TWI518137B - A hardened composition, a hardened product, and a hardened composition - Google Patents

Description

Method for using curable composition, cured product, and curable composition

The present invention relates to a curable composition of a cured product which is excellent in transparency and heat resistance 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 fixing a package or an optical component.

In the past, the curable composition has been variously modified according to the use, and is widely used in the industry as a raw material, an adhesive, a coating agent, and the like as an optical component or a prototype. For example, a curable composition of a cured product having excellent transparency is formed as a raw material or a coating agent for an optical component, and a curable composition having a cured product having a high adhesion is formed, and can be suitably used as an adhesive or Coating agent.

In addition, in the case of manufacturing an optical element package, the curable composition is used as a composition for an optical element fixing material such as an adhesive for an optical element fixing material or an encapsulant for an optical element fixing material.

The optical element includes a light-emitting element such as a semiconductor laser (LED) or a light-emitting diode such as a light-emitting diode (LED), a light-receiving element, a composite optical element, and an optical unit circuit. In recent years, optical elements of blue light or white light having shorter wavelengths of light-emitting peaks have been developed and widely used. With the advancement of the high luminance of the light-emitting element having such a short wavelength of the light-emitting peak, the heat generation amount of the optical element tends to become larger.

However, in recent years, with the increase in the brightness of the optical element, the cured product of the composition for the optical element fixing material is exposed to higher-energy light or high-temperature heat generated by the optical element for a long period of time, thereby causing cracking, Peeling and other issues.

In order to solve this problem, in the patent documents 1 to 3, a composition for an optical element fixing material containing a polysilsesquioxane compound as a main component is proposed.

However, even if it is a cured product of a composition for an optical element fixing material containing a polysilsesquioxane compound as a main component described in Patent Documents 1 to 3, it is difficult to maintain a sufficient adhesive force to obtain heat resistance and transparency. Sexual situation.

Further, as a composition for optical element packaging, Patent Document 4 proposes an epoxy resin composition using an alicyclic epoxy resin, and Patent Document 5 proposes an epoxy resin composition containing a polythiol compound. Things.

However, even in the case of using these compositions, sufficient light deterioration resistance cannot be satisfied with the change over time, or there is a case where the adhesion is lowered.

Therefore, it has been desired to develop a curable composition of a cured product which is excellent in heat resistance, transparency, and high adhesion.

[Advanced technical literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-359933

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-263869

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2006-328231

[Patent Document 4] Japanese Patent Laid-Open No. Hei 7-309927

[Patent Document 5] Japanese Special Closed 2009-001752

The present invention has been made in view of the circumstances of the prior art, and a problem is to provide a hardenable composition of a cured product which is excellent in heat resistance and transparency and has a high adhesion, and hardens the composition. A cured product and a method of using the composition as an adhesive for an optical element fixing material or a packaging material for fixing an optical element.

As a result of intensive research to solve the above problems, the present inventors have found that (A) has a specific decane compound copolymer, (B) an epoxy resin, and (C) an alicyclic acid anhydride having a carboxyl group and other alicyclic anhydrides. The cured product of the composition can be a cured product which can maintain excellent transparency and heat resistance for a long period of time and can have a high adhesion even at a high temperature, and the present invention has been completed.

Therefore, according to the first aspect of the present invention, the curable composition of the following [1] to [8] can be provided.

[1] A curable composition comprising: (A) (i) and (ii), (i) among the repeating units represented by the following formulas (i), (ii) and (iii) in the molecule; And (iii), (ii) and (iii) or (i), (ii) and (iii) repeating units, a decane compound copolymer having a weight average molecular weight of 1,000 to 30,000; (B) an epoxy compound; (C) A sulphuric acid anhydride having a carboxyl group and a hardener containing other alicyclic anhydrides, and the mass ratio of (A) to [(B) + (C)] is (A): [(B) + (C )]==200:20~100:60 ratio: In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X ⁰ represents a halogen atom, a cyano group or a group represented by the formula: OG (wherein G represents a protecting group of a hydroxyl group), D represents a single bond or a linking group, 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 [1], wherein the decane compound copolymer of the above (A) is in the form of a group represented by the formula: R ¹ -CH(X ⁰ )-D- ([R ^{1 -CH (X 0) -D]} ) with R ² present in an amount of ([R ^2]) the molar ^{ratio, [R 1 -CH (X 0} ) -D]: [R 2] = 55: 45 ~25:75 decane compound copolymer.

[3] A hardenable composition comprising: (A') such that: (1): R ¹ -CH(X ⁰ )-D-Si(OR ³ ) _p (X ¹ ) _3-p R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X ⁰ represents a halogen atom, a cyano group or a group represented by the formula: OG (wherein G represents a protecting group of a hydroxyl group), and D represents At least one of a decane compound (1) represented by a single bond or a linking group, R ³ is an alkyl group having 1 to 6 carbon atoms, and X ¹ is a halogen atom, and p is an integer of 0 to 3, and 2): R ² Si(OR ⁴ ) _q (X ² ) _3-q [wherein R ² represents an alkyl group having 1 to 20 carbon atoms or a phenyl group which may have a substituent, and R ⁴ represents a carbon number of 1 of ~ 6 alkyl group, X ² represents a halogen atom based, q represents an integer of Department] 0 ~ 3 of the illustrated Silane compound (2) of a mixture of at least one of an alkoxy silicon compound condensation, weight average molecular weight of 1,000 to 30,000 a decane compound copolymer; (B) an epoxy compound; and (C) a sulphuric acid anhydride having a carboxyl group and a hardener containing other alicyclic anhydrides, the quality of (A') and [(B) + (C)] The ratio is (A'): [(B) + (C)] = 100: 20 ~ 100: 60 ratio. [4] The curable composition according to [3], wherein the (A') decane compound copolymer is a molar ratio of a decane compound (1) to a decane compound (2) [decane compound (1) ]: [decane compound (2)] = 55:45 to 25:75 ratio of the obtained decane compound copolymer.

[5] The curable composition according to [1] or [3] wherein the mass ratio of the hardener of the above (C) is (fatty acid anhydride having a carboxyl group): (other fatty acid anhydride) = 50: 50~ 10:90.

[6] The curable composition according to [1] or [3], further comprising an antioxidant.

[7] The curable composition according to [6], wherein the antioxidant is a phosphorus-based antioxidant.

[8] The curable composition according to [1] or [3], which is a composition for a light element fixing material.

According to the second aspect of the present invention, the cured products of the following [9] and [10] can be provided.

[9] A cured product obtained by curing the curable composition according to [1] or [3].

[10] The cured product according to [9], which is a light element fixing material.

According to the third aspect of the present invention, the following use cases of [11] and [12] can be provided. A method of inventing a curable composition.

[11] A method according to [1] or [3], wherein the curable composition is used as an adhesive for an optical element fixing material.

[12] A method according to [1] or [3], wherein the curable composition is used as an encapsulant for an optical element fixing material.

According to the curable composition of the present invention, even when it is irradiated with high-energy light or a high-temperature state, it does not color and lowers transparency, and can have excellent transparency for a long period of time, and high temperature can also have high adhesion. Hardened material.

When the curable composition of the present invention is used for forming an optical element fixing material, it can be suitably used as an adhesive for fixing an optical element and an encapsulant for an optical element fixing material.

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) Sturdy composition

The curable composition of the present invention is characterized in that (A) has (i) and (ii) among the repeating units represented by the following formulas (i), (ii) and (iii) in the molecule; i) and (iii), (ii) and (iii) or (i), (ii) and (iii) repeating units, a decane compound copolymer having a weight average molecular weight of 1,000 to 30,000; (B) an epoxy compound; And (C) an alicyclic acid anhydride having a carboxyl group and a hardener containing another alicyclic acid anhydride, which are contained in a ratio (mass ratio) of (A): [(B) + (C)] = 100: 20 to 100: 60. :

(A) decane compound copolymer

The curable composition of the present invention contains, as component (A), (i) and (ii), (i) among the repeating units represented by the above formulas (i), (ii) and (iii). And a repeating unit of (iii), (ii) and (iii) or (i), (ii) and (iii), a decane compound copolymer having a weight average molecular weight of 1,000 to 30,000 (hereinafter, referred to as "decane compound copolymerization" (A)").

The decane compound copolymer (A) may have one of the repeating units represented by (i), (ii), and (iii), or two or more kinds thereof.

In the formulae (i) to (iii), R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and preferably a hydrogen atom.

The alkyl group having 1 to 6 carbon atoms represented by R ¹ may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, t-butyl or n-pentane. Base, n-hexyl, etc.

X ⁰ represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodide; and a cyano group or a group represented by the formula: OG.

G is a protecting group of a hydroxyl group. The protecting group for the hydroxyl group is not particularly limited, and a conventional protecting group known as a protecting group for a hydroxyl group can be mentioned. For example, an anthracene-based protecting group; a decyl-based protecting group such as a trimethylsulfanyl group, a triethylsulfanyl group, a tert-butyldimethylmethylalkyl group or a tert-butyldiphenylsulfanyl group; An acetal protecting group of an oxymethyl group, a methoxy group, an oxymethyl group, a 1-oxyethyl group, a tetrahydropyran-2-yl group, a tetrahydrofuran-2-yl group; a third butoxy carboxyl group; And other alkoxycarboxyl protecting groups; methyl, ethyl, tert-butyl, octyl, allyl, triphenylmethyl, benzyl, p-methoxybenzyl, decyl, trityl An ether-based protecting group such as a diphenylmethyl group. Among these, G is preferably an anthracene-based protecting group.

The oxime-based protecting group, specifically, is represented by the formula: -C(=O)R ⁵ . In the formula, R ⁵ represents a carbon number of 1 to 6 such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl or n-pentyl. An alkyl group; or a phenyl group which may have a substituent.

The substituent of the phenyl group which may have a substituent represented by R ⁵ may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group or a t-butyl group. An alkyl group such as n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group or isooctyl group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; or an alkoxy group such as a methoxy group or an ethoxy group.

Among these, X ⁰ is easy to start, and a cured product having a high adhesion is obtained, and is selected from a group represented by a formula: OG' from a chlorine atom (wherein, G' represents a protection of an anthracene group). The group of the cyano group and the cyano group are preferably selected from the group consisting of a chlorine atom, an ethoxy group and a cyano group, and particularly preferably an ethoxy group.

D represents a single bond or a linker.

The linking group may be a divalent organic group which may have a substituent. The carbon number of the organic group is preferably from 1 to 20, more preferably from 1 to 10.

The divalent organic group which may have a substituent, and, for example, an alkylene group which may have a substituent, an alkenylene group which may have a substituent, an alkynylene group which may have a substituent, an arylene group which may have a substituent, A divalent group or the like which may have a combination of an alkylene group, an alkenylene group or an alkynylene group and an arylene group which may have a substituent.

An alkylene group which may have a substituent alkylene group, and may have a carbon number of a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group or a hexamethylene group. ~20, preferably an alkylene group having 1 to 10 carbon atoms.

The alkenylene group which may have a substituent alkenylene group may, for example, be an alkenylene group having 2 to 20 carbon atoms such as a vinylidene group, a propenylene group, a butenylene group or a pentenylene group, and have a carbon number of 2 to 10 Alkenylene is preferred.

The alkynylene group having an alkynylene group having a substituent may, for example, be an alkynylene group having 2 to 20 carbon atoms such as an ethynylene group or a propylene group, and preferably an alkynylene group having 2 to 10 carbon atoms.

The arylene group which may have an arylene group of a substituent may, for example, be an arylene group having 6 to 20 carbon atoms such as an o-phenylene group, a m-phenylene group, a p-phenylene group or a 2,6-naphthylene group. The arylene group having a carbon number of 6 to 10 is preferred.

Examples of the substituent of the above alkylene group, alkenylene group, and alkynylene group include a halogen atom such as a fluorine atom or a chlorine atom; an alkoxy group such as a methoxy group or an ethoxy group; a methylthio group or an ethylthio group; An alkylthio group; an alkoxycarboxy group such as a methoxycarboxy group or an ethoxycarboxy group; and the like.

Examples of the substituent of the above arylene group include a halogen atom such as a cyano group, a nitro group, a fluorine atom, a chlorine atom or a bromine atom; an alkyl group such as a methyl group or an ethyl group; and an alkoxy group such as a methoxy group or an ethoxy group. An alkylthio group such as a methyl group, a methylthio group or an ethylthio group.

The substituents may be bonded to any of the alkylene, alkenylene, alkynylene and arylene groups at any position, and may be the same or different plural bonds.

A divalent group which may be a combination of an (alkylene group, an alkenylene group or an alkynylene group) which may have a substituent and an arylene group which may have a substituent, and the above-mentioned (alkylene group, which may have a substituent) At least one of an alkenylene group or an alkynylene group is bonded to at least one of the above-mentioned arylene groups having a substituent. Specifically, a group represented by the following formula can be mentioned.

Among these, as D, it is preferred to obtain a cured product having a high adhesion, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, or a methylene group or Ethylene is particularly preferred.

In the formulae (ii) to (iii), R ² represents an alkyl group having 1 to 20 carbon atoms or a phenyl group which may have a substituent.

The alkyl group having 1 to 20 carbon atoms represented by R ² may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group, a t-butyl group or a n-butyl group. Base, n-hexyl, n-octyl, isooctyl, n-decyl, n-decyl, n-dodecyl and the like.

The substituent of the phenyl group which may have a substituent represented by R ² may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, an isobutyl group or a t-butyl group. An alkyl group such as n-pentyl, n-hexyl, n-heptyl, n-octyl or isooctyl; an alkoxy group such as a methoxy group or an ethoxy group; a halogen atom such as a fluorine atom or a chlorine atom; and the like.

In R ² represents the phenyl group may have a specific example of the substituent can be cited phenyl, 2-chlorophenyl, 4-methylphenyl, 3-ethylphenyl, 2,4-dimethylphenyl , 2-methoxyphenyl and the like.

In the decane compound copolymer (A), the amount of the group represented by the formula: R ¹ -CH(X ⁰ )-D- ([R ¹ -CH(X ⁰ )-D]) and the amount of R ² ( The molar ratio of [R ² ]), [R ¹ -CH(X ⁰ )-D]: [R ² ]=55:45 to 25:75 is preferred. Within this range, the cured product can be obtained with excellent transparency and adhesion, and excellent heat resistance can suppress the deterioration of these properties even after being placed at a high temperature.

The amount represented by the formula: R ¹ -CH(X ⁰ )-D- and the amount of R ² can be quantified, for example, by measuring the NMR spectrum of the decane compound copolymer (A).

The unit structure of the decane compound copolymer (A) is not particularly limited, and examples thereof include a random copolymer, a block copolymer, a graft copolymer, and an interactive copolymer. The random copolymer is particularly preferable.

The weight average molecular weight (Mw) of the decane compound copolymer (A) is in the range of 1,000 to 30,000, and is in the range of 1,500 to 6,000. By this range, a cured product excellent in workability of the composition and excellent in adhesion and heat resistance can be obtained. The weight average molecular weight (Mw) can be determined, for example, from a standard polystyrene equivalent value of gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

The molecular weight distribution (Mw/Mn) of the decane compound copolymer (A) is not particularly limited, but is usually in the range of 1.0 to 3.0 and preferably in the range of 1.1 to 2.0. By this range, a cured product excellent in adhesion and heat resistance can be obtained.

The decane compound copolymer (A) may be used alone or in combination of two or more.

The decane compound copolymer (A) is a ladder-structured poly-sesquioxide compound.

The polysesquioxanes have a ladder structure, and can be confirmed, for example, by infrared absorption spectrum measurement, X-ray diffraction measurement, or NMR measurement of the reaction product.

In the curable composition of the present invention, the decane compound copolymer (A) of the component (A) may further comprise:

Formula (1): R ¹ -CH(X ⁰ )-D-Si(OR ³ ) _p (X ¹ ) _3-p

At least one of the illustrated decane compounds (1), and

Formula (2): R ² Si(OR ⁴ ) _q (X ² ) _3-q

a mixture of a decane compound of at least one of the decane compounds (2) shown, a decane compound copolymer having a weight average molecular weight of 1,000 to 30,000 (hereinafter, referred to as a "decane compound copolymer (A')" The decane compound copolymer (A) is preferably a decane compound copolymer (A').

[decane compound (1)]

The decane compound (1) is a compound represented by the formula (1): R ¹ -CH(X ⁰ )-D-Si(OR ³ ) _p (X ¹ ) _3-p . By using the decane compound (1), a decane compound copolymer having good transparency and adhesion after curing can be obtained.

Formula (1), R ^1, specific examples of X ⁰ and D can move in Silane compound copolymer (A) the R & lt illustrated ^a, X ⁰ and D.

R ³ represents a carbon number of 1 to 6 such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a second butyl group, an isobutyl group, a t-butyl group, a n-pentyl group or a n-hexyl group. alkyl.

X ¹ represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The p system represents an integer from 0 to 3.

When P is 2 or more, OR ³ may be the same or different from each other. Further, when (3-p) is 2 or more, X ¹ may be the same or different from each other.

Specific examples of the decane compound (1) include chloromethyltrimethoxydecane, bromomethyltriethoxydecane, 2-chloroethyltripropoxydecane, and 2-bromoethyltributoxydecane. , 3-chloropropyltrimethoxydecane, 3-chloropropyltriethoxydecane, 3-chloropropyltripropoxydecane, 3-chloropropyltributoxydecane, 3-bromopropyltrimethyl Oxydecane, 3-bromopropyltriethoxydecane, 3-bromopropyltripropoxydecane, 3-bromopropyltributoxydecane, 3-fluoropropyltrimethoxydecane, 3-fluoro Propyltriethoxydecane, 3-fluoropropyltripropoxydecane, 3-fluoropropyltributoxydecane, 3-iodopropyltrimethoxydecane, 2-chloroethyltrimethoxydecane, 3-chloropropyltrimethoxydecane, 4-chlorobutyltrimethoxydecane, 5-chloropentyltrimethoxydecane, 2-chloropropyltrimethoxydecane, 3-chloro-3-ethylidenepropyl Trimethoxydecane, 3-chloro-3-methoxycarbonylpropyltrimethoxydecane, o-(2-chloroethyl)phenyltripropoxydecane, m-(2-chloroethyl)phenyltripropyl Oxydecane, p-(2-chloroethyl)phenyltripropoxydecane, p-(2-fluoroethyl)phenyltripropoxyfluorene Etc. X ⁰ trialkoxy silane-based compound of a halogen atom; chloromethyltrichlorosilane, Silane, dimethyl Silane bromo bromide, 2-chloroethyl-dichloro Silane methoxy, 2-bromoethyl two Chloroethoxy decane, 3-chloropropyltrichloromethane, 3-chloropropyltribromodecane, 3-chloropropyldichloromethoxydecane, 3-chloropropyldichloroethoxysilane, 3- Chloropropyl chlorodimethoxydecane, 3-chloropropyl chlorodiethoxy decane, 3-bromopropyldichloroethoxy decane, 3-bromopropyltribromodecane, 3-bromopropyltrichloride Decane, 3-bromopropylchlorodimethoxydecane, 3-fluoropropyltrichlorodecane, 3-fluoropropylchlorodimethoxydecane, 3-fluoropropyldichloromethoxydecane, 3-fluoro Propyl chlorodiethoxy decane, 3-iodopropyl trichloro decane, 4-chlorobutyl chloride diethoxy decane, 3-chloro-n-butyl chloride diethoxy decane, 3-chloro-3-B Silane dichloroethoxy acyl propyl, 3-chloro-3-methoxycarbonyl-propyl group or the like tribromo Silane X ⁰ is a halogen atom of a halogenated silicon alkyl compounds; cyanomethyl trimethoxy Silane, cyanomethyl Triethoxy decane, 1-cyanoethyltrimethoxydecane, 2-cyanoethyltrimethoxyfluorene 2-cyanoethyltriethoxydecane, 2-cyanoethyltripropoxydecane, 3-cyanopropyltrimethoxydecane, 3-cyanopropyltriethoxydecane, 3- Cyanopropyltripropoxydecane, 3-cyanopropyltributoxydecane, 4-cyanobutyltrimethoxydecane, 5-cyanopentyltrimethoxydecane, 2-cyanopropyl Trimethoxydecane, 2-(cyanomethoxy)ethyltrimethoxydecane, 2-(2-cyanoethoxy)ethyltrimethoxydecane, o-(cyanomethyl)phenyltripropane Oxydecane, m-(cyanomethyl)phenyltrimethoxynonane, p-(cyanomethyl)phenyltriethoxydecane, p-(2-cyanoethyl)phenyltrimethoxydecane, etc. X ⁰ is a cyanotrial alkoxy decane compound; cyanomethyl trichlorodecane, cyanomethyl bromide dimethoxy decane, 2-cyanoethyl dichloromethoxy decane, 2-cyano group Ethyl dichloroethoxy decane, 3-cyanopropyl trichloro decane, 3-cyanopropyl tribromodecane, 3-cyanopropyl dichloromethoxy decane, 3-cyanopropyl dichloride Ethoxy decane, 3-cyanopropyl chlorodimethoxy decane, 3-cyanopropyl chlorodiethoxy decane, 4-cyano Butyl chloride diethoxy decane, 3-cyano-n-butyl chloride diethoxy decane, 2-(2-cyanoethyl) phenyl trichloro decane, 2-(2-cyanoethyl) Bromodiethoxydecane, 2-(2-cyanoethyl)ethyldichloropropoxydecane, o-(2-cyanoethyl)phenyltrichlorodecane, m-(cyanoethyl) ) Silane bromo-dimethoxy phenyl, p- (2-cyanoethyl) phenyl dimethoxy silane-chloro, X ⁰ to (2-cyanoethyl) phenyl tribromo Silane is a cyano group or the like of Halogenated halogenated compounds; 3-ethyloxypropyltrimethoxydecane, 3-ethyloxypropyltriethoxydecane, 3-ethyloxypropyltripropoxydecane, 3-ethylhydrazine Oxypropyl tributoxy decane, 3-propoxy propyl tributoxy decane, 3-propoxy propyl triethoxy decane, 3-benzyl methoxy propyl trimethoxy Decane, 3-benzyloxypropyltriethoxydecane, 3-benzyloxypropyltripropoxydecane, 3-benzylidenepropyltributoxydecane, 2-three Methyl methoxyethyl trimethyl decane, 3-triethyl methoxy propyl triethoxy decane, 3-(2-tetrahydropyranyloxy) propyl tripropoxy decane, 3- (2- Hydropyranyloxy)propyltributoxydecane, 3-methoxymethyloxypropyltrimethoxydecane, 3-methoxyethoxymethyloxypropyltriethoxydecane, 3- (1-ethoxyethyloxy)propyltripropoxydecane, 3-(t-butoxycarbonyloxy)propyltrimethoxynonane, 3-tert-butoxypropyltrimethoxydecane, X ⁰ of 3-benzyloxypropyltriethoxydecane, 3-triphenylmethoxypropyltriethoxydecane, or the like is a trimethoxy decane compound of the above formula: OG; 3-Ethyloxypropyltrichloromethane, 3-ethoxymethoxypropyltribromodecane, 3-ethyloxypropyldichloromethoxydecane, 3-ethyloxypropyldichloroethane Oxy decane, 3-ethoxymethoxypropyl chlorodimethoxy decane, 3-ethoxypropyl propyl diethoxy decane, 3-benzyl methoxy propyl trichloro decane, 3-three Methyl methoxypropyl chlorodimethoxy decane, 3-triethyl methoxy propyl dichloro methoxy decane, 3-(2-tetrahydropyranyloxy) propyl chlorodiethoxy Decane, 3-(2-tetrahydrofuranyloxy)propyldichloroethoxydecane, 3-methoxymethyloxypropyltribromodecane, 3-methoxyethoxy Methyloxypropyl trichlorodecane, 3-(1-ethoxyethyl propyl)propyl chlorodimethoxy decane, 3-tert-butoxycarbonyloxypropyl dichloromethoxy decane, 3 X ⁰ of the third butoxypropyl chloride dichloroethoxy decane, 3-triphenylmethoxypropyl dichloroethoxy decane, 3-benzyloxypropyl tribromodecane, etc. : Halogenated decane compounds represented by OG, and the like.

These decane compounds (1) may be used alone or in combination of two or more.

Among these, the decane compound (1) is derived from a hardened product having more excellent adhesion, a trialkoxy decane compound having X ⁰ as a halogen atom, and a trialkoxy decane having a cyano group of X ^{0 .} The compound or X ⁰ is a trialkyloxydecane compound of the above formula: OG, preferably a 3-alkoxydecane compound having a 3-chloropropyl group, having 3-ethyloxypropane More preferably, a trialkoxide decane compound, a trialkoxyquinane compound having a 2-cyanoethyl group, or a trialkoxy decane compound having a 3-cyanopropyl group.

[decane compound (2)]

The decane compound (2) is a decane compound represented by the formula (2): R ² Si(OR ⁴ ) _q (X ² ) _3-q .

In the formula (2), a specific example of R ² is exemplified by the decane compound copolymer (A) as R ² .

R ⁴ represents the same alkyl group having 1 to 6 carbon atoms as the above R ³ .

X ² represents the same halogen atom as the above X ¹ .

The q system represents any integer from 0 to 3.

When q is 2 or more, OR ⁴ may be the same or different from each other. Further, when (3-q) is 2 or more, X ² may be the same or different from each other.

Specific examples of the decane compound (2) include methyl trimethoxy decane, methyl triethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, n-propyl trimethoxy decane, n-Butyl triethoxy decane, isobutyl trimethoxy decane, n-pentyl triethoxy decane, n-hexyl trimethoxy decane, isooctyl triethoxy decane, dodecyl trimethoxy decane An alkyltrimethoxy decane compound such as methyl dimethoxyethoxy decane or methyl diethoxy methoxy decane; methyl chlorodimethoxy decane, methyl dichloro methoxy Decane, methyl chlorodiethoxy decane, ethyl chlorodimethoxy decane, ethyl dichloromethoxy decane, n-propyl chlorodimethoxy decane, n-propyl dichloromethoxy decane, etc. Alkyl halide alkoxydecanes; alkyltrichlorodecane, methyltribromodecane, ethyltrichlorodecane, ethyltribromodecane, n-propyltrichlorodecane, and the like; Phenyltrimethoxydecane, 4-methoxyphenyltrimethoxydecane, 2-chlorophenyltrimethoxydecane, phenyltriethoxydecane a phenyltrialkoxydecane compound which may have a substituent such as 2-methoxyphenyltriethoxydecane, phenyldimethoxyethoxysilane, phenyldiethoxymethoxydecane or the like Phenyl chlorodimethoxy decane, phenyl dichloromethoxy decane, phenyl chloromethoxy ethoxy decane, phenyl chlorodiethoxy decane, phenyl dichloroethoxy decane, etc. Phenyl halide alkoxydecane compounds which may have a substituent; phenyl trichloromethane, phenyl tribromodecane, 4-methylphenyl trichloromethane, 2-chlorophenyl trichloromethane, 2-ethoxy A phenyltrihalide compound which may have a substituent such as phenyltrichloromethane or the like.

These decane compounds (2) may be used alone or in combination of two or more.

[mixture of decane compounds]

The mixture of the decane compound used in the production of the decane compound copolymer (A') may be a mixture of the decane compound (1) and the decane compound (2), and may further contain other decanes within a range not inhibiting the object of the present invention. A mixture of the compounds, preferably a mixture of the decane compound (1) and the decane compound (2).

The ratio of the decane compound (1) to the decane compound (2) is preferably a molar ratio of [decane compound (1)]: [decane compound (2)] = 55:45 to 25:75.

The method of condensing the mixture of the above decane compounds is not particularly limited, and the decane compound (1), the decane compound (2), and other desired decane compounds are dissolved in a solvent, and a predetermined amount of catalyst is added thereto. The method of setting the temperature to agitation.

The catalyst used may be any of an acid catalyst and a base catalyst.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid, and trifluoroacetic acid.

The base catalyst may, for example, be trimethylamine, triethylamine, lithium diisopropylamide, lithium bis(trimethylsulfonyl)amine, pyridine or 1,8-diazabicyclo[5.4.0] An organic base such as monocarb-7-ene, aniline, picoline, 1,4-diazabicyclo[2.2.2]octane, imidazole, etc.; tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. Organic salt hydroxide; metal alkoxide such as sodium methoxide, sodium ethoxide, sodium butoxide, potassium butoxide; metal hydride such as sodium hydride or calcium hydride; metal such as sodium hydroxide or potassium hydroxide A metal carbonate such as sodium carbonate, potassium carbonate or magnesium carbonate: a metal hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate.

Among these, the catalyst used is preferably an acid catalyst and more preferably a mineral acid.

The amount of the catalyst used is usually from 0.1 mol% to 10 mol%, based on the total mole amount of the decane compound, in the range of from 1 mol% to 5 mol%.

The solvent to be used can be appropriately selected depending on the type of the decane compound and the like. For example, aromatic hydrocarbons such as water, benzene, toluene, and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, and methyl propionate; acetone, methyl ethyl ketone, methyl isobutyl ketone, and ring; Ketones such as ketone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, and third butanol. The solvent may be used singly or in combination of two or more.

Among them, water, an aromatic hydrocarbon, and a mixed solvent thereof are preferred, and a mixed solvent of water and toluene is particularly preferable. When water and toluene are used, the ratio of water to toluene (volume ratio) is 1:9. ~9:1 is better, 7:3~3:7 is better.

The amount of the solvent to be used is 1 liter equivalent of the solvent, and the total molar amount of the decane compound is usually 0.1 mol to 10 mol, more preferably 0.5 mol to 10 mol.

The temperature at which the decane compound is condensed (reacted) is usually in the range of from 0 ° C to the boiling point of the solvent to be used, preferably in the range of from 20 ° C to 100 ° C. When the reaction temperature is too low, the progress of the condensation reaction may be insufficient. On the other hand, when the reaction temperature is too high, it is difficult to suppress gelation. The reaction is usually completed in 30 minutes to 20 hours.

When an acid catalyst is used, an alkaline aqueous solution such as sodium hydrogencarbonate is added to the reaction solution, and when an alkali catalyst is used, an acid such as hydrochloric acid is added to the reaction solution to neutralize the salt. The desired decane compound tool can be obtained by filtration or water washing or the like.

(B) epoxy compound

The curable composition of the present invention contains an epoxy compound (hereinafter, "epoxy compound (B)") as the component (B).

The curable composition of the present invention contains the epoxy compound (B) as the epoxy compound (B), and may be a compound having an epoxy group in the molecule, but a compound having two or more epoxy groups is preferred. .

Examples of the epoxy compound having two or more epoxy groups include glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcin, phenol, cresol, and the like; butanediol and polyethylene glycol. a glycidyl ether of an alcohol such as polypropylene glycol; a glycidyl ether of a carboxylic acid such as phthalic acid, isophthalic acid or terephthalic acid; and an alicyclic structure comprising a carbon-carbon double arrow a so-called alicyclic epoxy compound in which the double bond of the compound is oxidized to introduce an epoxy group; a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, an alicyclic ring Oxygen resin, cresol novolac type epoxy resin, phenol novolak type epoxy resin, biphenyl type epoxy resin, glycidylamine type epoxy resin, glycidyl ether type epoxy resin, B-type epoxy resin, acrylic acid denaturation Epoxy resin (epoxy acrylate), phosphorus-containing epoxy resin, styrene-based epoxy resin, hydroquinone epoxy resin, naphthalene skeleton epoxy resin, tetrahydroxyphenylethane epoxy Resin, DPP (di-n-pentyl phthalate) epoxy resin, trihydroxyphenylmethane epoxy resin, two Pentadiene phenol type epoxy resin, bismuth-containing epoxy resin, bisphenol A ethylene oxide addition diglycidyl ether, bisphenol A type propylene oxide addition diglycidyl ether, cyclohexane dimethanol A glycidyl ether, a polyglycidyl ether of an aliphatic polyhydric alcohol, a polyglycidyl ether of a polybasic acid, an epoxy resin such as a halide (such as a brominated epoxy resin) or a hydrogenated product, or the like. These may be used alone or in combination of two or more.

Among these, it is preferable to use an alicyclic epoxy resin compound from the viewpoint of obtaining a cured product having a high adhesion even at a high temperature. The alicyclic epoxy resin compound may have 3 or more epoxy rings in the molecule, and 3,4-epoxycyclohexylmethyl ester of 3,4-epoxycyclohexanecarboxylic acid represented by the following formula (a) , vinyl cyclohexene diepoxide, and the like. Among these, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylic acid is particularly preferred.

(C) hardener

The curable composition of the present invention contains, as the component (C), an alicyclic acid anhydride having a carboxyl group and a curing agent containing another alicyclic acid anhydride (hereinafter referred to as "hardener (C)"). .

Since the curable composition of the present invention contains the curing agent (C), a cured product excellent in heat resistance can be obtained.

An alicyclic acid anhydride having a carboxyl group, which is an alicyclic acid anhydride having at least one carboxyl group.

Specific examples of the alicyclic acid anhydride include phthalic anhydride, 3-methyl-1,2,3,6-tetrahydrophthalic anhydride, and 4-methyl-1,2,3,6-tetrahydrogen. Phthalic anhydride, tetrahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl Nadic anhydride, 5-bicycloheptene-2,3-biscarboxylic anhydride, bicycloheptene-2,3-biscarboxylic anhydride, methyl-5-heptene-2,3-biscarboxylic anhydride, methyl-ene -2,3-biscarboxylic anhydride or the like.

The carboxyl group may be substituted at any position of the alicyclic structure of the alicyclic acid anhydride, and the number of substitution positions or the number of substituted carboxyl groups is not particularly limited.

Among these, hexahydrophthalic anhydride is substituted for the carboxyl group of cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride, cyclohexane-1,2,3-tricarboxylic acid-1. 2 anhydride is preferred, and cyclohexane-1,2,4-tricarboxylic acid-1,2 anhydride is particularly preferred. The compound may exist as a stereoisomer, and any of the isomers may be used.

An alicyclic anhydride having a carboxyl group, either alone or in combination Used above.

Other alicyclic acid anhydrides are alicyclic acid anhydrides having no carboxyl group. The other alicyclic acid anhydride may be the same as the alicyclic acid anhydride exemplified above for the alicyclic acid anhydride having a carboxyl group. Among them, 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride are preferred, and 4-methyl-hexahydrophthalic anhydride is particularly preferred.

Other alicyclic acid anhydrides may be used alone or in combination of two or more.

In the hardened material (C), the ratio of the alicyclic acid anhydride having a carboxyl group to the other alicyclic acid anhydride, the mass ratio of the alicyclic acid anhydride having a carboxyl group to the other alicyclic acid anhydride, (the alicyclic ring having a carboxyl group) Anhydride): (other alicyclic anhydrides) = 50:50~10:90 is preferred.

In the curable composition of the present invention, the components (A), (B) and (C) are mass ratios of (A) to [(B) + (C)], and (A): [(B) ) +(C)]=100:20~100:60 ratio is used to make the above (A'), (B), and (C) components, (A') and [(B)+(C)] The mass ratio is used in the ratio of (A':[(B)+(C)]=100:20~100:60. If the ratio of (B)+(C) is less than 20, sufficient adhesion cannot be obtained. When the amount is more than 60, the compatibility with the component (A) or the component (A') is deteriorated, and excellent transparency cannot be obtained.

Further, the ratio of use of the components (B) and (C) is preferably a mass ratio (B): (C) = 4:6 to 6:4, and particularly preferably 5:5.

By using each component in such a ratio, a curable composition of a cured product having excellent long-term transparency and heat resistance and having a high adhesion even at a high temperature can be obtained.

The curable composition of the present invention further preferably contains an antioxidant which prevents oxidation upon heating in the above component.

The antioxidant is preferably a phosphorus-based antioxidant, a phenol-based antioxidant, or a sulfur-based antioxidant. Among them, a phosphorus-based antioxidant is preferred.

Examples of the phosphorus-based antioxidant include triphenyl phosphate, diphenylisodecyl phosphate, phenyl diisononyl phosphate, tris(nonylphenyl) phosphate, and diisodecyl isopentenyl phosphate. Tris(2,4-di-t-butylphenyl) phosphate, cyclooctylpentane tetrakis(bis-octadecyl) phosphate, cyclooctyl phosphate tetra-bis (2,4-di-third) Phenyl) ester, cyclooctyl phosphate tetrakis(2,4-di-t-butyl-4-methylphenyl), bis[2-t-butyl-6-methyl-4- a phosphate such as {2-(octadecyloxycarboxy)ethyl}phenyl]hydrogenated phosphorus, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 10-decyloxy-9,10- An oxaphosphorus phenanthrene oxide such as dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

Examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, dibutylhydroxytoluene, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, Monophenols such as stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate; 2,2'-methylenebis(4-methyl-6- Tributylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-t-butyl Phenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 3,9-bis[1,1-dimethyl-2-{β-(3-third Bisphenols such as butyl-4-hydroxy-5-methylphenol)propenyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane; 1,1, 3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetra[methylene-3-(3',5 '-Di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis(4'-hydroxy-3'-t-butylphenyl)butanoic acid]diol Ester, 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione A polymer phenol such as tocopherol.

The sulfur-based antioxidants include dilauryl-3,3'-thiodiacrylate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'- Thio diacrylate and the like.

The antioxidant may be used singly or in combination of two or more.

The amount of the antioxidant to be used is 0.01 to 10 parts by mass to 100 parts by mass of the decane compound copolymer (A) or (A').

The curable composition of the present invention may further contain other components in a range that does not inhibit the object of the present invention.

Other components include ultraviolet absorbers, photosensitizers, and diluents.

The ultraviolet absorber is added for the purpose of improving the light resistance of the obtained cured product.

Examples of the ultraviolet absorber include phenyl ruthenate, butyl phthalate, and octyl phenyl phthalate; 2, 4-hydroxybenzophenone, 2-hydroxy-4; -Methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methyl Oxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, 2- (2'-hydroxy-5'-methyl Phenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butyl Phenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3 ',5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-third-pentylphenyl)benzotriazole, 2 -{(2'-hydroxy-3',3'',4'',5'',6''-tetrahydrophthaleneiminemethyl)-5'-methylphenyl}benzo Triazole, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6,-pentamethyl-4-piperidinyl) Azelaic acid ester, bis(1,2,2,6,6,-pentamethyl-4-piperidinyl)[{3,5-bis(1,1-dimethylethyl)-4- A hindered amine such as hydroxyphenyl}methyl]butyl malonate.

These ultraviolet absorbers may be used alone or in combination of two or more.

The amount of the ultraviolet absorber to be used is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the decane compound copolymer (A) or (A').

The light stabilizer is added for the purpose of improving the light resistance of the obtained cured product.

The light stabilizer may, for example, be poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2) ,2,6,6-tetramethyl-4-piperidinyl)imido}hexamethylene {(2,2,6,6-tetramethyl-4-piperidinyl)imido}}] Hindered amines.

These light stabilizers may be used alone or in combination of two or more.

The amount of the ultraviolet absorber to be used is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the decane compound copolymer (A) or (A').

The diluent is added to adjust the viscosity of the curable composition.

The diluent may, for example, be glycerol diglycidyl ether, butanediol diglycidyl ether, diglycidyl aniline, octyl glycol glycidyl ether, cyclohexane dimethanol diglycidyl ether or alkylene condensed water. Glycerol ether, polyglycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, 4-vinylcyclohexene epoxide, cyclohexene dioxide Ethylene, methylated cyclohexene ethylene oxide, and the like.

These diluents may be used singly or in combination of two or more.

In the curable composition of the present invention, for example, the components (A) or (A'), (B), and (C), and the desired antioxidant and other components are blended in a predetermined ratio, and mixed by a conventional method. Defoaming.

According to the curable composition of the present invention obtained as described above, it is possible to obtain excellent transparency and long-lasting force for a long period of time without causing coloration or lowering transparency even when irradiated with high-energy light or a high temperature state. Hardened matter.

Therefore, the curable composition of the present invention can be suitably used as a raw material, an adhesive, a plating agent, or the like as an optical component or a molded article. In particular, the curable composition of the present invention can be suitably used as a composition for an optical element fixing material in order to solve the problem of deterioration of the optical element fixing material in accordance with the increase in the brightness of the optical element.

2) Hardened material

The second aspect of the present invention is a cured product of the curable composition of the present invention.

The method of hardening the curable composition of the present invention is heat hardening. The heating temperature during hardening is usually 100~200°C, and the heating time is usually 10 It is preferably 20 minutes to 10 hours, preferably 30 minutes to 10 hours.

The cured product of the present invention can obtain a cured product having high adhesion and high adhesion even when it is irradiated with high-energy light or at a high temperature, without coloring or lowering transparency.

Therefore, the cured product of the present invention can be suitably used for an optical component or a molded article, an adhesive layer, a plating layer, or the like. In particular, the curable composition of the present invention can be suitably used as a composition for an optical element fixing material in order to solve the problem of deterioration of the optical element fixing material in accordance with the increase in the brightness of the optical element.

The cured product of the present invention has a high adhesion, and can be confirmed, for example, by the following force measurement. That is, the surface of the tantalum wafer is coated with a curable composition, and the coated surface is placed on the object to be pressure-bonded, and heat-treated to be cured. This was placed on a measuring stand of a tester which was previously heated to a predetermined temperature (for example, 23 ° C) for 30 seconds, and a horizontal method (cutting direction) was applied to the succeeding surface from the position of the height of the object to be 50 μm. Stress, measure the adhesion between the test piece and the object.

The adhesion of the cured product is preferably 110 N/2 mm □ or more at 23 ° C.

The cured product is excellent in transparency and can be confirmed by measuring the light transmittance. The light transmittance of the cured product is preferably 80% or more in light having a wavelength of 450 nm, more preferably 85% or more.

The cured product is excellent in long-term heat resistance, and can be confirmed by leaving the cured product at a high temperature for a long period of time and having a small change in transparency. The transparency was set at 150 ° C for 300 hours, and the transmittance at a wavelength of 450 nm was 80% or more of the initial transmittance.

3) How to use the hardenable composition

According to a third aspect of the present invention, the curable composition of the present invention is used as an adhesive for an optical element fixing material or an encapsulant for an optical element fixing material.

Examples of the optical element include a light-emitting element such as an LED or an LD, a light-receiving element, a composite optical element, and an optical unit circuit.

<Binder for optical element fixing material>

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 fixing an optical element, and the composition is applied to one or both of the following materials (such as an optical element and a substrate thereof), and the composition is applied. Thereafter, it is heat-hardened so that the materials of the object are firmly adhered to each other.

Next, 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 alloys of the metals; Metals such as (SUS302, SUS304, SUS304L, SUS309, etc.); polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-ethyl acetate copolymer , polystyrene, polycarbonate, polymethylpentene, polyfluorene, polyetheretherketone, polyether oxime, polyphenylene sulfide, polyetherimide, polyamidamine, polyamine, acrylic resin, drop A synthetic resin such as a borneol-based resin, a cycloolefin resin, or a glass epoxy resin.

The heating temperature at the time of heat curing is usually 100 to 200 ° C depending on the curable composition or the like. The heating time is usually from 10 minutes to 20 hours, preferably from 30 minutes to 10 hours.

(Packaging agent for optical component fixing materials)

The curable composition of the present invention can be suitably used as an encapsulant for an optical element package.

When the curable composition of the present invention is used as a method for encapsulating an optical element fixing material, for example, the composition is molded into a desired shape, and a molded body of the inner optical element is obtained, which is then heat-cured. A method of manufacturing an optical element package or the like.

The method of molding the curable composition of the present invention into a desired shape is not particularly limited, and a conventional transfer molding method or a conventional molding method such as injection molding can be employed.

The heating temperature at the time of heat curing is usually 100 to 200 ° C depending on the curable composition used. The heating time is usually from 10 minutes to 20 hours, preferably from 30 minutes to 10 hours.

In the obtained optical element package, since the curable composition of the present invention is used, even if a short wavelength of a light-emitting peak wavelength of 400 to 490 nm such as a white or blue LED is used in the optical element, color deterioration does not occur due to heat or light. It is excellent in transparency and heat resistance.

[Examples]

The present invention will now be described in more detail by way of examples and comparative examples, but the invention should not be construed as limited.

(weight average molecular weight determination)

The weight average molecular weight (Mw) of the decane compound copolymer obtained in the production example was measured by the following apparatus and conditions in terms of standard polystyrene.

Device name: HLC-8220GPC TOSO company

Column: TSKgelGMHXL, TSKgelGMHXL and TSKge12000HXL are connected in sequence.

Solvent: tetrahydrofuran

Injection volume: 80μl

Measuring temperature: 40 ° C

Flow rate: 1ml/min

Sensor: differential refractometer

(Measurement of IR spectrum)

The IR spectrum of the decane compound copolymer obtained in the production example was measured using the following apparatus.

Fourier transform infrared spectrometer (Spectrum100, manufactured by PerkinElmer)

(Manufacturing Example 1)

In a 300 ml water drop bottle, 16.7 g (84 mmol) of phenyltrimethoxydecane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a decane compound (2), 3-ethyloxypropyltrimethoxydecane (manufactured by AZMAX Co., Ltd.). 8.0 g (36 mmol) was added as a decane compound (1), and 120 ml of toluene was added as a solvent, and 60 ml of distilled water was added thereto, and 0.15 g (1.5 mmol) of phosphoric acid (manufactured by Kanto Chemical Co., Ltd.) was added as a catalyst, and further stirred at room temperature. hour.

After completion of the reaction, 100 ml of ethyl acetate was added to the reaction mixture, and the mixture was neutralized with a saturated aqueous sodium hydrogen carbonate solution. After standing for a while, the water was removed and 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 ml with a reduced pressure concentrator, and this was added dropwise to a large amount of n-hexane to reprecipitate, and the precipitate was separated by decantation. The obtained precipitate was dissolved in methyl ethyl ketone (MEK), and the solvent was evaporated under reduced pressure in vacuo to dryness to dryness to afford 14.7 g of decane compound copolymer (A1).

The decane compound copolymer (A1) had a weight average molecular weight (Mw) of 2,500 and a molecular weight distribution of (Mw/Mn) of 1.53.

Further, the IR spectrum data of the decane compound copolymer (A1) is shown below.

Si-Ph: 699 cm ^-1 , 741 cm ^-1 , Si-O: 1132 cm ^-1 , -CO: 1738 cm ^-1

(Manufacturing Example 2)

In the production example 1, decane was obtained in the same manner as in Production Example 1, except that the amount of the phenyltrimethoxydecane used was 14.3 g (72 mmol) and 3-methoxypropyloxytrimethoxydecane (0.77 g (48 mmol)). The compound copolymer (A2) was 15.9 g.

The decane compound copolymer (A2) had a weight average molecular weight (Mw) of 2,600 and a molecular weight distribution (Mw/Mn) of 1.51.

Further, the IR spectrum data of the decane compound copolymer (A2) is shown below.

Si-Ph: 699 cm ^-1 , 741 cm ^-1 , Si-O: 1132 cm ^-1 , -CO: 1738 cm ^-1

(Manufacturing Example 3)

In the production example 1, decane was obtained in the same manner as in Production Example 1, except that the amount of the phenyltrimethoxydecane used was 11.9 g (60 mmol) and 3-ethyloxypropyltrimethoxydecane (3.3 g) (60 mmol). The compound copolymer (A3) was 15.3 g.

The decane compound copolymer (A3) had a weight average molecular weight (Mw) of 2,600 and a molecular weight distribution (Mw/Mn) of 1.60.

Further, the IR spectrum data of the decane compound copolymer (A3) is shown below.

Si-Ph: 700 cm ^-1 , 742 cm ^-1 , Si-O: 1132 cm ^-1 , -CO: 1738 cm ^-1

(Manufacturing Example 4)

In Production Example 1, phenyltrimethoxydecane was used in an amount of 16.7 g (84 mmol), and 3-ethoxymethoxypropyltrimethoxydecane (8.0 g) (36 mmol) was used, and phenyltrimethoxydecane (Tokyo) was used. A decane compound copolymer (A4) was obtained in the same manner as in Production Example 1 except that 11.9 g (60 mmol) and 3-glyceryl propyl trimethoxy sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) 14.2 (60 mmol). 16.3g.

The decane compound copolymer (A4) had a weight average molecular weight (Mw) of 2,800 and a molecular weight distribution (Mw/Mn) of 1.56.

Further, the IR spectrum data of the decane compound copolymer (A4) is shown below.

Si-Ph: 700 cm ^-1 , 742 cm ^-1 , Si-O: 1132 cm ^-1 , epoxy: 1254 cm ^-1

(Manufacturing Example 5)

11.9 g (60 mmol) of phenyltrimethoxydecane (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed as a decane compound (2), 3-chloropropyltrimethoxydecane (manufactured by Tokyo Chemical Industry Co., Ltd.), 11.9. g (60 mmol) as a decane compound (1), 60 ml of toluene and 30 ml of distilled water were added as a solvent, and 0.15 g (1.5 mmol) of phosphoric acid (manufactured by Kanto Chemical Co., Ltd.) was added as a catalyst while stirring, and further stirred at room temperature for 16 hours. .

After completion of the reaction, it was neutralized with a saturated aqueous sodium hydrogencarbonate solution. 100 ml of ethyl acetate was added thereto, and the mixture was stirred for a while. After standing, the organic layer was washed twice with distilled water and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the mixture was poured into a large amount of n-hexane to reprecipitate, and the precipitate was taken out by removing hexane. The obtained precipitate was dissolved in methyl ethyl ketone (MEK), and the solvent was evaporated under reduced pressure in vacuo to dryness to dryness to afford 12.9 g of decane compound (A5).

The decane compound copolymer (A5) had a weight average molecular weight (Mw) of 3,600 and a molecular weight distribution of (Mw/Mn) of 1.63.

Further, the IR spectrum data of the decane compound copolymer (A5) is shown below.

Si-Ph: 700 cm ^-1 , 741 cm ^-1 , Si-O: 1133 cm ^-1 , -Cl: 648 cm ^-1

(Manufacturing Example 6)

In the same manner as in Production Example 5 except that the amount of the phenyltrimethoxydecane used was 16.7 g (84 mmol) and the amount of 3-chloropropyltrimethoxydecane used was 7.15 g (36 mmol). The decane compound copolymer (A6) was 13.4 g.

The decane compound copolymer (A6) had a weight average molecular weight (Mw) of 3,300 and a molecular weight distribution (Mw/Mn) of 1.59.

Further, the IR spectrum data of the decane compound copolymer (A6) is shown below.

Si-Ph: 700 cm ^-1 , 742 cm ^-1 , Si-O: 1133 cm ^-1 , -Cl: 648 cm ^-1

(Manufacturing Example 7)

In the same manner as in Production Example 5 except that the amount of the phenyltrimethoxydecane used was 14.3 g (72 mmol) and the amount of 3-chloropropyltrimethoxydecane used was 9.54 g (48 mmol). The decane compound copolymer (A7) was 13.1 g.

The decane compound copolymer (A7) had a weight average molecular weight (Mw) of 3,400 and a molecular weight distribution (Mw/Mn) of 1.61.

Further, the IR spectrum data of the decane compound copolymer (A7) is shown below.

Si-Ph: 699 cm ^-1 , 741 cm ^-1 , Si-O: 1132 cm ^-1 , -Cl: 648 cm ^-1

(Manufacturing Example 8)

In the production example 5, a decane compound was obtained in the same manner as in Production Example 5 except that 10.5 g (60 mmol) of 2-cyanoethyltrimethoxydecane (manufactured by AZMAX) was used instead of 11.9 g of 3-chloropropyltrimethoxydecane. The copolymer (A8) was 12.3 g.

The decane compound copolymer (A8) had a weight average molecular weight (Mw) of 3,500 and a molecular weight distribution (Mw/Mn) of 1.61.

Further, the IR spectrum data of the decane compound copolymer (A8) is shown below.

Si-Ph: 700 cm ^-1 , 742 cm ^-1 , Si-O: 1133 cm ^-1 , -CN: 2252 cm ^-1

(Manufacturing Example 9)

In the same manner as in Production Example 8, except that the amount of the phenyltrimethoxydecane used was 16.7 g (84 mmol) and the amount of 2-cyanoethyltrimethoxydecane used was 6.31 g (36 mmol). The decane compound copolymer (A9) was obtained in an amount of 13.3 g.

The decane compound copolymer (A9) had a weight average molecular weight (Mw) of 3,200 and a molecular weight distribution (Mw/Mn) of 1.64.

Further, the IR spectrum data of the decane compound copolymer (A9) is shown below.

Si-Ph: 699 cm ^-1 , 742 cm ^-1 , Si-O: 1131 cm ^-1 , -CN: 2253 cm ^-1

(Manufacturing Example 10)

In the same manner as in Production Example 8, except that the amount of the phenyltrimethoxydecane used was 14.3 g (72 mmol) and the amount of 2-cyanoethyltrimethoxydecane used was 7.01 g (48 mmol). The decane compound copolymer (A10) was obtained in an amount of 12.9 g.

The decane compound copolymer (A10) had a weight average molecular weight (Mw) of 3,300 and a molecular weight distribution (Mw/Mn) of 1.62.

Further, the IR spectrum data of the decane compound copolymer (A10) is shown below.

Si-Ph: 699 cm ^-1 , 742 cm ^-1 , Si-O: 1131 cm ^-1 , -CN: 2253 cm ^-1

(Example 1)

10 g of the decane compound copolymer (A1) obtained in Production Example 1 was added as a component (B) to 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Sikma Eldi) 1.5 g of cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a carboxy-alicyclic alicyclic acid anhydride as a component (C), Further, 1.35 g of 4-methylcyclohexane-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), which is an alicyclic acid anhydride, was sufficiently mixed and defoamed to obtain a curable composition.

(Examples 2 to 8)

In Example 1, the decane compound copolymer, the component (B), and the component (C) were obtained in the same manner as in Example 1 except that the types and blending amounts described in the following Table 1 were used. Compositions (2) to (8).

(Examples 9, 10)

Further, in the same manner as in Examples 4 and 5, the curable compositions (9) and (10) were obtained in the same manner as in Examples 4 and 5, except that 0.5 parts by mass of a phosphorus-based antioxidant IRGAFOS 168 (manufactured by Ciba. Japan Co., Ltd.) was further added.

(Comparative Examples 1, 2)

In the first embodiment, the decane compound copolymer, the component (B), and the component (C) were each hardened in the same manner as in Example 1 except that the types and blending amounts described in the following Table 1 were used. Sex compositions (11), (12).

(Comparative Example 3)

In the same manner as in Example 1, except that 1.5 g of the alicyclic amine-based curing agent (trade name: EH3895, manufactured by ADEKA Co., Ltd.) was used as the component (C), the curable composition (13) was obtained.

(Comparative Example 4)

In the first embodiment, in place of the component (C), 1.45 g of 4-methylcyclohexane-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and triphenylphosphine (manufactured by Kanto Chemical Co., Ltd.) of a curing catalyst were used. In the same manner as in Example 1, a curable composition (14) was obtained.

(Comparative Example 5)

In the same manner as in Example 3 except that 10 g of the decane compound copolymer (A4) obtained in Production Example 4 was used as the substituted decane compound copolymer (A2), a curable composition (15) was obtained.

(Examples 11 to 16, Comparative Examples 6 to 13)

In the first embodiment, the decane compound copolymer, the component (B), and the component (C) were each hardened in the same manner as in Example 1 except that the types and blending amounts described in the following Table 1-2 were used. Sex composition (16) ~ (29).

With respect to the cured products of the curable compositions (1) to (29) obtained in Examples 1 to 16 and Comparative Examples 1 to 13, the adhesion, the initial transmittance, and the transmittance after heating were measured as follows.

The measurement results are shown in Tables 2 and 2 below.

(Continue force test)

The mirror-coated hardenable composition of the 2 mm square silicon wafer was formed to have a thickness of about 2 μm, and the coated surface was placed on the object (silver-plated copper plate). Thereafter, the mixture was heat-treated at 180 ° C for 2 hours to be hardened to obtain a subject to which a test piece was attached. The object to which the test piece is attached is placed on a measuring stand of a tester (Series 4000, manufactured by DAGE Co., Ltd.) which is previously heated to a predetermined temperature (for example, 23 ° C, 100 ° C) for 30 seconds, and is placed by the object. The position of the height of 50 μm was applied to the bonding surface at a speed of 200 μm/s in a horizontal method (cutting direction), and the adhesion between the test piece at 23 ° C and 100 ° C and the object was measured.

(Measurement of initial penetration rate)

The curable composition was poured into a mold to grow 25 mm, 20 mm wide, and 1 mm thick, and was heated at 140 ° C for 6 hours to be hardened to prepare test pieces. In the obtained test piece, the initial transmittance (%) at a wavelength of 450 nm was measured with a spectrophotometer (MPC-3100, manufactured by Shimadzu Corporation).

(Measurement of penetration after heating)

Each of the test pieces for measuring the initial transmittance was placed in an oven at 150 ° C for 100 hours and 300 hours, and again, the transmittance (%) at a wavelength of 450 nm was measured.

From the second table-1 and the second table-2, the cured products of Examples 1 to 16 had high adhesion at 23 ° C and 100 ° C, and were excellent in initial transmittance and transmittance after heating.

On the other hand, the cured products of Comparative Examples 1, 6, and 10, followed by the difference in force, and the cured products of Comparative Examples 2, 7, and 11 had low transmittance after heating, and Comparative Examples 3, 4, 8, 9, and The hardened material of 13 has a poor force and a low transmittance after heating. Compared with the hardened material, the penetration rate will decrease after heating for 300 hours.

Claims (12)

A curable composition comprising: (A) (i) and (ii), (i) and (in) a repeating unit represented by the following formulas (i), (ii) and (iii); a repeating unit of iii), (ii) and (iii) or (i), (ii) and (iii), a decane compound copolymer having a weight average molecular weight of 1,000 to 30,000; (B) an epoxy compound; and (C) A hardener containing an alicyclic acid anhydride having a carboxyl group and an alicyclic acid anhydride having no carboxyl group, and the mass ratio of (A) to [(B) + (C)] is (A): [(B) + (C )]=100:20~100:60 ratio: In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X ⁰ represents a halogen atom, a cyano group or a group represented by the formula: OG (wherein G represents a protecting group of a hydroxyl group), D represents a single bond or a linking group, and R ² represents an alkyl group having 1 to 20 carbon atoms or a phenyl group which may have a substituent. The curable composition according to claim 1, wherein the decane compound copolymer of the above (A) is in the form of a group represented by the formula: R ¹ -CH(X ⁰ )-D- ([R ¹ -CH (X ⁰⁾ -D]) with R ² present in an amount ([R ^2]) the molar ^{ratio, [R 1 -CH (X 0} ) -D]: [R 2] = 55: 45 ~ 25:75 decane compound copolymer. A curable composition comprising: (A') containing formula (1): R ¹ -CH(X ⁰ )-D-Si(OR ³ ) _p (X ¹ ) _3-p [wherein R ¹ is a formula It represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X ⁰ represents a halogen atom, a cyano group or a group represented by the formula: OG (wherein G represents a protecting group of a hydroxyl group), and D represents a single bond or At least one of a decane compound (1) represented by a linking group, R ³ is an alkyl group having 1 to 6 carbon atoms, X ¹ is a halogen atom, and p is an integer of 0 to 3, and Formula (2): R ² Si(OR ⁴ ) _q (X ² ) _3-q [wherein R ² represents an alkyl group having 1 to 20 carbon atoms or a phenyl group which may have a substituent, and R ⁴ represents an alkane having 1 to 6 carbon atoms. group, X ² line represents a halogen atom, q lines represents an integer of 0 to 3, of] FIG the Silane compound (2) is at least a mixture of an alkoxy compound of silicon condensation, weight average molecular weight silicon 1,000 to 30,000 of an alkoxy compound copolymer (B) an epoxy compound; and (C) a hardener containing an alicyclic acid anhydride having a carboxyl group and an alicyclic acid anhydride having no carboxyl group, and a mass ratio of (A') to [(B) + (C)] For, (A'): [(B) + (C)] = 100: 20 ~ 100: 60 ratio. The hardenable composition according to claim 3, wherein the decane compound copolymer of the above (A') is a molar ratio of a decane compound (1) to a decane compound (2) [decane compound (1)] :[decane compound (2)] = 55:45~25:75 ratio of the decane compound copolymer obtained by condensation. The hardenable composition according to claim 1 or 3, wherein the mass ratio of the hardener (C) is (an alicyclic acid anhydride having a carboxyl group): (an alicyclic acid anhydride having no carboxyl group) = 50:50~10:90. The curable composition according to claim 1 or 3, further comprising an antioxidant. The curable composition according to claim 6, wherein the antioxidant is a phosphorus-based antioxidant. The curable composition according to claim 1 or 3, which is a composition for a light element fixing material. A cured product obtained by hardening a curable composition according to claim 1 or 3. The cured product according to claim 9, which is a light element fixing material. A method of using a curable composition according to claim 1 or 3 as an adhesive for an optical element fixing material. A method of using a curable composition according to claim 1 or 3 as a sealing agent for an optical element fixing material.