) (iii), 'R is a phenyl group having 1 to 2 carbon atoms or a phenyl group which may have a substituent. The alkyl group having 1 to 20 carbon atoms represented by R2 may, for example, be an alkyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a t-butyl-n-pentyl group or a hexyl group. Base, n-octyl, isooctyl, n-decyl, n-decyl, twelfthylene, and the like. The substituent of the phenyl group which may have a substituent represented by R2 may, for example, be a methyl group, a propyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a butyl group or a n-pentyl group. 11 201237103 group of n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, etc., an alkoxy group such as a methoxy group or an ethoxy group; a halogen atom such as a gas atom or a gas atom; Specific examples of the phenyl group which may have a substituent represented by R2 include a phenyl group, a 2-gas group, a 4-methylphenyl group, a 3-ethylphenyl group, a 2,4-dimethylphenyl group, and 2 - methoxyphenyl and the like. In the random copolymer of decane compound (A), the molar amount of the group represented by the formula: t - ciKCN)-!)- ([t-CHCCfO-D]) and the molar amount of R2 ([f]) 'With [R^CHCC^-D)] : [R2] = 5:95~50:50 is better, preferably 10:90~40:60. In this range, the obtained cured product is excellent in transparency and adhesion, and the heat resistance is excellent, and even if it is placed at a high temperature, the deterioration of the properties can be suppressed. The amount represented by the formula: t-CIKCiO-D- and the amount of R2 can be quantified by, for example, NMR spectroscopy using a random copolymer of decane compound (A). The weight average molecular weight (Mw) of the random copolymer (A) of the Shi Xiyuan compound is 1, 〇〇〇 30, and the range 〇〇〇 is preferably 500 Å, and the range of 〇〇〇 is preferable. In this range, the workability of the composition is excellent, and a cured product excellent in heat resistance can be obtained. The weight average molecular weight () can be determined, for example, by gel permeation chromatography (GPC) using tetrahydrogen flu (THF) as a solvent in a standard polystyrene conversion value. . The molecular weight distribution (Mw/Mn) of the decane compound random copolymer (A) is not particularly limited, and is usually 1.0 to 3.0, preferably in the range of 1. By this range, a cured product excellent in adhesion and heat resistance can be obtained. The decane compound random copolymer (A) may be used alone or in combination of two or more. 12 201237103 In the curable composition of the present invention, the above-mentioned (A) component decane compound random copolymer u) is condensed (A,) formula (1): Rl_CH(CN)_D_si(〇R3)p (X1)31 (wherein R1 represents a hydrogen atom or an alkyl group having a carbon number of ,, and D is a single bond or a carbon number of 20 which may have a substituent; 20 is an alkyl group having a carbon number of 6; a halogen atom, an integer represented by p), at least one of the decane compound (1); and a formula (2): R2si(〇R4)q(X)3-q (wherein R represents a carbon number 2 The base of the alkyl group or the group which may have a substituent, R represents an alkyl group having a carbon number of i to 6, and the oxime 2 represents a halogen atom, and the mouth system represents an integer of 0 3 ) a mixture of a compound of at least one kind of Xiyuan compound having a weight average molecular weight of 1, 〇〇〇~3〇,000 of a decane compound random copolymer (hereinafter, referred to as "decaneated. Random copolymer (Α' In the case of .), a random copolymer of decane compound (Α), preferably a random copolymer of decane compound (Α,). [decane compound (1)] The decane compound (1) is a compound represented by the formula (1): R1_CH(CN) D_Si(〇R3)p(X)3p. By using the Shi Xi Yuan compound (1), a random copolymer of a decane compound having transparency and good adhesion after hardening can be obtained. In the formula (1), R1 represents a hydrogen atom or an alkyl group having a carbon number of 6, and a hydrogen atom is preferred. Specific examples are exemplified as R of a random copolymer of a decane compound. In the formula (1), 'D' represents a single bond or a hexavalent organic group having 1 to 20 carbon atoms which may have a substituent. Specific examples of the divalent organic group are exemplified as D of the random copolymer of silane compound (4). R is a carbon number of 1 to 2, ethyl, n-propyl, isopropyl, n-butyl, 13 201237103 dibutyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, etc. 6 yard base. X1 represents a γ atom such as a fluorine atom, a gas atom or a bromine atom. P represents an integer of 0-3. When P is 2 or more, 〇R3 may be the same or different from each other. Further, when (3-p) is 2 or more, X1 may be the same or different from each other. Specific examples of the decane compound (1) include cyanomethyltrimethoxydecane, cyanomethyltriethoxydecane, 1-cyanoethyltrimethoxydecane, and 2-cyanoethyltributoxide. Baseline, 2-cyanoethyltriethoxydecane, 2-cyanoethyltripropoxydecane, 3-cyanopropyltrimethoxydecane, 3-cyanopropyltriethoxydecane, 3-cyanopropyltripropoxydecane, 3-cyanopropyltributoxydecane, 4-cyanobutyltrimethoxydecane, 5-cyanopentyltrimethoxydecane, 2-cyanopropyl Tris-methoxydecane, 2-(cyanomethoxy)ethyltrimethoxy decane, 2-(2-cyanoethoxy)ethyltrimethoxy oxime, o-(cyanoguanidino Stupyl tripropoxydecane 'm-(cyanomethyl)phenyl trimethoxy decane, p-(cyanoindolyl)phenyl triethoxy decane, p- 2 - cyanoethyl) phenyl triterpene a trialkoxy decane compound such as oxydecane; cyanodecyltrichlorodecane, cyanomethylbromodimethoxydecane, 2-cyanoethyldimethoxymethoxynonane, 2-cyanoethyl Dioxoethoxy decane ' 3 cyanopropyl trichloro decane, 3-cyano Propyltribromodecane, 3-cyanopropyldimethoxymethoxynonane, 3-cyanopropyldimethoxyethoxydecane, 3-cyanopropyldimethoxydecane, 3-cyanopropane Base gas diethoxy decane, 4-cyanobutyl gas diethoxy decane, 3-cyano-n-butyl chloride diethoxy decane, 2-(2-cyanoethoxy)ethyl three gas Decane, 2-(2-cyanoethoxy)ethylbromidediyl 14 201237103 Oxygen oxime, 2-(2-cyanoethoxy)ethyldichloromethane fluorenyl decane, o- (2 - cyanoethyl)phenyltrichloromethane, m-(2-cyanoethyl)phenylmethoxydihydrononane, p-(2-cyanoethyl)phenyldimethoxychlorodecane pair (2 A dentate decane compound such as cyanoethane or the like, or a combination of two or more kinds of phenyl tribromodecane, and the like. The decane compound (1) may be used alone. Among these, my compound (1), which is obtained from a hardened material having a more excellent adhesion, is preferably a tri-oxo-oxygen compound, and a dialkoxy decane compound having a 2-cyanoethyl group. Or a compound having a 3-cyanopropyl group of three compounds is more preferred. [decane compound (2)] The decane compound (2) is a compound represented by the formula (2): R2Si(〇R4)q(x2)3q. In the formula (2), R is a phenyl group having 1 to 2 carbon atoms or a phenyl group which may have a substituent. Specific examples are exemplified as R2 of the decane compound random copolymer (a). R4 represents an alkyl group having the same carbon number as the above R3. X2 represents the same halogen atom as the above Xi. The q system represents an integer of 0 to 3. When q is 2 or more, OR4 may be the same or different from each other. Further, when (3_q) is 2 or more, X2 may be the same or different from each other. Specific examples of the compound (2) of the Shi Xiyuan compound include mercaptotrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, n-propyltrimethoxydecane. , n-butyltriethoxydecane, isobutyltrimethyl 15 201237103 oxysulfonium, n-pentyltriethoxydecane, n-hexyltrimethoxy decane, isooctyltriethoxydecane, dodecane Alkylene trialkyl gas based on tris-methoxydecane, methyl dimethoxyethoxy decane, methyl diethyl methoxy decane, etc.; methyl dimethyl dimethoxy decane, Dioxaterpene, methyl dioxodecane, mercaptochlorodiethoxydecane, ethyl chlorodimethoxy oxime, ethyl dioxomethoxy decane, n-propyl hexane An alkyl halogenated alkoxy decane compound such as decyloxydecane or n-propyldimethoxymethoxydecane; methyl trioxane, methyltribromodecane, ethyl trioxane, ethyltribromodecane, Alkyltrifunctional decane compounds such as n-propyl trioxane; phenyltrimethoxydecane, 4-decyloxyphenyltrimethoxy矽, 2-phenylphenyl trimethoxy decane, phenyl triethoxy decane, 2- methoxy phenyl triethoxy decane, phenyl dimethoxy ethoxy decane, phenyl diethoxy a stupidyl trialkoxy decane compound which may have a substituent such as a methoxy oxane or the like; a phenyl dimethoxy decane, a phenyl dimethoxy methoxy decane, a phenyl methoxy ethoxy oxime a phenyl group which can have a substituent, a phenyl sulfonate compound, a phenyl trioxane, a phenyl trioxane, a phenyl trioxane a phenyl group which may have a substituent such as tribromodecan, 4-methoxyphenyl triazepine, phenyl trioxane, 2-ethoxyphenyl trioxane, 2-p-phenyltrioxane or the like three! | Hydrazine compounds. These decane compounds (2) may be used singly or in combination of two or more. 16 201237103 [Mixed mixture of decane compounds] The mixture of the smoldering compound used in the manufacture of the decane compound random copolymer (A') can be a mixture of the decane compound (1) and the decane compound (2). Further, a mixture of other decane compounds may be further included in the range which does not hinder the object of the present invention, but a mixture of the decane compound (1) and the cerium compound (2) is preferred. The ratio of the decane compound (1) to the decane compound (2) is preferably in the molar ratio of [decane compound (1)]: [decane compound (2)] = 5: 95-50:50 by 10: 90~40: 60 is better. The method of condensing the mixture of the above decane compounds is not particularly limited, and the pulverized compound (1), the ishixiyuan compound (2), and other desired ceramsite compounds are dissolved in a solvent, and the method is added. Amount of catalyst, a method of stirring at a given temperature. The catalyst used may be either an acid catalyst or an alkali catalyst. The acid catalyst may, for example, be an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid; or an organic acid of methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid or cesium trifluoroacetate. The catalyst can be exemplified by trimethylamine, triethylamine, lithium diisopropylamide, lithium bis(trimethylsulfonyl)amine, pyridine, L 8_diazabicyclo[5·4· 〇]_7_ An organic base such as undecene, strepamine, picoline, 1,4-diazabicyclo[2.2.2]octane or imidazole, tetramethylammonium hydroxide or tetraethylammonium hydroxide Organic alkali hydroxide; sodium alkoxide sodium ethoxide, metal alkoxide such as sodium butoxide, potassium butoxide; metal hydride such as sodium hydride or calcium hydride; sodium hydroxide, potassium hydroxide, A metal hydroxide such as calcium hydroxide; a metal carbonate such as sodium carbonate, 201237103, potassium carbonate or magnesium carbonate; or a metal hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate. The amount of the catalyst used is 1 mole in total of the decane compound, and is usually 〇. i. The mass portion or more is 10 parts by mass or less, and preferably 0.5 parts by mass or more and 5 parts by mass or less. The dissolution used may be appropriately selected depending on the kind of the decane compound. For example, water, stupid, stupid, dioxane and other aromatic hydrocarbons; esters of decyl acetate, ethyl acetate, propyl acetate, methyl propionate, etc.; acetone, acetophenone, decyl isobutyl ketone, A A ketone such as cyclohexanone; an alcohol 4 such as decyl alcohol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol or third butanol. The bath may be used singly or in combination of two or more. The amount of the bathing agent, the total molar amount of the decane compound per 1 liter of the solvent, is usually 0. ImoWOmol, preferably in an amount of 5 m〇1 to 10 m〇1. The temperature at which the decane compound is condensed (reacted) is usually in the range of from 〇 to the boiling point of the dissolved boiling point used, and it is preferably in the range of 2 〇 t: ~1 。. When the reaction temperature is too low, the progress of the condensation reaction in the shell 1 is insufficient, and on the other hand, when the reaction temperature is over-the-counter, it is difficult to suppress gelation. The reaction is terminated by a lapse of 30 minutes to 20 hours. When an acid catalyst is used, when an inert aqueous solution such as sodium hydrogencarbonate is added to the reaction solution, when the catalyst is used, # is added to the reaction solution by adding an acid such as hydrochloric acid to the reaction solution. The salt is removed by filtration or water washing to obtain a random copolymer of the desired decane compound. (β) a decane coupling agent having a reactive cyclic ether structure. The curable composition of the present invention as the component (8), and a decane coupling agent having a reactive cyclic ether machine having a decane coupling agent having a reaction structure of 18 201237103 (Hereinafter, there is a case called decane coupling agent (B)".). Since the curable composition of the present invention contains the Shi Xi Xuan coupling agent (B), it can be obtained without phase separation (white turbidity), and has excellent transparency and high adhesion. The structure of the reactive cyclic ether of the breaker coupling agent (B) is a structure having a reactive cyclic ether group. The reactive cyclic ether group may, for example, be an epoxy group; a cyclohexene oxide group such as a cyclopentadienyl group; an oxetanyl group; a tetrahydrofuranyl group; a tetrahydropyranyl group; Among these, an epoxy group, a cyclohexene oxide group, an oxa% butane group is preferred, a cyclohexene oxide group is more preferred, and a 3,4_ rabbitoxycyclohexyl group is particularly preferred. Specific examples of the structure of the reactive cyclic ether include the groups shown by the following (E丨) to (£3):

The base of the h series 2 to 8 is particularly preferred.

19 201237103 Preferably, the compound represented by the formula (3) is exemplified. dSi—(〇Rb)k (a) In the formula (a), E represents a reactive cyclic ether structure, and Ra represents an alkyl group having 1 to 6 carbon atoms or a stupid group which may have a substituent, and Rb represents a carbon. The alkyl group has a number of 1 to 6, i represents an integer of 1 3, j represents an integer of 〇 2, and k represents an integer of 1 to 3, and i + j + k = 4. In the formula (a), Γ and Rb represent an alkyl group having a carbon number of 1-6, and the above R1 is an alkyl group having 1 to 6 carbon atoms, and is represented by the same group as exemplified above, and is represented by the above R. The phenyl group which may have a substituent may, for example, be exemplified as the same group as the stupid group which may have a substituent represented by the above R2. Specific examples of the decane coupling agent (B) represented by the above formula (a) include 2-(3'4-epoxycyclohexyl)ethyltrimethoxy decane and 2-(34-epoxycyclohexyl). a cyclohexene oxide-based decane coupling agent such as ethyl triethoxy decane; 3-glycidyl ether propyl trimethoxy decane, 3-glycidyl ether propyl triethoxy decane, 3-glycidol a glycidyl ether-based decane coupling agent such as ether propyl methyl dimethoxy decane or 3 _ glycidyl ether propyl methyl ethoxy oxane; (oxetane-3-yl)methyltrimethoxy Decane, (oxetane-3-yl)methyltriethoxydecane, (oxetane-3-yl)methylmethyl-methoxydecane, (oxetane-3 -yl)methylmethyldiethoxydecane (oxetan-3-yl)methylethyldimethoxydecane, (oxetan-3-yl)methylethyldiethyl Oxydecane, (oxetane-yungyl) = 20 201237103-based dimethoxydecane, (oxetane-3-yl)nonylphenyldiethoxydecane, 2-(oxo-heterocycle) Butyryl)ethyltrimethoxy decane, 2_(oxa 3-yl) ethyl triethoxy silane-oxetanyl like a silane-coupling agent and the like. The viewpoint of the hardened material is preferably a compound represented by the following formula (b) which is easy to obtain and has a high adhesion.

(CH 丨 3) E2-+-S1-(〇Rb)k 〇,) In the formula (b), 'E2, Rb, i, j, and k are the same as the above. Rb' is preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent such as a methyl group, an ethyl group, a propyl group or a decyloxymethyl group. Specific examples of the decane coupling agent represented by the formula (b) include 2-(3,4-epoxyfluorenyl)ethyltrimethoxy decane '2-(3,4-epoxycyclohexyl)B. Base trimethoxy decane and the like. The decane coupling agent (B) may be used alone or in combination of two or more. In the curable composition of the present invention, the components (A) and (B) are contained in a ratio of (a):(b) = 95:5 to a mass ratio of (a) to (B). By using the components (A) and (B) in such a ratio, it is possible to obtain a curable composition of a cured product which is excellent in transparency and adhesion, and which is excellent in heat resistance and which is not easily lowered even at a high temperature. From this point of view, the ratio of (A): (B) = 95: 5 to 85:15 is preferred, and the ratio of 92:8 to 87:13 is particularly good. The curable composition of the present invention 'adds the components (A) and (B), and contains (c) a metal complex of a metal atom of cerium, zirconium or titanium (hereinafter, referred to as "metal 21 201237103 complex ( c) The situation".) is better. By using the metal complex (c), the hardening reaction can be promoted, and a cured product having a higher adhesion can be obtained. The metal complex (a) in which the metal atom is aluminum may be exemplified by diisopropoxy aluminum acetoacetate monooleate s, #isopropoxy red-branched acetic acid dioleyl-based, monoisomeric: oxy aluminum Monooleate ethyl acetate ethyl acetate, diisopropoxy aluminum acetoacetate monolaurin vinegar, diisopropoxy aluminum acetoacetate monostearyl ester, diisopropoxy acetonitrile acetic acid monoisostearyl § Purpose, monoisopropoxy hydride U gu 1 - alanine vinegar acetoacetate monolauric vinegar, triethyl hydrazine propionate and so on, the acetic acid complex; succinic acid sulphate Butyl ethanoacetate) integrator, succinic acid monosuccinate (2-ethylhexyl ethoxyacetic acid) chelate, monoethyl phthalic acid succinyl (dodecyl acetoacetate) chelate, single An aluminum acetopropionic acid complex such as a bismuth (oleylacetic acid) chelate compound. The metal complex (c) in which the metal atom is wrong may be a chitosan complex such as a second butyl group, an ethoxy group, or a third butyl group. Styrene-acid complex; a wrong base metal complex such as tetraisopropoxy lead, etc. β may be titanium tetraisopropoxide, titanium triethanolamine dipropionate, tetraoctyl glycolate, silver Alcohol S is a complex. a metal atom as a metal complex of titanium (c), a titanium hydride complex of tetra-n-butoxytitanium, tetra-ethylhexyloxytitanium or an ammonium salt of titanium lactate; dioctyloxy acid The titanium dimetal complex (C) such as bis(octyl glycol ester) may be used alone or in combination of two or more. When the metal complex (6) is used, the content is in the component (1) or the mass portion. The quality department is more than 10 parts by mass or less. quality. The score is better than 5 quality parts. 22 201237103 The curable composition of the present invention 'adds the components (A) and (b), and contains (D) an alicyclic acid anhydride having a carboxyl group (hereinafter referred to as "alicyclic acid anhydride (D)"). good. By using the alicyclic anhydride (D), a hardener having a higher adhesion can be obtained. The alicyclic anhydride (D) is at least one carboxyl-substituted alicyclic anhydride. Specific examples of the alicyclic acid anhydride include 3-methyl-1,2,3,6-tetrahydron-butyric acid, 4-methyl-1,2,3,6-tetrazolium phthalate liver , tetrahydro-o-st-one-formic acid liver, 3_mercapto-hexazone, benzoic acid, 4-mercapto-hexahydrophthalic anhydride, hexahydrophthalic anhydride, decyl norbornene Diacid Xuan, 5_ norbornazole dilute-2, 3 - di-anhydrous anhydride, reduced calcination-2,3 - bis-alkali anhydride, methyl _5_ norbornene dilute-2, 3-dione acid needle, methyl-lower Obtained -2,3 - bis-anhydride and the like. The carboxyl group may be substituted at any position of the alicyclic structure of the alicyclic acid anhydride, and the substitution position and the number of substituted carboxyl groups are not particularly limited. Alicyclic anhydride (D) 'substituted cyclohexyl-1,2,4-tricarboxylic acid-1,2-anhydride, cyclohexane-1,2,3- substituted with hexahydrophthalic anhydride The tricarboxylic acid-i, 2-oxan is preferred, and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride is particularly preferred. Although the compound has the existence of a stereoisomer, it may be any anisotropic body. The alicyclic acid anhydride (D) may be used singly or in combination of two or more. When the alicyclic acid anhydride (D) is used, the content of the component (A) or the component (A') is preferably 0 parts by mass or more and 10 parts by mass or less, more preferably 5% by mass or less. The curable composition of the present invention may further contain other components as long as it does not inhibit the object of the present invention. Other components include a decane coupling agent other than the above (B), an oxidation prevention 23 201237103 agent, an ultraviolet absorber, a photostabilizer, a diluent, and the like. The decane coupling agent other than the above (B) is a sulphur coupling agent other than the decane coupling agent (β), and is not particularly limited as long as it does not inhibit the object (4) of the present invention. Among them, a decane coupling agent having an acid needle structure is preferably used from the viewpoint of obtaining a cured product having a higher adhesion. Specific examples of the decane coupling agent include 2-triethoxydecylsuccinic anhydride and 3-triethyldecyl succinic anhydride. The Shixiyuan coupling agent of the acid needle structure may be used alone or in combination of two or more. When a decane coupling agent having an acid anhydride structure is used, the amount of the decane coupling agent used is 100 parts by mass of the (α) component or (A,) component, usually less than or equal to the mass portion 卩〇. 5 mass parts or more! 5 quality parts are better. The above oxidation preventing agent is added to prevent deterioration of oxidation during heating. Examples of the oxidation inhibitor include a phosphorus oxidation inhibitor, a phenol oxidation inhibitor, and a sulfur oxidation inhibitor. Examples of the phosphorus-based oxidation preventing agent include phosphates and oxaphosphorus oxides. A monophenol, a bisphenol, a polymeric phenol, etc. are mentioned. It can be used as a sulphur-based oxidation inhibitor of dilauro-3, 3'-thiodipropionic acid-thiodipropionate, distearyl-3,3'-sulfur-based oxidation inhibitor, and two meats. Myristyl 3, 3, substituted dipropionate and the like. These oxidation inhibitors may be used singly or in combination of two or more. The amount of the oxidation preventing agent to be used is usually 1 part by mass or less per part of the component (A) or the component (A). 24 201237103 The above-mentioned ultraviolet absorber is added to the purpose of improving the light resistance of the cured product. The ultraviolet absorber is an acid absorber, a benzophenone, a benzotriazole or a hindered amine. The ultraviolet absorbers ' may be used singly or in combination of two or more. The amount of the ultraviolet absorber to be used is usually 10 parts by mass or less for the (A) component or the (A') component 100 mass portion. The above-mentioned light female mites are added for the purpose of improving the light resistance of the cured product. The light stabilizer "for example, polytetradecylbutyl)amino-1'3,5-triazine-2,4-yl}{(2,2,6,6-tetradecyl-4-ispiperidine a hindered amine such as an imido}hexamethylene {(2,2,6,6-tetramethyl-4-piperidinyl)imido}}. These photosensitizers may be used singly or in combination of two or more kinds of photosensitizers, and the mass of the component (A) or the component (A) is usually 10 parts by mass or less. The diluent is added to adjust the viscosity of the curable composition. The diluent may, for example, be glycerol diglycidyl shunt, butanediol dimer: oleyl ether, diglycidyl aniline, neopentyl glycol glycidyl ether, cycloheximide dimethanol glycidyl ether, subditch Diglycidyl St, polyglycol ^ propanol diglycidyl ether, trimethylol propyl diglycidyl ether, ether, glycerol triglycidyl ether, I 2-epoxy-4-vinylcyclohexene &amp; Emulsified cyclohexene ethylene, cerium oxide-based vinyl cyclohexene, and the like. The diluent such as hydrazine may be used singly or in combination of two or more. 25 201237103 The curable component of the present invention and the 'composition' obtained by mixing and defoaming according to a desired method can be prepared by, for example, blending the other components of the above (A) and (B) in a predetermined ratio. The present invention obtained as described above can have an excellent transparent compound for a long period of time at the time of high-energy light irradiation or high-temperature property. The curable composition can be obtained in a state where it does not color or reduce transparency and has a high adhesion force. Therefore, the curable composition of the present invention can be favorably used as a raw material for an optical component or a molded body. , adhesive, coating agent. In particular, the curable composition of the present invention can be suitably used as a composition for a fixing member for an optical element because it can solve the problem of deterioration of the fixing member of the optical element with the increase in the brightness of the optical element. 2) Hardened material The second aspect of the present invention is a cured product obtained by curing the curable composition of the present invention. The method of hardening the curable composition of the present invention is heat hardening. The heating temperature at the time of hardening is usually from 100 to 2001: and the heating time is usually from 1 Torr to 20 hrs, preferably from 1 minute to 1 hr. The cured product of the present invention has excellent transparency and long-lasting force even if it is irradiated with high-energy light or in the south/in-state state without coloring or lowering transparency. Therefore, the cured product of the present invention can solve the problem of deterioration of the optical element fixing material with the increase in brightness of the optical element. The curable composition of the present invention can be suitably used as an optical element fixing material. Composition 26 201237103. For example, it can be suitably used for an optical toner, a material for coating a molded article, and a hardened material of the present invention, which has a high degree of hardenability. The force ' can be confirmed, for example, by measuring the contact force as follows, that is, the mirror-coated hardening property of the hard-day film is placed on the object to be attached, and heated. Treatment to harden it. —, σιίε, the enemy is preheated to the 疋/ 度 degree (eg 23t, l〇 (Tc) and then test the crying, day, ^, — on the test bench of the state of the state for 30 seconds , by the position of the body at a height of 5 0 # m, the butt joint surface is applied with a horizontal method (shear direction) to measure the adhesion between the test piece and the object. The adhesion of the hardened object lies in the coffee. And 1〇〇t, it is better to look at 2 Longkou or above '80N/2mm□ or more. The cured product is excellent in transparency and can be confirmed by measuring the light transmittance. The light transmittance of the cured product is Light having a wavelength of 4 〇〇 nm is preferably 8 〇 % or more, and particularly preferably m or more, and light having a wavelength of 45 〇 nm. Preferably, the cured product is excellent in heat resistance, and can be confirmed by changing the force and transparency after the cured product is placed at a high temperature. The adhesive force is placed at 100 ° C for 30 seconds. It is preferable to maintain the adhesion force of 5〇% or more at 23t, and to maintain the force more than 65%, and the transparency is better. The transparency is set at a wavelength of 4〇〇nm after being placed at 15〇°C for 500 hours. 3% or more of the initial transmittance is preferable. 3) Method of using the curable composition The third embodiment of the present invention is used for the adhesive agent for an optical element fixing material or an optical element fixing material. In the case of the encapsulant, the light-emitting element, the light-receiving element, the composite optical element, the optical integrated circuit, etc. of LED, LD, etc., etc. <Adhesive for optical element fixing material> The hardening property of this invention The composition can be suitably used as an adhesive for fixing an optical element. The curable composition of the present invention is used as a method for using an adhesive for an optical element fixing material, and the material to be used (the optical element and the optical element thereof) One of the boards, etc.) The composition is applied to the adhesive surface of the square or both sides, and after crimping, it is heated and hardened. The method of adhering the materials of the object to each other is firmly followed. Next, the main substrate material of the optical element is sodium glass and heat resistance. Glass such as hard glass; ceramics; metal such as iron, copper, aluminum, gold, silver, platinum, ruthenium, metal alloys, stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.); polyparaphenylene Ethylene glycol dicarboxylate, poly(p-butylene dicarboxylate), polybutylene naphthalate, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polydecylene, polysulfone Synthesis of polyetheretherketone, polyethersulfone, polyphenylene sulfide, polyetherimide, polyimine, polyamine, acrylic resin, norbornene resin, cyclic olefin resin, glass epoxy resin, etc. Resin, etc. The heating temperature at the time of heat curing is usually 1 〇 〇 〜 2 0 0 depending on the hardenable composition used. (: The heating time is usually from 10 minutes to 20 hours, preferably from 30 minutes to 1 hour. <Encapsulant for optical element fixing material> The curable composition of the present invention can be favorably used as light Element 28 201237103 Sealing the entire encapsulating agent. The curable composition of the present invention is used as a sealing agent for an optical element fixing material, and for example, the composition is molded into a desired shape to obtain an inner optical element. After the molded body, the method of producing the optical element package by heating and hardening it is used. The method of forming the curable composition of the present invention into a desired shape is not particularly limited, and a general transfer can be employed. Conventional casting method such as material formation or injection molding method. ^The heating temperature during heat curing is usually 100 to 200 ° C depending on the curable composition used, etc. The heating time is usually 1 minute to 2 inches. The hour is '30 minutes to 10 hours. The obtained optical element package uses the curable composition of the present invention, so that the peak of the light emitted by the white and blue light-emitting LEDs is used even in the optical element. The short-wavelength of 400 to 490 nm is not excellent in transparency and heat resistance due to heat or light. [Examples] Next, the present invention will be described in more detail by way of examples and comparative examples. The invention is not limited to the following examples. (Measurement of weight average molecular weight) The weight average molecular weight (Mw) of the random copolymer of decane compound obtained in the production example is determined by the following apparatus and conditions in terms of standard polystyrene conversion value. Device name: HLC-8220GPC, TOSO company system

Column: TSKgelGMHXL—TSKgelGMHXL~TSKgel 200 0HXL 29 201237103 Solvent: tetrahydrofuran

Measurement temperature: 4 (TC flow rate: 1 m 1 /minator: differential refractometer (measurement of IR spectrum) The IR spectrum of the random copolymer of decane compound obtained in the production example was measured using the following apparatus. Fourier transform infrared spectrometer (Spectrum 100, manufactured by Perkin Elmer Co., Ltd.) (Production Example 1) Into a 300 ml water-drop flask, a nonyloxydecane (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in an amount of 20. 2 g (102 mmol), 2 5g(1) 1 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 5mmo 1) As a catalyst, stirring was continued for 16 hours at room temperature. After the reaction was completed, it was concentrated to 5 〇m with a reduced pressure concentrator, and then added with ethyl acetate acetonitrile 10 0 m 1 and neutralized with a saturated aqueous solution of sodium hydrogencarbonate. After standing for a while, the organic layer was separated. Then, the organic layer was washed twice with distilled water and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the filtrate was concentrated to 50 m 1 using a vacuum condenser. This is dripped into a large number of homes in the courtyard. The precipitate was separated by decantation. The obtained precipitate was dissolved in methyl ethyl ketone (MEK), and the solvent was depressurized under reduced pressure. The vacuum was dried to obtain a random copolymer of Shi Xiyuan compound (A1) 1 3 5 g. The weight average molecular weight (Mw) of the smoldering compound random copolymer (A1) is 30 201237103 1,900. Further, the IR spectrum data of the decane compound random copolymer (A1) is expressed as follows.

The amount of phenyl tridecyloxy decane is 16. 7g. The amount of phenyl trimethoxy decane used is 16.7g. 9克。 The decane compound random copolymer (A2) 12. 9g was obtained in the same manner as in Production Example 1. The weight average molecular weight (||^) of the random copolymer (A2) of the broth compound is 2,000 Å. Further, the IR spectrum data of the compound random copolymer (A2) is expressed as follows.

Si-Ph: 698cm·' 5 740cm'1 » Si-0 : 1132cm'1 &gt; -CN : 2255cm·1 (Production Example 3) Into a 300ml water drop type flask, put in a stupid trimethoxy stone court (east) 11g (60mmol), 3-glycidyl ether propyl trimethoxy sulphate (made by Tokyo Chemical Industry Co., Ltd.) 14·2g (6〇mm〇l), as dissolved toluene 60ml, steamed After 30 ml of water, 0.15 g (1 - 5 mmol) of phosphoric acid (manufactured by Kanto Chemical Co., Ltd.) was added as a catalyst, and the mixture was continuously allowed to fall for 16 hours at room temperature. After the end of the reaction, the reaction mixture was added with ethyl acetate 1 〇 〇 m 1 31 201237103 and neutralized with a saturated aqueous solution of sodium hydrogencarbonate. After standing for a while, the organic layer was taken. Next, the organic layer was washed twice with distilled water and then dried with anhydrous sulfuric acid. After filtering the magnesium sulfate, the filtrate was concentrated to 50 m i with a reduced pressure concentrator, and the mixture was dropped into a large amount of Zhenghexi to precipitate it, and the sediment was separated by decantation. The decane compound random copolymer (A3) 16.3 g was obtained by a solution of the decane compound random copolymer (A3). The weight average molecular weight (Mw) of the random copolymer of the Shi Xiyuan compound (A3) was 2,800. Further, the IR spectrum data of the random compound of the broken compound (A3) is shown below.

Si-Ph: 699 cm-1 'WlcnT1, Si-0: 1132CHT1, epoxy group: 1 254 cm'1 (Example 1) The random copolymer of decane compound (A1) obtained in Production Example 1 was 1 Og, and 2-(2) was added. 3'4-Epoxycyclohexyl)ethyltrimethoxydecane (manufactured by Tokyo Chemical Industry Co., Ltd.) 1. Og as a decane coupling agent (B), which is sufficiently mixed and defoamed to obtain a curable composition ( 1). (Example 2) In the same manner as in Example 1, except that the amount of the 2-(3,4-epoxycyclohexyl)ethyltrimethoxyxanthene was changed to 1.5 g, the hardening was carried out in the same manner as in Example 1. Sex composition (2). (Example 3) The hardening property was obtained in the same manner as in Example 1 except that the decane compound random copolymer (A1) was used in Example 1, except that the decane compound random copolymer (A2) obtained in Production Example 2 was used. Composition (3). (Example 4) In Example 1 'as a metal complex (C), zirconium tetraacetate pyruvate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added (in the following Table 1, it is described as "C1"). In the same manner as in Example 1, except for 0· Olg, a curable composition (4) was obtained. (Example 5) A curable composition (5) was obtained in the same manner as in Example 4 except that the amount of zirconium tetraacetate pyruvate was changed to 〇.〇5g. (Example 6) A curable composition (6) was obtained in the same manner as in Example 4 except that the amount of the tetraethylpyruvate hammer was changed to 〇. lg. (Example 7) A curable composition (7) was obtained in the same manner as in Example 4 except that the amount of ruthenium tetraacetate pyruvate was changed to 1.0 g. (Example 8) In the first embodiment, aluminum triacetate pyruvate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as the metal complex (C) (in the following Table 1, it is described as "C2"). The curable composition (8) was obtained in the same manner as in Example 1 except that 0 5 g. (Example 9) In Example 1 'as a metal complex (C), further, dioctyloxybisbis(octyl glycolate) (Matsumoto Fine Chemical Co., Ltd. 33 201237103 'Orgatics TC-200) was added ( In the following Table 1, it is described as "C3".) 〇. Other than 05g, the curable composition (9) was obtained in the same manner as in Example 。. (Example 10) In Example 10, as a alicyclic acid anhydride (D) having a carboxyl group, a cycloheximide 1,2,4-trisoleic acid-1,2-anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was further added. The curable composition (10) was obtained in the same manner as in Example 1 except for 0 5 g. (Example 11) The curing property was obtained in the same manner as in Example 1 except that the amount of the cyclohexane 1,2,4-tricarboxylic acid-1,2-anhydride was changed to 1.0 g. Composition (11). (Comparative Example 1) The curability was obtained in the same manner as in Example 1 except that the amount of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane was changed to 0.1 g. Composition (12). (Comparative Example 2) The curability was obtained in the same manner as in Example 1 except that the amount of 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane was changed to 3. 0 g. Composition (13). (Comparative Example 3) A curable composition was obtained in the same manner as in Example 6 except that the random copolymer (A1) of the decane compound was used in the same manner as in Example 6 except that the random copolymer (A3) of the decane compound obtained in Production Example 3 was used. (14). 34 201237103 (Comparative Example 4) The curable composition was obtained in the same manner as in Example 10 except that the random copolymer (A3) of the substituted decane compound (A1) was used in the same manner as in Example 10 except that the decane compound random copolymer (A3) obtained in Production Example 3 was used. (1 5). 35 201237103 CQ AJ •. tt(4) Q Na 1 &lt; CO ii oo CT3 C75 CJ3 CD C^&gt; CD ii CO CNJ O- Bu CH) CD SSS sss CH) OD alicyclic anhydride (8) (mass ratio) 1 1 1 1 1 1 1 1 t 1 1 LO CD CD CD 1 1 1 LO cr&gt; o Metal complex (C) (mass ratio) CO 1 1 1 1 1 1 1 1 LO 〇) o' 1 1 1 1 i 1 〇〇1 1 1 1 1 1 1 LO o czi 1 1 1 1 1 1 1 1 4 1 1 1 o CD LO 〇CD 1 &lt; o Q 1 1 1 1 1 1 LO o 1 decane coupling agent (B) ( Quality Department) Ο LO 〇) τ—Η O r—H C5 CZ5 1 〇” ·Η oo OH oi—H 1 &lt; CZ? CD CO cr> 〇矽 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物 化合物Cr&gt; o 〇&gt;〇&gt; Ο cr&gt; CZD ooooo cr&gt; TTMH composition ratio (mole °/0) decane compound (3) 1 1 1 1 1 1 1 1 1 1 1 1 1 ss CNI a3 LO Oo LO oo LO oo LO oo LO oo LO OO LO oo LO OO LO OO LO oo LO oo LO OO ss decane compound (1) LO ii LO LO LO LO LO LO LO LO LO LO Type Γ-- t &quot; t τ—H i 1 iiiir 1 1 1&quot;· &lt; r-_H i−l τ—H CO CO hardening constituent substance Ρ···( &lt;N1 C O inch LO CO OO o τ - HF ) OO CO 呀 ii in - &lt; Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Implementation Example 11 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 9ε 201237103 The cured product of the curable composition of Example 11 and Comparative Examples 1 to 4 was measured for the adhesion, initial transmittance, and heating as follows. After the penetration rate, the heat resistance, the initial transparency, and the heat resistance (transparency after heating) were evaluated. The measurement results and evaluation are shown in Table 2 below. (Continuous force test) The curable composition 1 to 15 was applied to the mirror surface of the 2 mm square stone wafer to have a thickness of about 2 cm, and the coated surface was placed on the object (silver-plated copper plate). Thereafter, it was heat-treated at 180 °C for 2 hours to be hardened, and a subject with a test piece was obtained. The object to which the test piece is attached is placed on a test stand preheated to a predetermined temperature (23 ° C, 1 〇 (TC), tester (Series 4000, manufactured by DAGE), 3 sec. The body is placed at a height of 50&quot; m, and the horizontal surface (shear direction) is applied to the joint surface at a speed of 200 &quot; ni/s, and the measurement is at 23t, 1〇〇. The test piece and the object are followed by the object. force). (Subsequent to heat resistance) is the 100 C adhesion test. When the force is 8〇N/2_□ or more, it is 'flattened as 〇,' and 6〇N/2mm□ or more is less than 8〇N/2mm□. "x" when less than 60N/2mm□. (Measurement of initial penetration rate) The curable composition 15 was poured into a mold having a length of 25 mm, a width of 2 Å, and a thickness of 1 mm, and was heated at 14 Torr for 6 hours to be hardened, and a test piece was prepared. The obtained test piece was measured for the initial transmittance (%) at a wavelength of 4 Torr and 45 Å (10) by a spectrophotometer (MPC-3100, manufactured by Shima Seisakusho Co., Ltd.). 201237103 (Initial transparency) In the initial transmittance measurement, the transmittance at 400 nm is 80% or more, and it is evaluated as "〇", 70% or more is less than 8〇%, then "△", and less than 7〇% is "χ". . (Measurement of penetration rate after heating) Each test piece for measuring the initial transmittance was placed in an oven of 5 〇〇c for 5 hrs, and the transmittance (%) at a wavelength of 400 nm and 45 〇 nm was measured. This is taken as the penetration rate after heating. [Heat resistance (transparency after heating)] The transmittance after heating is measured. The transmittance at 4 〇〇 nm is estimated to be “〇” at 80% or more of the initial transmittance, and 7〇% or less is less than 8〇. % is "△", less than 70% is "X". Table 2

Curing composition adhesion force (N/2mm匚) initial penetration rate (%) initial transparency after heating (v/h) heat resistance (transparency after heating) 23〇C 10(TC followed by heat resistance 400nm 450 nm 400 nm 450 nm Example 1 1 122.1 93.7 〇90.1 90.7 〇84.7 88.4 〇Example 2 2 110.3 86.2 〇88.9 90.6 〇84.2 88.2 〇Example 3 3 115.4 95.1 〇89.3 91.4 〇85.1 88.5 〇Example 4 4 “149.2 110.6 〇 88.6 90.5 〇84.4 89.0 〇Example 5 5 168.5 128.9 〇88.2 90.2 〇84.0 88.3 〇Example 6 6 172.7 121.4 〇87.6 90.1 〇83.9 87.7 〇Example 7 7 137.0 69.5 Δ 87.8 90.4 〇80.5 85.8 〇Example 8 8 130.0 103.8 〇88.1 90.3 〇84.2 87.1 〇Example 9 9 155.6 117.3 〇88.5 90. 6 〇83.3 86.8 〇Example 10 10 157.2 110.0 〇87.7 89.9 〇83.5 85.9 〇Example 11 11 142.0 73.3 Δ 89.2 90.8 〇78.4 82.6 〇Compare Example 1 12 71.3 58.1 X 89.8 91.0 〇86.3 88.8 〇Comparative Example 2 13 60.9 35.7 X 86.9 89.8 〇82.2 86.2 〇Comparative Example 3 14 148.6 105.8 〇88.3 90.4 〇14.4 50.7 X Comparative Example 4 15 163.5 110.2 〇87.2 90.8 〇10.4 46.1 X As is clear from the second table, 'the cured product of the curable composition 1 to u of Examples 1 to 11' is at 23 ° C and 10 (both of TC, both) 6〇N/2mm□ or more, 38 201237103 The adhesion and subsequent heat resistance are excellent. In addition, the initial transmittance at a wavelength of 4〇〇nm and 45〇nm and the transmittance after heating are high. 'Initial transparency and heat resistance. (The transparency after heating is also excellent.) On the other hand, the cured products of the curable compositions 12 and 13 of Comparative Examples 1 and 2 have poor adhesion, and the curable compositions i 4 and 15 of Comparative Examples 3 and 4. The hardened material, heating, will greatly reduce the penetration rate. [Simple description of the schema] Benefits [Description of main component symbols]

Claims (1)

201237103 VII. Patent application scope: 1. A curable composition, which is a random copolymer of (A) decane compound, which is in a molecule and is represented by the following formulas (i), (ii) and (iii) A recurring unit having (i) and (ii), (i) and (iii), (ii) and (iii), or (i), (ii) and (iii), having a weight average molecular weight of 1, 〇 〇〇~30, 〇〇〇; and (B) a decane coupling agent having a reactive cyclic ether structure with a mass ratio of (a) to (B) to (A): (B) = 95: 5 to 80 : The ratio of 20 is included: Wherein R 1 represents a hydrogen atom or an alkyl group having a carbon number of 6; D is a single bond or a divalent organic group having 1 to 20 carbon atoms which may have a substituent; and R 2 represents an alkyl group having 1 to 20 carbon atoms. Or a phenyl group which may have a substituent. 2. The curable composition according to claim 1, wherein the random copolymer of the above-mentioned (A) decane compound is in the presence of a group represented by the formula Ri-CH(CN)_D_ ([f-CHCCiO -D-]), the amount of R2 present ([R2])' is a random copolymer of decane compound with a molar ratio of [Ri_CH(CN)_D_]: [R2] = 5:95~5〇:5〇. 40 201237103 4 3. A curable composition comprising a (A') decane compound random copolymer of the formula (i): ri_ch(cn)__d - SiCOlOpU1)3. a mixture of at least one of the decane compounds shown; and a mixture of the decane compounds of the formula (2): at least one of the decane compounds (2) represented by R2Si(0R4)q(X2)3-q, the weight average molecular weight Between 1,000 and 30, 000; and (B) a decane coupling agent having a reactive cyclic ether structure, with (A') and (B) to mass ratio, (A,): (B) = 95:5 The ratio of ~80:20 includes: wherein R represents a hydrogen atom or a carbon number of 1 to 6, and is a single bond or a divalent organic group having 1 to 20 carbon atoms which may have a substituent; R3 The system represents a carbon number of the alkyl group, wherein X1 represents a halogen atom, and ρ represents an integer of 〇~3; wherein R2 represents an alkyl group having 1 to 20 carbon atoms or a stupid group which may have a substituent, and the R series is The alkyl group having no carbon number of 1 to 6, the oxime 2 is a halogen atom, and the q is an integer of 0 to 3. 4. The curable composition according to claim 3, wherein the random copolymer of the above (A) decane compound is a decane compound (丨) and a decane compound (2) in a molar ratio of [decane compound] (1)]: [decane compound (2)] 5 . 9 5 to 5 0 : 5 0 ratio of the obtained sulphur compound compound random copolymer. 5. The sclerosing agent according to any one of claims 1 to 4, wherein the decane coupling agent has a cyclohexene oxide group D. The hardenable composition according to any one of items 1 to 5, wherein the step (b) contains (6) a metal atom as a metal, a metal, or a titanium metal 41 201237103 complex compound (C) component content (a) component Or (a,) component loo mass part 'includes more than 〇 mass part, and 1 〇 mass part or less. The curable composition as described in any one of claims 1 to 5 which further contains (D) an alicyclic acid anhydride having a carboxyl group, and the content of the component (D) is (A) component or (A) ,) The component 1 〇〇 mass part includes 〇 mass part or more '10 mass parts or less. 8. The curable composition as described in any one of claims 1 to 7 which is a composition for an optical element fixing material. A hardened composition according to any one of the first to seventh aspects of the present invention. 1A. The cured product according to claim 9, which is a fixing member for an optical element. 11. A method of using the curable composition according to any one of claims 1 to 7 for use as an adhesive for an optical element fixing material 12. The method of applying the patent range 1 to The curable composition according to any one of the items 7 is used as an encapsulant for an optical element fixing material. 42 201237103 IV. Designated representative drawings: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. In this case, when there is a chemical formula, please reveal the chemical formula that best describes the characteristics. R1 VI. Description of the Invention: [Technical Field to Which the Invention Is Applicable] The present invention relates to a hardenable composition which is excellent in transparency and heat resistance and which has a hardened material; it is obtained by hardening the composition, and using the same The composition is used as an adhesive for an optical element fixing material or a secondary encapsulating agent for a fixing material. Prior Art] So far, the hardening composition has been modified according to the use. 2 201237103 No. 10 Replacement page, the date of the month, the above (B) decane coupling agent has cyclohexene 1. Oxygen-. - the public, the smoulder mixture. [6] The curable composition according to any one of [1] to [5] further comprising (C) a metal complex of a metal atom of aluminum, ruthenium or titanium, and a content of (c) component (A) component or (A,) component 100 mass parts, including a mass part or more, and 10 mass parts or less. [7] The curable composition according to any one of [1], wherein the hydrazine further contains (D) a content of the alicyclic anhydride having a carboxyl group as the component (A) or ( A') Component 1〇〇 The mass portion includes the mass portion or more and the mass portion or less. [8] The curable composition according to any one of [1] to [7], which is a composition for a fixing member for a light element. According to the second aspect of the present invention, the cured product of the following [9] and [1] can be provided. [9] A cured product which is a hardenable composition according to any one of [7] to [7]. [10] The cured product according to [9], which is a light element fixing material. According to the third aspect of the present invention, there is provided a method of using the curable composition of the present invention as described in [u] and [12] below. [11] A method of using the curable composition according to any one of [A] to [7] as an adhesive for an optical element fixing material. [12] The curable composition according to any one of [1] to [7], which is used as an encapsulant for an optical element fixing material. [Effect of the Invention] According to the curable composition of the present invention, even when irradiated with high-energy light 7 201237103 or a high-temperature state, it is possible to reduce the transparency without coloring, and it is excellent in transparency for a long period of time. And has a hardened object of the ancient + $ very back. The curable composition of the present invention can be used for forming an optical element fixing material. In particular, τ is favorably used as an encapsulant for an optical element and an encapsulant for an optical element fixing material. [Embodiment] Hereinafter, the present invention will be described in detail with reference to 1) a curable composition, 2) a cured product, and 3) a method of using a curable composition. 1) Curable composition The curable composition of the present invention is characterized in that (A) a random compound of a broken compound is attached to a molecule, as shown by the following formulas (i), (ii) and (iii) Among the recurring units, the recurring units of (i) and (ii), (i) and (iii), (ii) and (iii), or (i), (ii) and (iii) have a weight average molecular weight of 1,0 00~30, 〇〇〇; and (B) a decane coupling agent having a reactive cyclic ether structure, with (^) and (^) and mass ratio, (^): ") = 95:5~ The ratio of 80:2 包含 is included: 201237103 No. 10, April 24, 101, revised replacement page - raw material, adhesive, and coating agent which can be suitably used for optical parts or molded bodies. - Curable composition of the present invention The cured product has a high bonding force, and can be confirmed, for example, by measuring the adhesion force as follows, that is, applying a curable composition to the mirror surface of the tantalum wafer, and placing the coated surface on the object. Crimping, heat treatment to harden it. Place this on a test bench preheated to a predetermined temperature f (for example, 2 generations, 10 (rc) and then the tester for 3 seconds, 〇 Stress is applied to the joint surface at a position of 胄50 ^ in the horizontal direction (shear direction), and the adhesion between the test piece and the object is measured. The adhesion of the hardened material is 23t and l〇 (TC, It is preferably 6 〇 n / 2 mD or more, preferably 80 N / 2 mm □ or more. The cured product is excellent in transparency and can be confirmed by measuring the light transmittance. The light transmittance of the cured product is at a wavelength of 4 〇〇. The light of nm is preferably 8 〇 or more, particularly preferably 86% or more, and the light having a wavelength of 45 〇 nm is preferably 87% or more. ϋ The cured product has excellent heat resistance and can be hardened by even After the object is placed at a high temperature, the change in the force and transparency is small. Confirm the force. After the pressure is placed on the loot: after 30 seconds, the adhesion is maintained at 5% or more of the adhesion force of 23 t, and the adhesion is preferably maintained at 65% or more. The force is better. The transparency is 15 〇. After 500 hours of standing, the transmittance at a wavelength of 4 〇〇 nm is preferably 80% or more of the initial transmittance. 3) The method of using the curable composition According to a third aspect of the invention, the curable composition of the present invention is used as a fixing member for an optical element. Next, the method of the encapsulant for an optical element fixing material is 201237103. The following: a light-emitting element such as an LED or an LD, a light-receiving element, a composite optical element, an optical unit circuit, etc. The curable composition of the present invention can be suitably used as an adhesive for an optical element fixing material. The curable composition of the present invention is used as a method for using an adhesive for an optical element fixing material, and The coating of the material (the optical element and its circuit board, etc.) or the surface of the two sides is applied to the composition, and after the crimping, heating is performed to harden it, and then the materials of the object are firmly adhered to each other. The main substrate material of the optical element may be glass such as soda glass or heat-resistant hard glass; ceramics; iron, copper, aluminum, gold, silver, platinum, chromium, titanium, and metal alloys thereof, stainless steel (SUS3) Metals such as 〇2, SUS3〇4, SUS3 04L, SUS309, etc.; polyethylene terephthalate, polybutylene terephthalate, butylene naphthalate, ethylene - vinyl acetate copolymer, polystyrene, polycarbonate, polydecylpentene, polysulfone 1 ketone, polyether mill, polyphenylene sulfide, polyether phthalimide, polyimine, poly A synthetic resin such as a brewing amine, an acrylic resin, a norbornene resin, a cycloolefin resin, or a glass epoxy resin. The heating temperature at the time of heat curing is usually from 100 to 200 depending on the hardenable composition to be used. (: The heating time is usually 10 minutes to 20 hours, preferably 30 minutes to 10 hours. <Packaging agent for optical element fixing material> The curable composition of the present invention can be favorably used as the optical element 28 201237103 10 No. 4, the correction of the replacement page, the cured products of the curable compositions 丨 to j 5 obtained in Examples 1 to 11 and Comparative Examples 1 to 4 were measured as follows, and the adhesion, initial transmittance, and penetration after heating were measured as follows. Rate, evaluation followed by heat resistance, initial transparency, and heat resistance (transparency after heating). The measurement results and evaluations are shown in Table 2 below. (Continuous force test) Coating on the mirror surface of a 2 mm square tantalum wafer The curable composition 1 to 15 is formed to have a thickness of about 2/m, and the coated surface is placed on the substrate (silver-plated copper plate) and pressure-bonded thereto. Thereafter, it is 180. (: heat treatment for 2 hours to harden it) The object with the test piece is obtained, and the subject with the test piece is placed in a preheated temperature (2 3 C, 1 〇〇) and then tested 5| (Series 4000, MGE) 3 sec on the test bench, by the position of 被50 // m The stress was applied to the joint surface at a speed of 200 m/s in the horizontal direction (shear direction), and the measurement was at 23 t, 1 〇 (the test piece of rc and the adhesion force of the object (N/2_〇). Heat resistance) 在于 In the adhesion test of 100c, the evaluation is "〇" when the force is 8 ON/2mm□ or more, and "△" when 60N/2mm□ or more is less than 8〇N/2_□, less than 60N/ In the case of 2 mm □, it is "X". (Measurement of initial penetration rate) The curable compositions 1 to 15 were poured into a mold having a length of 25 mm, a width of 20 mm, and a thickness of 1 mm, and were cured by heating for 14 hours for 14 hours. The test piece was prepared, and the obtained test piece was measured for the initial transmittance (%) at a wavelength of 4 〇〇 nm and 45 〇 nm by a spectrophotometer (MPC-3100, manufactured by Shimadzu Corporation). 37 201237103 (Initial transparency) In the initial transmittance measurement, the transmittance at 400 nm is estimated to be 〇 〇 〇 , , , , , , , , , , , , , , , , , , 〇 〇 〇 〇 70 〇 〇 70 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Measurement of the penetration rate) Each test piece for measuring the initial penetration rate was placed in an oven of 15 〇t 5 〇〇, and again, the wavelength was measured 4 〇nm, the transmittance (%). This is taken as the transmittance after heating. [Heat resistance (transparency after heating)] Measured by the transmittance after heating, the transmittance at 400 nm is 80% of the initial transmittance. % or more is evaluated as "〇", 7〇% or more is less than 8〇%, then "△", and less than 70% is "x_j. See 2 Table ------ -- Sturdy composition 0 Next force /2πιιη[ ) Initial transmittance (%) Initial transparency, transmittance after heating (%) Heat resistance (transparency after heating) 23 °C loot: Next heat resistance 400 nm 450 nm 400 nm 450 nm Example 1 1 122.1 93. 7 〇90.1 90.7 〇84.7 88.4 〇^example 2 2 110.3 86.2 〇88.9 90.6 〇84.2 88.2 〇例3 3 115.4 95.1 〇89.3 91.4 〇85.1 88.5 〇_夏施例4 4 149.2 110.6 〇88.6 90. 5 〇84.4 89.0 〇_ ^&amp;Example 5 5 168.5 128.9 〇88.2 90. 2 〇84.0 88.3 〇Example 6 6 172.7 121.4 〇87.6 90.1 〇83.9 87.7 〇Example 7 7 1 137.0 69.5 Δ 87.8 90.4 〇80.5 85.8 〇_ _^ Example 8 8 130.0 103.8 〇88.1 90.3 〇84.2 87.1 〇Example 9 9 155.6 117.3 〇88.5 90.6 〇83.3 86.8 _^Example 10 10 157.2 110.0 〇87.7 89. 9 〇83.5 85.9 〇11 11 142.0 73.3 Δ 89.2 90.8 〇78.4 82.6 〇例1 12 71.3 58. 1 X 89.8 91. 0 〇86.3 88.8 〇__^Example 2 13 60.9 35.7 X 86.9 89.8 〇82.2 86.2 〇__^ Comparative Example 3 14 148.6 105.8 〇88.3 90.4 〇14.4 50.7 ------ X Example 4 15 163.5 110.2 〇87.2 90.8 〇10.4 46.1 X From Table 2, Example The cured product of the hardening compositions 1 to 11 of 1 to 11 is 6 〇N/2_□ or more at both 23 ° C and 10 ° C.